JPWO2016125822A1 - Photoelectric conversion element and organic semiconductor compound used therefor - Google Patents

Abstract

An object of the present invention is to provide a photoelectric conversion element that develops a high open-circuit voltage using a polymer compound into which various skeletons and substituents can be introduced. A photoelectric conversion element having a structure in which a base material, an anode, an active layer, and a cathode are arranged in this order, wherein the active layer has a benzobisthiazole structural unit represented by formula (1) A photoelectric conversion element comprising a molecular compound. [In Formula (1), T 1 and T 2 are each independently substituted with a thiophene ring, hydrocarbon group or organosilyl group which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom or a trifluoromethyl group. B1 and B2 each represents a thiophene ring optionally substituted with a hydrocarbon group, a thiazole ring optionally substituted with a hydrocarbon group, or an ethynylene group. ]

Description

  The present invention relates to a photoelectric conversion element having a structure in which a substrate, an anode, an active layer, and a cathode are arranged in this order, and a photoelectric conversion containing a polymer compound having a specific structural unit of a benzobisthiazole skeleton It relates to an element.

  An organic semiconductor compound is one of the most important materials in the field of organic electronics, and can be classified into an electron-donating p-type organic semiconductor compound and an electron-accepting n-type organic semiconductor compound. Various elements can be manufactured by appropriately combining p-type organic semiconductor compounds and n-type organic semiconductor compounds. For example, such elements include excitons (exciton) formed by recombination of electrons and holes. ), The organic thin film solar cell that converts light into electric power, and the organic thin film transistor that controls the amount of current and voltage.

  Among these, organic thin-film solar cells are useful for environmental preservation because they do not release carbon dioxide into the atmosphere, and demand is increasing because they are easy to manufacture with a simple structure. However, the photoelectric conversion efficiency of the organic thin film solar cell is still not sufficient. The photoelectric conversion efficiency η is calculated by the product “η = open circuit voltage (Voc) × short circuit current density (Jsc) × curve factor (FF)” of the short circuit current density (Jsc), the open circuit voltage (Voc), and the fill factor (FF). In order to increase the photoelectric conversion efficiency, it is necessary to improve the short circuit current density (Jsc) and the fill factor (FF) in addition to the improvement of the open circuit voltage (Voc).

  The open circuit voltage (Voc) is proportional to the energy difference between the HOMO (highest occupied orbital) level of the p-type organic semiconductor compound and the LUMO (lowest unoccupied orbital) level of the n-type organic semiconductor compound. In order to improve (Voc), it is necessary to deepen (lower) the HOMO level of the p-type organic semiconductor.

  The short circuit current density (Jsc) correlates with the amount of energy received by the organic semiconductor compound. In order to improve the short circuit current density (Jsc) of the organic semiconductor compound, from the visible region to the near infrared region. It is necessary to absorb light in a wide wavelength range. Of the light that can be absorbed by the organic semiconductor compound, the wavelength of the light with the lowest energy (the longest wavelength) is the absorption edge wavelength, and the energy corresponding to this wavelength corresponds to the band gap energy. Therefore, in order to absorb light in a wider wavelength range, it is necessary to narrow the band gap (energy difference between the HOMO level and the LUMO level of the p-type semiconductor).

  On the other hand, Patent Document 1 proposes a compound having a benzobisthiazole skeleton, but the conversion efficiency is not clear.

JP 2007-238530 A

  The subject of this invention is providing the photoelectric conversion element which expresses a high open circuit voltage. In addition, the ability of the photoelectric conversion element depends on the type and combination of the organic semiconductor compound, and since HOMO and the open circuit voltage are closely related to each other, more various skeletons and substituents can be introduced. It is providing the photoelectric conversion element using a high molecular compound.

  In order to improve the conversion efficiency, that is, to improve the short-circuit current density (Jsc) while improving the open circuit voltage (Voc), the present inventors have made the p-type organic semiconductor absorb light in a wide wavelength range and simultaneously perform HOMO. We found it useful to make the level moderately deep. And as a result of earnestly examining paying attention to the correlation between the conversion efficiency and the chemical structure in the p-type organic semiconductor compound, by using the organic semiconductor polymer having a specific structure, the entire visible light region has a wide light absorption. At the same time, it was found that the short circuit current density (Jsc) can be improved while improving the open circuit voltage (Voc) because the HOMO level and the LUMO level can be adjusted to appropriate ranges. And when such an organic-semiconductor polymer was used, it discovered that a charge separation could be easily caused between a p-type organic semiconductor and an n-type organic semiconductor, and completed this invention.

  That is, the present invention is a photoelectric conversion element having a structure in which a substrate, an anode, an active layer, and a cathode are arranged in this order, and the active layer has a specific benzox represented by the formula (1). It contains a polymer compound having a structural unit of a bisthiazole skeleton (hereinafter sometimes referred to as “polymer compound (1)”).

[In Formula (1),
T ¹ and T ² are each independently a thiophene ring which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group, a thiazole which may be substituted with a hydrocarbon group or an organosilyl group A ring, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is represented.
B ¹ and B ² represent a thiophene ring that may be substituted with a hydrocarbon group, a thiazole ring that may be substituted with a hydrocarbon group, or an ethynylene group. ]

In the formula (1), T ¹ and T ² are each preferably a group represented by any of the following formulas (t1) to (t5).

Wherein (t1) ~ (t5), R 13 ~R 14 each independently represent a hydrocarbon group having 6 to 30 carbon atoms. R ¹⁵ to R ¹⁶ are each independently a hydrocarbon group having 6 to 30 carbon atoms, ^{or,, * - Si (R 18} ) a group represented by _3. R ^{15 ′} represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by * —Si (R ¹⁸ ) ₃ . R ¹⁷ represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, * —O—R ¹⁹ , * —S—R ²⁰ , * —Si (R ¹⁸ ) ₃ , or * —CF ₃ . R ¹⁸ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ¹⁸ may be the same or different. R ^{19 to} R ²⁰ represent a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond bonded to the thiazole ring of benzobisthiazole. ]

In Formula (1), B ¹ and B ² are each preferably a group represented by any of the following Formulas (b1) to (b3).

[In the formulas (b1) to (b3),
R ²¹ , R ²² and R ^{21 ′} represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms.
* Represents a bond, and in particular, * on the left side represents a bond bonded to the benzene ring of the benzobisthiazole compound. ]

  The polymer compound (1) contained in the photoelectric conversion element of the present invention is preferably a donor-acceptor type semiconductor polymer.

  The active layer preferably further contains an n-type organic semiconductor compound, and the n-type semiconductor compound is preferably fullerene or a derivative thereof.

  The photoelectric conversion element of the present invention preferably has a hole transport layer between the anode and the active layer, and preferably has an electron transport layer between the cathode and the active layer. The anode is preferably a transparent electrode, and the cathode is preferably a metal electrode.

The polymer compound (1) used in the present invention can form a planar cross-shaped skeleton by intramolecular S—N interaction. As a result, π conjugation is extended to a planar cross-shaped skeleton, so that it exhibits multiband light absorption derived from a plurality of π-π ^* transitions and can absorb a wide range of light from the visible region to the near infrared region. Thereby, it becomes possible to obtain both a high open circuit voltage (Voc) and a short circuit current density (Jsc), and it is possible to obtain a high photoelectric conversion efficiency η. In addition, it is possible to introduce various substituents as substituents into the benzobisthiazole skeleton constituting the polymer compound (1) used in the present invention, and materials that have various influences on the characteristics of photoelectric conversion elements Characteristics (crystallinity, film-forming property, absorption wavelength) can be controlled.

FIG. 1 shows an element structure of a photoelectric conversion element in which a substrate, an anode, an active layer, and a cathode are arranged in this order.

  Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist.

1. Photoelectric Conversion Element The photoelectric conversion element according to the present invention is a photoelectric conversion element having a structure in which a substrate, an anode, an active layer, and a cathode are arranged in this order, and the active layer is represented by the formula (1). A polymer compound having a benzobisthiazole structural unit represented is contained.

  A photoelectric conversion element (VII) according to an embodiment of the present invention is shown in FIG. FIG. 1 shows a photoelectric conversion element used for a general organic thin film solar cell, but the photoelectric conversion element according to the present invention is not limited to the configuration of FIG.

  The photoelectric conversion element (VII) has a structure in which a substrate (I), an electrode (anode) (II), an active layer (IV), and an electrode (cathode) (VI) are arranged in this order. The photoelectric conversion element (VII) preferably further has a buffer layer (hole transport layer) (III) and a buffer layer (electron transport layer) (V). That is, the photoelectric conversion element (VII) includes a base material (I), an anode (II), a buffer layer (hole transport layer) (III), an active layer (IV), and a buffer layer (electron transport layer) (V ) And the cathode (VI) are preferably arranged in this order. However, the photoelectric conversion element according to the present invention may not have the hole transport layer (III) and the electron transport layer (V). Hereinafter, each of these parts will be described.

1.1 Active layer (IV)
The active layer (IV) refers to a layer in which photoelectric conversion is performed, and usually includes a single or a plurality of p-type semiconductor compounds and a single or a plurality of n-type semiconductor compounds. Specific examples of the p-type semiconductor compound include, but are not limited to, the polymer compound (1) and the organic semiconductor compound (11) described later. In the present invention, it is necessary to use at least the polymer compound (1) as the p-type semiconductor compound. When the photoelectric conversion element (VII) receives light, the light is absorbed by the active layer (IV), electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is the anode (II) and It is taken out from the cathode (VI). In the present invention, the polymer compound (1) is used as a p-type semiconductor compound.

  The thickness of the active layer (IV) is preferably 70 nm or more, more preferably 90 nm or more, may be 100 nm or more, preferably 1000 nm or less, more preferably 750 nm or less, and still more preferably 500 nm or less.

  When the film thickness of the active layer (IV) is moderately large, improvement in conversion efficiency of the photoelectric conversion element (VII) can be expected. Moreover, it is also preferable that the film thickness of the active layer (IV) is moderately thick in that a through-short circuit in the film can be prevented. It is preferable that the thickness of the active layer (IV) is moderately thin because the internal resistance is small and the distance between the electrodes (II) and (VI) is not too far and the charge diffusion is good. Furthermore, when the film thickness of the active layer (IV) is in the above range, it is preferable in terms of improving reproducibility in the process of producing the active layer (IV).

  In general, the thicker the active layer, the longer the distance traveled by the charge generated in the active layer to the electrode or the electron transport layer or hole transport layer, thus hindering the transport of charge to the electrode. It is done. As described above, when the active layer (IV) is thick, the region capable of absorbing light is increased, but it is difficult to transport charges generated by light absorption, so that the photoelectric conversion efficiency is lowered. Therefore, it is preferable to make the film thickness of the active layer (IV) in the above range from the viewpoint of securing voltage and improving conversion efficiency.

1.1.1 Layer Configuration of Active Layer As a layer configuration of the active layer (IV), a thin film stacked type in which a p-type semiconductor compound and an n-type semiconductor compound are stacked, or a p-type semiconductor compound and an n-type semiconductor compound, Bulk heterojunction type having a layer in which is mixed. Among these, a bulk heterojunction type active layer is preferable in that the photoelectric conversion efficiency can be further improved.

Bulk heterojunction active layer A bulk heterojunction active layer has a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed. The i layer has a structure in which the p-type semiconductor compound and the n-type semiconductor compound are phase-separated, carrier separation occurs at the phase interface, and the generated carriers (holes and electrons) are transported to the electrode.

  Among the p-type semiconductor compounds contained in the i layer, a polymer compound (1) having a benzobisthiazole structural unit represented by the formula (1) (preferably a benzobisthiazole structural unit represented by the formula (1) And the proportion of the polymer compound (1-1) comprising the copolymer component (2) described later is usually 50% by mass or more, preferably 70% by mass or more, more preferably in 100% by mass of the p-type semiconductor compound. 90% by mass or more. Since the polymer compound (1) has properties suitable as a p-type semiconductor compound, it is particularly preferable that the p-type semiconductor compound contains only the polymer compound (1).

  The mass ratio of the p-type semiconductor compound to the n-type semiconductor compound in the i layer (p-type semiconductor compound / n-type semiconductor compound) is 0 from the viewpoint of improving the photoelectric conversion efficiency by obtaining a good phase separation structure. 0.5 or more is preferable, more preferably 1 or more, 4 or less is preferable, 3 or less is more preferable, and 2 or less is particularly preferable.

  The i layer can be formed by any method including a coating method and an evaporation method (for example, a co-evaporation method), and it is preferable to use the coating method because the i layer can be formed more easily. Since the polymer compound (1) according to the present invention has solubility in a solvent, it is preferable from the viewpoint of excellent coating film-forming properties. When the i layer is produced by a coating method, a coating solution containing a p-type semiconductor compound and an n-type semiconductor compound may be prepared, and this coating solution may be applied. The coating liquid containing the p-type semiconductor compound and the n-type semiconductor compound may be prepared by preparing a solution containing the p-type semiconductor compound and a solution containing the n-type semiconductor compound, respectively, and mixing them. The semiconductor compound and the n-type semiconductor compound may be dissolved.

  The total concentration of the p-type semiconductor compound and the n-type semiconductor compound in the coating solution is preferably 1.0% by mass or more based on the entire coating solution from the viewpoint of forming an active layer having a sufficient thickness. It is preferable that it is 4.0 mass% or less with respect to the whole coating liquid from a viewpoint of fully dissolving a semiconductor compound.

  Examples of coating methods include spin coating, ink jet, doctor blade, drop casting, reverse roll coating, gravure coating, kiss coating, roll brushing, spray coating, air knife coating, and wire barber coating. , Pipe doctor method, impregnation / coating method or curtain coating method, flexo coating method and the like. You may perform the drying process by heating etc. after application | coating of a coating liquid.

  As the solvent for the coating solution, those capable of uniformly dissolving the p-type semiconductor compound and the n-type semiconductor compound are preferable. For example, aliphatic hydrocarbons such as hexane, heptane, octane, isooctane, nonane or decane; toluene, xylene, Aromatic hydrocarbons such as mesitylene, cyclohexylbenzene, chlorobenzene or orthodichlorobenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin or decalin; methanol, ethanol or propanol; Lower alcohols such as anisole; aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone or cyclohexanone; acetophenone or Aromatic ketones such as lopiophenone; esters such as ethyl acetate, isopropyl acetate, butyl acetate or methyl lactate; halogen hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane or trichloroethylene; ethyl ether, tetrahydrofuran, cyclopentyl methyl ether, Examples include ethers such as dibutyl ether, diphenyl ether, and dioxane; or amides such as dimethylformamide, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), and dimethylacetamide.

  Among them, aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, chlorobenzene or orthodichlorobenzene; cycloaliphatic carbonization such as cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, tetralin or decalin Hydrogen; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; or ethers such as ethyl ether, tetrahydrofuran or dioxane.

  When the bulk heterojunction active layer is formed by a coating method, an additive may be further added to the coating solution containing the p-type semiconductor compound and the n-type semiconductor compound. The phase separation structure of the p-type semiconductor compound and the n-type semiconductor compound in the bulk heterojunction active layer affects light absorption, exciton diffusion, exciton separation (carrier separation), carrier transport, and the like. It is considered that good photoelectric conversion efficiency can be realized by optimizing the separation structure. By containing an additive having a high affinity for the p-type semiconductor compound or the n-type semiconductor compound in the coating solution, an active layer having a preferable phase separation structure can be obtained, and the photoelectric conversion efficiency can be improved.

  The additive is preferably solid or has a high boiling point in that the additive is less likely to be lost from the active layer (IV).

  Specifically, when the additive is solid, the melting point (1 atm) of the additive is usually 35 ° C. or higher, preferably 50 ° C. or higher, more preferably 80 ° C. or higher, more preferably 150 ° C. or higher. Particularly preferably, it is 200 ° C. or higher, preferably 400 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 300 ° C. or lower.

  When the additive is a liquid, the boiling point (1 atm) is 80 ° C. or higher, more preferably 100 ° C. or higher, particularly preferably 150 ° C. or higher, preferably 300 ° C. or lower, more preferably 250 ° C. or lower, More preferably, it is 200 degrees C or less.

  Examples of the additive include an aliphatic hydrocarbon compound having 10 to 20 carbon atoms which may have a substituent as long as it is solid or an aromatic hydrocarbon having 10 to 20 carbon atoms which may have a substituent. An aromatic compound having 10 to 20 carbon atoms is preferable. Specific examples include naphthalene compounds, and compounds in which 1 to 8 substituents are bonded to naphthalene are particularly preferable. Substituents bonded to naphthalene include halogen atom, hydroxyl group, cyano group, amino group, amide group, carbonyloxy group, carboxy group, carbonyl group, oxycarbonyl group, silyl group, alkenyl group, alkynyl group, alkoxy group , Aryloxy group, alkylthio group, arylthio group or aromatic group.

  If the additive is liquid, an aliphatic hydrocarbon compound having 8 to 9 carbon atoms which may have a substituent or an aromatic compound having 8 to 9 carbon atoms which may have a substituent, etc. Can be mentioned. Specific examples include dihalogenated hydrocarbon compounds, and compounds in which 1 to 8 substituents are bonded to octane are particularly preferable. Examples of the substituent bonded to octane include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, an amino group, a carbamoyl group, a carbonyloxy group, a carboxyl group, a carbonyl group, or an aromatic group, such as fluorine, chlorine, Halogen atoms such as bromine and iodine are preferred. Another example of the additive is a benzene compound to which 4 or more and 6 or less halogen atoms are bonded.

  The amount of the additive contained in the coating solution containing the p-type semiconductor compound and the n-type semiconductor compound is preferably 0.1 volume / volume% or more, more preferably 0.5 volume / volume% or more with respect to the entire coating solution. preferable. Moreover, 10 volume / volume% or less is preferable with respect to the whole coating liquid, and 5 volume / volume% or less is more preferable. When the amount of the additive is within this range, a preferable phase separation structure can be obtained.

1.1.2 p-type semiconductor compound The active layer (IV) contains at least the polymer compound (1) as a p-type semiconductor compound.

Polymer compound (1)
The polymer compound used in the photoelectric conversion element of the present invention (hereinafter sometimes referred to as “polymer compound (1)”) is a kind of p-type semiconductor compound, and is a benzoate represented by the formula (1). It has a bis-thiazole structural unit (hereinafter sometimes referred to as “structural unit represented by formula (1)”).

[In Formula (1),
T ¹ and T ² are each independently a thiophene ring which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group, a thiazole which may be substituted with a hydrocarbon group or an organosilyl group A ring, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is represented.
B ¹ and B ² represent a thiophene ring that may be substituted with a hydrocarbon group, a thiazole ring that may be substituted with a hydrocarbon group, or an ethynylene group. ]

Since the polymer compound used in the present invention has a benzobisthiazole structural unit represented by the formula (1), the band gap can be narrowed while deepening the HOMO level, which is advantageous for increasing the photoelectric conversion efficiency. It is. The polymer compound (1) is preferably a donor-acceptor type semiconductor polymer obtained by copolymerizing a structural unit represented by the formula (1) and a copolymerization component (2) described later. The donor-acceptor type semiconductor polymer means a polymer compound in which donor units and acceptor units are alternately arranged. The donor unit means an electron donating structural unit, and the acceptor unit means an electron accepting structural unit. The donor-acceptor type semiconductor polymer is preferably a polymer compound in which a structural unit represented by the formula (1) and a copolymer component (2) described later are alternately arranged. With such a structure, it can be suitably used as a p-type semiconductor compound.
In the present specification, the organosilyl group means a monovalent group in which one or more hydrocarbon groups are substituted on Si atoms, and the number of hydrocarbon groups substituted on Si atoms is two or more. It is preferably 3 or less, more preferably 3.

In the benzobisthiazole structural unit represented by the formula (1), T ¹ and T ² may be the same or different from each other, but are preferably the same from the viewpoint of easy production.
In the benzobisthiazole structural unit represented by the formula (1), T ¹ and T ² are preferably groups represented by the following formulas (t1) to (t5), respectively. Specifically, the alkoxy group of T ¹ and T ² is preferably a group represented by the following formula (t1), and the thioalkoxy group is preferably a group represented by the following formula (t2). As the thiophene ring optionally substituted with a group or an organosilyl group, a group represented by the following formula (t3) is preferable, and as the thiazole ring optionally substituted with a hydrocarbon group or an organosilyl group, the following formula ( The group represented by t4) is preferable, and the phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is represented by the following formula (t5). ) Is preferred. When T ¹ and T ² are groups represented by the following formulas (t1) to (t5), they can absorb short-wavelength light and have high planarity, so that π-π stacking is efficiently performed. Therefore, photoelectric conversion efficiency can be further increased.

Wherein (t1) ~ (t5), R 13 ~R 14 each independently represent a hydrocarbon group having 6 to 30 carbon atoms. R ¹⁵ to R ¹⁶ are each independently a hydrocarbon group having 6 to 30 carbon atoms, ^{or,, * - Si (R 18} ) a group represented by _3. R ^{15 ′} represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by * —Si (R ¹⁸ ) ₃ . R ¹⁷ represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, * —O—R ¹⁹ , * —S—R ²⁰ , * —Si (R ¹⁸ ) ₃ , or * —CF ₃ . R ¹⁸ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ¹⁸ may be the same or different. R ^{19 to} R ²⁰ represent a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond bonded to the thiazole ring of benzobisthiazole. ]

In the above formulas (t1) to (t5), the hydrocarbon group having 6 to 30 carbon atoms of R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ , and R ^{15 ′} is preferably a branched hydrocarbon group. More preferably, it is a branched chain saturated hydrocarbon group. The hydrocarbon groups of R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ , and R ^{15 ′} can increase the solubility in organic solvents by having a branch, and the polymer compound of the present invention has an appropriate crystallinity. Can be obtained. The larger the number of carbon atoms in the hydrocarbon groups of R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ , and R ^{15 ′} , the more the solubility in organic solvents can be improved. As a result, the synthesis of the polymer compound becomes difficult. Therefore, the carbon number of the hydrocarbon group of R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ , R ^{15 ′} is preferably 8 to 25, more preferably 8 to 20, and still more preferably 8 to 16. is there.

Examples of the hydrocarbon group having 6 to 30 carbon atoms represented by R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ and R ^{15 ′} include a C ₆ alkyl group such as an n-hexyl group; an n-heptyl group and the like. C ₇ alkyl group: n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-methylheptyl group A C ₈ alkyl group such as 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group; n-nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2,3,3,4-tetramethylpen Le group, 3,5,5 C ₉ alkyl group such as trimethyl hexyl group; n-decyl group, 1-n-Penchirupenchiru group, 1-n-butyl hexyl group, 2-n-butyl hexyl group, 1- n- propyl-heptyl group, 1-ethyl-octyl group, 2-ethyl-octyl group, 1-methylnonyl group, 2-methylnonyl group, C ₁₀ alkyl group such as 3,7-dimethyl octyl group; n- undecyl group, 1-n -C ₁₁ alkyl groups such as butyl heptyl group, 2-n-butyl heptyl group, 1-n-propyl octyl group, 2-n-propyl octyl group, 1-ethyl nonyl group, 2-ethyl nonyl group; n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 2-n-butyloctyl group, 1-n-propylnonyl group, 2-n-propylnonyl C ₁₂ alkyl group such as; n-tridecyl group, 1-n-pentyl-octyl group, 2-n-pentyl-octyl group, 1-n-Buchirunoniru group, 2-n-Buchirunoniru group, 1-methyl-dodecyl group, 2- C ₁₃ alkyl group such as a methyl dodecyl group; n-tetradecyl group, 1-n-heptyl-heptyl group, 1-n-hexyl-octyl group, 2-n-hexyl-octyl group, 1-n-Penchirunoniru group, 2-n - Penchirunoniru C ₁₄ alkyl group such group; n-pentadecyl group, 1-n-heptyl-octyl group, 1-n-hexyl-nonyl group, 2-n- C ₁₅ alkyl group such as hexyl nonyl group; n-hexadecyl group , 2-n-hexyl-decyl group, 1-n-octyl-octyl group, 1-n-Hepuchirunoniru group, C ₁₆ alkyl group such as 2-n-Hepuchirunoniru group; n-heptadecyl group, 1- - C ₁₇ alkyl group such as octyl nonyl group; n- octadecyl, C ₁₈ alkyl group such as 1-n- Nonirunoniru group; C ₁₉ alkyl group such as n- nonadecyl; n- eicosyl group, 2-n- octyl C ₂₀ alkyl group such as dodecyl group; C ₂₁ alkyl group such as n-heneicosyl group; C ₂₂ alkyl group such as n-docosyl group; C ₂₃ alkyl group such as n-tricosyl group; n-tetracosyl group, 2-n - C ₂₄ alkyl group such as decyl tetradecyl group; and the like. Preferably a C ₈ -C ₂₈ alkyl group, more preferably a C ₈ -C ₂₆ alkyl group, more preferably a C ₈ -C ₂₆ branched alkyl group, even more preferably C ₈ -C ₂₄ It is a branched alkyl group. In particular, preferably 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-n-butyloctyl group, 2-n-hexyldecyl group, 2-n-octyldodecyl group, 2-n-decyltetradecyl group is there. When R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ , and R ^{15 ′} are the above groups, the polymer compound of the present invention has improved solubility in an organic solvent and has appropriate crystallinity.

In the above formulas (t1) to (t5), in the group represented by * -Si (R ¹⁸ ) ₃ of R ^{15 to} R ¹⁷ and R ^{15 ′} , the number of carbon atoms of the aliphatic hydrocarbon group of R ¹⁸ is preferably Is 1-18, More preferably, it is 1-8. Examples of the aliphatic hydrocarbon group for R ¹⁸ include alkyl groups such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group, an octyl group, and an octadecyl group. The carbon number of the aromatic hydrocarbon group for R ¹⁸ is preferably 6 to 8, more preferably 6 to 7, and particularly preferably 6. Examples of the aromatic hydrocarbon group for R ¹⁸ include a phenyl group. Among them, R ¹⁸ is preferably an aliphatic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group, and particularly preferably an isopropyl group. The plurality of R ¹⁸ may be the same or different, but are preferably the same. When R ^{15 to} R ¹⁷ and R ^{15 ′} are a group represented by * —Si (R ¹⁸ ) ₃ , the polymer compound of the present invention has improved solubility in an organic solvent.

In the above formulas (t1) to (t5), as the group represented by * -Si (R ¹⁸ ) ₃ of R ^{15 to} R ¹⁷ and R ^{15 ′} , specifically, a trimethylsilyl group, a triethyldimethylsilyl group, Alkylsilyl groups such as isopropyldimethylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triethylsilyl group, triisobutylsilyl group, tripropylsilyl group, tributylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group; And arylsilyl groups such as triphenylsilyl group and tert-butylchlorodiphenylsilyl group. Among them, an alkylsilyl group is preferable, and a trimethylsilyl group and a triisopropylsilyl group are particularly preferable.

In the above formula (t5), when R ¹⁷ is a halogen atom, any of fluorine, chlorine, bromine and iodine can be used. R ¹⁷ is preferably a halogen atom or * -CF ₃ .

R ^{15 ′} is a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms exemplified as R ¹⁵ , or a group similar to the group represented by * —Si (R ¹⁸ ) ₃ , and is a hydrogen atom. It is preferable.

As the electron donating groups of T ¹ and T ² , groups represented by formulas (t1), (t3), and (t5) are preferable from the viewpoint of excellent planarity as a whole structural unit represented by formula (1). More preferably, a group represented by the formula (t3) is more preferable, and groups represented by the following formulas (t3-1) to (t3-16) are particularly preferable. In the formula, * represents a bond.

As T ¹ and T ² , an electron donating group or an electron withdrawing group can be used. Examples of the electron donating group include groups represented by formulas (t1) to (t3).

[In formulas (t1) to (t3), * represents a bond, and R ^{13 to} R ¹⁵ and R ^{15 ′} represent the same groups as described above. * Represents a bond. ]

Examples of the electron withdrawing group that can be used as T ¹ and T ² include groups represented by formulas (t4) to (t5).

[In the formulas (t4) to (t5), R ¹⁶ represents the same group as described above. R ¹⁷ represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, * —O—R ¹⁹ , * —S—R ²⁰ , * —Si (R ¹⁸ ) ₃ , or * —CF ₃ . * Represents a bond. ]

In the benzobisthiazole structural unit represented by the formula (1), B ¹ and B ² may be the same or different from each other, but are the same from the viewpoint of easy production. Preferably there is. In the structural unit represented by the formula (1), B ¹ and B ² are each preferably a group represented by any of the following formulas (b1) to (b3). When B ¹ and B ² are groups represented by the following formulas (b1) to (b3), the obtained polymer compound has good planarity, and the photoelectric conversion efficiency can be further improved.

[In the formulas (b1) to (b3), R ²¹ , R ²² and R ^{21 ′} represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms.
* Represents a bond, and in particular, * on the left side represents a bond bonded to the benzene ring of the benzobisthiazole compound. ]

Examples of the hydrocarbon group having 6 to 30 carbon atoms of R ²¹ , R ²² and R ^{21 ′} are exemplified as the hydrocarbon group having 6 to 30 carbon atoms of R ^{13 to} R ¹⁷ , R ^{19 to} R ²⁰ and R ^{15 ′} . A group can be preferably used.
It is preferable that R ²¹ , R ²² , and R ^{21 ′} are hydrogen atoms because a donor-acceptor type semiconductor polymer can be easily formed. In addition, it is preferable that R ²¹ , R ²² , and R ^{21 ′} are hydrocarbon groups having 6 to 30 carbon atoms because the photoelectric conversion efficiency may be further increased.

In addition, in the benzobisthiazole structural unit represented by the formula (1), the whole structural unit represented by the formula (1) is excellent in flatness, and the resulting polymer compound as a whole is also excellent in flatness, B ¹ and B ² are more preferably groups represented by the formulas (b1) and (b2). When B ¹ and B ² are groups represented by the formulas (b1) and (b2), an interaction between an S atom and an N atom occurs in the benzobisthiazole structural unit (1), and planarity is further improved. . As B ¹ and B ² , specifically, a group represented by the following formula is preferable. In the formula, * represents a bond, and * on the left side is bonded to the benzene ring of benzobisthiazole.

  Moreover, as a structural unit represented by Formula (1), the structural unit represented by following formula (1-1)-(1-48) is mentioned, for example.

  It is preferable to use a copolymerization component (2) (donor unit or acceptor unit) that forms a donor-acceptor type semiconductor polymer in combination with the structural unit represented by the formula (1). A conventionally well-known structural unit can be used as a copolymerization component (2). Specifically, the following structural units can be mentioned. Among these, structural units represented by the formulas (c1), (c3) to (c5), (c7), (c9), (c12), (c21), (c27), (c37), and (c42) are preferable.

[In the formulas (c1) to (c43), R ^{30 to} R ⁷³ and R ^{75 to} R ⁷⁶ each independently represents a hydrocarbon group having 4 to 30 carbon atoms, and R ⁷⁴ represents a hydrogen atom or 4 carbon atoms. Represents ~ 30 hydrocarbon groups. A ³⁰ and A ³¹ each independently represent the same group as T ¹ and T ^2, and j represents an integer of 1 to 4. ● represents a bond bonded to B ¹ or B ² of the structural unit represented by the formula (1). ]

Examples of the hydrocarbon group having 4 to 30 carbon atoms represented by R ^{30 to} R ⁷⁶ include a C ₄ alkyl group such as an n-butyl group; a C ₅ alkyl group such as an n-pentyl group; an n-hexyl group and the like. C ₆ alkyl group; n-heptyl C ₇ alkyl group such as: n-octyl group, 1-n-Buchirubuchiru group, 1-n-propyl pentyl group, 1-ethylhexyl group, a 2-ethylhexyl group, 3-ethylhexyl A C ₈ alkyl group such as a group, 4-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group; n -Nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyl Corruptible group, 2,3,3,4- tetramethyl-pentyl group, 3,5,5 C ₉ alkyl group such as trimethyl hexyl group; n-decyl group, 1-n-Penchirupenchiru group, 1-n-Bed Tilhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-dimethyloctyl group, etc. C ₁₀ alkyl group; n-undecyl group, 1-n-butyl-heptyl group, 2-n-butyl-heptyl group, 1-n-propyl-octyl group, 2-n-propyl-octyl group, 1-Echirunoniru group, 2- Echirunoniru C ₁₁ alkyl group such group; n-dodecyl group, 1-n-pentyl-heptyl group, 2-n-pentyl-heptyl group, 1-n-butyl-octyl group, 2-n-butyl-octyl group, 1- - propyl nonyl group, 2-n-propyl-C ₁₂ alkyl group such as a nonyl group; n-tridecyl group, 1-n-pentyl-octyl group, 2-n-pentyl-octyl group, 1-n-Buchirunoniru group, 2-n - Buchirunoniru group, 1-methyl-dodecyl group, C ₁₃ alkyl group such as 2-methyl-dodecyl group; n-tetradecyl group, 1-n-heptyl-heptyl group, 1-n-hexyl-octyl group, 2-n-hexyl-octyl group , 1-n-Penchirunoniru group, C ₁₄ alkyl group such as 2-n-Penchirunoniru group; n-pentadecyl group, 1-n-heptyl-octyl group, 1-n-hexyl-nonyl group, 2-n-hexyl-nonyl C ₁₅ alkyl group such group; n-hexadecyl group, 2-n-hexyl-decyl group, 1-n-octyl-octyl group, 1-n-Hepuchirunoniru group, 2-n-Hepuchirunoniru group N- heptadecyl group, 1-n- octyl C ₁₇ alkyl group such as a nonyl group;; C ₁₆ alkyl group n- octadecyl, C ₁₈ alkyl group such as 1-n- Nonirunoniru group; such as n- nonadecyl C ₁₉ alkyl group; C ₂₀ alkyl group such as n-eicosyl group and 2-n-octyldodecyl group; C ₂₁ alkyl group such as n-heneicosyl group; C ₂₂ alkyl group such as n-docosyl group; n-tricosyl group and the like n- tetracosyl group, C ₂₄ alkyl group such as 2-n- decyl tetradecyl group;; C ₂₃ alkyl group, and the like. Preferably a C ₈ -C ₂₈ alkyl group, more preferably a C ₈ -C ₂₆ alkyl group, more preferably a C ₈ -C ₂₆ branched alkyl group, even more preferably C ₈ -C ₂₄ A branched alkyl group, particularly preferably 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-n-butyloctyl group, 2-n-hexyldecyl group, 2-n-octyldodecyl group, 2- n-decyltetradecyl group. When R ^{30 to} R ⁷³ , R ^{75 to} R ⁷⁶ are the above groups, and R ⁷⁴ is a hydrogen atom or the above groups, the polymer compound of the present invention has improved solubility in an organic solvent, It has crystallinity.

The groups represented by the above formulas (c1) to (c30) are groups that act as acceptor units, and the groups represented by formulas (c32) to (c43) are groups that act as donor units. It is. The group represented by the formula (c31) may act as an acceptor unit or may act as a donor unit depending on the types of A ³⁰ and A ³¹ .

  The repeating ratio of the structural unit represented by the formula (1) in the polymer compound (1) used in the present invention is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, further preferably. Is 30 mol% or more, and is usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and still more preferably 70 mol% or less.

  The ratio of the repeating unit of the copolymer component (2) in the polymer compound (1) is usually 1 mol% or more, preferably 5 mol% or more, more preferably 15 mol% or more, and further preferably 30 mol% or more. It is usually 99 mol% or less, preferably 95 mol% or less, more preferably 85 mol% or less, and still more preferably 70 mol% or less.

  In the polymer compound (1) according to the present invention, the arrangement state of the structural unit represented by the formula (1) of the repeating unit and the copolymer component (2) may be any of alternating, block and random. That is, the polymer compound (1) according to the present invention may be an alternating copolymer, a block copolymer, or a random copolymer. Preferably, they are arranged alternately.

  In the polymer compound (1), the structural unit represented by the formula (1) and the copolymer component (2) may each contain only one type. Moreover, 2 or more types of structural units represented by Formula (1) may be included, and 2 or more types of copolymerization components (2) may be included. The type of the structural unit represented by the formula (1) and the copolymer component (2) is usually 8 or less, preferably 5 or less. Particularly preferred is a polymer compound (1) containing one type of structural unit represented by formula (1) and one type of copolymer component (2) alternately, and most preferred is formula (1). ) And a polymer compound (1) containing only one type of copolymer component (2) alternately.

Preferred specific examples of the polymer compound (1) are shown below. However, the polymer compound (1) according to the present invention is not limited to the following examples. In the following specific examples, R ^T is an n-octyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-n-butyloctyl, 2-n-hexyldecyl group, 2-n-octyldodecyl group, It represents a 2-n-decyltetradecyl group or a triisopropylsilyl group. R ^{30 to} R ⁷³ and R ^{75 to} R ^{76 each} represents an n-octyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-n-butyloctyl group, or a 2-n-hexyldecyl group; ⁷⁴ is a hydrogen atom, or n-octyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-n-butyloctyl, 2-n-hexyldecyl group, 2-n-octyldodecyl group, 2- An n-decyltetradecyl group or a triisopropylsilyl group is represented. When the polymer compound (1) includes a plurality of types of repeating units, the ratio of the number of each repeating unit is arbitrary.

  The polymer compound (1) used in the present invention preferably has absorption in a long wavelength region (preferably 600 nm or more, more preferably 650 nm or more). Moreover, the photoelectric conversion element using a high molecular compound (1) shows a high open circuit voltage (Voc), and shows a high photoelectric conversion characteristic. When the polymer compound (1) is a p-type semiconductor compound and the fullerene compound is combined as an n-type semiconductor compound, particularly high photoelectric conversion characteristics are exhibited. Further, the polymer compound (1) according to the present invention has an advantage that it has a low HOMO energy level and is not easily oxidized.

  Moreover, since the high molecular compound (1) exhibits high solubility in a solvent, there is an advantage that coating film formation is easy. In addition, since the range of choice of solvent is widened when performing coating film formation, a solvent suitable for film formation can be selected, and the film quality of the formed active layer can be improved. This is also considered to be a factor that the photoelectric conversion element using the polymer compound (1) according to the present invention exhibits high photoelectric conversion characteristics.

  In general, the weight average molecular weight and number average molecular weight of the polymer compound (1) of the present invention are preferably 2,000 or more and 500,000 or less, more preferably 3,000 or more and 200,000 or less. is there. The weight average molecular weight and number average molecular weight of the polymer compound (1) of the present invention can be calculated based on a calibration curve prepared using polystyrene as a standard sample using gel permeation chromatography.

  The polymer compound (1) according to the present invention preferably has a light absorption maximum wavelength (λmax) of 400 nm or more, more preferably 450 nm or more, and is usually 1200 nm or less, preferably 1000 nm or less, more preferably 900 nm or less. Moreover, a half value width is 10 nm or more normally, Preferably it is 20 nm or more, and is 300 nm or less normally. Moreover, it is desirable that the absorption wavelength region of the polymer compound (1) according to the present invention is closer to the absorption wavelength region of sunlight.

  The solubility of the polymer compound (1) according to the present invention is preferably 0.1% by mass or more, more preferably 0.4% by mass or more, further preferably 0.8% by mass or more, with respect to chlorobenzene at 25 ° C. It is usually 30% by mass or less, preferably 20% by mass. High solubility is preferable in that a thicker active layer can be formed.

  The polymer compound (1) according to the present invention preferably interacts between molecules. In the present invention, the interaction between molecules means that the distance between polymer chains is shortened due to the interaction of π-π stacking between molecules of the polymer compound. The stronger the interaction, the higher the polymer compound tends to exhibit higher carrier mobility and / or crystallinity. That is, in a polymer compound that interacts between molecules, charge transfer between molecules is likely to occur. Therefore, the p-type semiconductor compound (polymer compound (1)) in the active layer (IV) and the n-type semiconductor compound It is considered that holes generated at the interface can be efficiently transported to the anode (II).

Method for Producing Polymer Compound (1) The method for producing the polymer compound (1) used in the present invention includes, for example, 2,6-diiodobenzo [1,2-d: 4,5-d ′] bisthiazole, and A compound represented by the formula (3), starting from one compound selected from the group consisting of 2,6-dibromobenzo [1,2-d: 4,5-d ′] bisthiazole,

[In Formula (3), T ¹ and T ² are each independently a thiophene ring, hydrocarbon group or organosilyl group optionally substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group. It represents a thiazole ring which may be substituted, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group. ]

  A compound represented by formula (4),

[In Formula (4), T ¹ and T ² each represent the same group as described above. X ¹ and X ² represent chlorine, bromine or iodine. ]

  A compound represented by formula (5),

[In Formula (5), T ¹ and T ² represent the same groups as described above. B ¹ and B ² represent a thiophene ring which may be substituted with a hydrocarbon group, a thiazole ring which may be substituted with a hydrocarbon group, or an ethynylene group. ]
It is manufactured by the manufacturing method characterized by passing through.

  The manufacturing method of the high molecular compound (1) used for this invention is a compound further represented by Formula (6)

[In formula (6), T ¹ and T ² represent the same groups as described above. B ³ and B ⁴ are the same groups as B ¹ and B ² . R ^{1 to} R ⁴ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. M ¹ and M ² each independently represent a boron atom or a tin atom. R ¹ and R ² may form a ring together with M ¹ , and R ³ and R ⁴ may form a ring together with M ² . m and n each represents an integer of 1 or 2. When m and n are 2, the plurality of R ¹ and R ³ may be the same or different. ]
It is preferable to go through.

The compound of the said Formula (6) can be manufactured as follows, for example.
First step: Formula (7) and / or Formula (8) in the presence of 2,6-dihalogenated benzobisthiazole and a metal catalyst

[In formulas (7) and (8), T ¹ and T ² each represent the same group as described above. R ⁵ and R ⁶ each independently represents a hydrogen atom or * -M ³ (R ⁷ ) _k R ⁸ . R ⁷ and R ⁸ each independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. M ³ represents a boron atom or a tin atom. * Represents a bond. R ⁷ and R ⁸ may form a ring together with M ³ . k represents an integer of 1 or 2. When k is 2, the plurality of R ⁷ may be the same or different. ]
The process of obtaining the compound represented by Formula (3) by making the compound represented by these react

Second step: A step of reacting a compound represented by formula (3) with a base and a halogenating reagent to obtain a compound represented by formula (4).

  Furthermore, it is possible to obtain the compound represented by formula (6) by including the following third step, fourth step and fifth step.

Third step: The compound represented by formula (4) is reacted with a compound represented by the following formula (9) and / or formula (10) in the presence of a metal catalyst, and represented by formula (5). Obtaining a compound.

[In Formulas (9) and (10), B ¹ and B ² each represent the same group as described above. R ^{9 to} R ¹² are each independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms. Represents an aryloxy group. M ⁴ and M ^{5 each} represent a boron atom, a tin atom, or a silicon atom. R ⁹ and R ¹⁰ may form a ring together with M ⁴ , and R ¹¹ and R ¹² may form a ring together with M ⁵ . p represents an integer of 1 or 2. When p is 2, the plurality of R ⁹ may be the same or different. ]

Fourth step: a step of obtaining a compound represented by the formula (6) by reacting a compound represented by the formula (5) with a base and a tin halide compound.
In the present invention, B ¹ and B ² of the compound represented by the formula (5) may be a thiophene ring (preferably a group represented by the formula (b1)) which may be substituted with a hydrocarbon group, or In the case of a thiazole ring (preferably a group represented by the formula (b2)) which may be substituted with a hydrocarbon group, the fourth step is preferably included.

Coupling reaction Furthermore, the polymer compound (1) is combined with the structural unit represented by the formula (1) and the copolymerization component (2) alternately by a coupling reaction to form a donor-acceptor type. It can be produced as a polymer compound (donor-acceptor type semiconductor polymer).

  The coupling reaction can be performed by reacting with a compound represented by the formula (6) and any of the compounds represented by the following formulas (C1) to (C43) in the presence of a metal catalyst. Among these, compounds represented by the formulas (C1), (C3) to (C5), (C7), (C9), (C12), (C21), (C27), (C37), and (C42) are preferable.

[In the formulas (C1) to (C43), R ^{30 to} R ⁷³ and R ^{75 to} R ⁷⁶ each independently represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms, and R ⁷⁴ represents a hydrogen atom. Or a C4-C30 hydrocarbon group is represented. A ³⁰ and A ³¹ each independently represent the same group as T ¹ and T ^2, and X represents a halogen atom. j represents an integer of 1 to 4. ]

Other p-type semiconductor compounds The active layer (IV) contains at least the polymer compound (1) according to the present invention as a p-type semiconductor compound. However, a p-type semiconductor compound different from the polymer compound (1) can be mixed and / or laminated with the polymer compound (1). Examples of other p-type semiconductor compounds that can be used in combination include an organic semiconductor compound (11). Hereinafter, the organic semiconductor compound (11) will be described. The organic semiconductor compound (11) may be a high molecular organic semiconductor compound or a low molecular organic semiconductor compound, but is preferably a high molecular organic semiconductor compound.

Organic semiconductor compound (11)
Examples of the organic semiconductor compound (11) include conjugated copolymer semiconductor compounds such as polythiophene, polyfluorene, polyphenylene vinylene, polythienylene vinylene, polyacetylene or polyaniline; copolymer semiconductors such as oligothiophene substituted with an alkyl group or other substituents Compounds and the like. Moreover, the copolymer semiconductor compound which copolymerized 2 or more types of monomer units is also mentioned. Conjugated copolymers are described in, for example, Handbook of Conducting Polymers, 3rd Ed. (2 volumes in total), 2007, J.M. Polym. Sci. Part A: Polym. Chem. 2013, 51, 743-768, J. MoI. Am. Chem. Soc. 2009, 131, 13886-13887, Angew. Chem. Int. Ed. 2013, 52, 8341-8344, Adv. Mater. Copolymers that can be synthesized by a combination of a copolymer described in publicly known documents such as 2009, 21, 2093-2097, derivatives thereof, and the monomers described can be used. The organic semiconductor compound (11) may be a kind of compound or a mixture of plural kinds of compounds. By using the organic semiconductor compound (11), an increase in the amount of light absorption due to the addition of the absorption wavelength band can be expected.

  Specific examples of the organic semiconductor compound (11) include the following, but are not limited to the following.

  HOMO (highest occupied molecular orbital) of p-type semiconductor compound (polymer compound (1) or a mixture of polymer compound (1) and other p-type semiconductor compound, preferably polymer compound (1)) ) The energy level can be selected depending on the type of the n-type semiconductor compound described later. In particular, when a fullerene compound is used as an n-type semiconductor compound, the lower limit of the HOMO energy level of the p-type semiconductor compound is usually −7 eV or more, more preferably −6.5 eV or more, and particularly preferably −6.2 eV or more. It is. On the other hand, the upper limit of the HOMO energy level is usually −4.0 eV or less, more preferably −4.5 eV or less, and particularly preferably −5.1 eV or less. The HOMO energy level of the p-type semiconductor compound is appropriately increased to improve the characteristics as a p-type semiconductor, and the HOMO energy level of the p-type semiconductor compound is appropriately suppressed to thereby increase the p-type semiconductor compound. And the open circuit voltage (Voc) is also improved.

  The LUMO (lowest unoccupied molecular orbital) energy level of the p-type semiconductor compound can be selected according to the type of the n-type semiconductor compound described later. In particular, when a fullerene compound is used as an n-type semiconductor compound, the LUMO energy level of the p-type semiconductor compound is usually −4.5 eV or more, preferably −4.3 eV or more, and usually −2.5 eV or less, preferably -2.7 eV or less. Since the LUMO energy level of the p-type semiconductor is moderately suppressed, the band gap is adjusted, light energy having a long wavelength can be effectively absorbed, and the short-circuit current density is improved. By appropriately increasing the LUMO energy level of the p-type semiconductor compound, electron transfer to the n-type semiconductor compound is likely to occur, and the short-circuit current density is improved.

As a method for calculating the LUMO energy level and the HOMO energy level, there are a theoretically calculated method and a method of actually measuring. The theoretically calculated values include semi-empirical molecular orbital methods and non-empirical molecular orbital methods. Examples of the actual measurement method include measurement of the ionization potential with an ultraviolet photoelectron analyzer (“AC-3” manufactured by Riken Keiki Co., Ltd.) under a UV-visible absorption spectrum measurement method or at normal temperature and pressure.
Among them, AC-3 measurement is preferable, and the AC-3 measurement method is used in the present invention.

1.1.3 n-type semiconductor compound An n-type organic semiconductor compound is generally a π-electron conjugated compound having a lowest unoccupied orbital (LUMO) level of 3.5 to 4.5 eV. , Fullerenes or derivatives thereof, octaazaporphyrins, etc., perfluoro compounds in which hydrogen atoms of p-type organic semiconductor compounds are substituted with fluorine atoms (for example, perfluoropentacene or perfluorophthalocyanine), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic Examples thereof include aromatic carboxylic acid anhydrides such as acid diimide, perylene tetracarboxylic acid anhydride, and perylene tetracarboxylic acid diimide, and polymer compounds containing an imidized product thereof as a skeleton.

Among these n-type organic semiconductor compounds, fullerene or a derivative thereof is preferable because charge separation can be performed at high speed and efficiently from the p-type semiconductor compound of the present invention (particularly, the polymer compound (1) having a specific structural unit). .
Fullerenes and derivatives thereof include C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, C84 fullerene, C240 fullerene, C540 fullerene, mixed fullerene, fullerene nanotubes, and some of them are hydrogen atoms, halogen atoms, substituted or non-substituted Examples include fullerene derivatives substituted with a substituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, and the like.

  As the fullerene derivative, phenyl-C61-butyric acid ester, diphenyl-C62-bis (butyric acid ester), phenyl-C71-butyric acid ester, phenyl-C85-butyric acid ester or thienyl-C61-butyric acid ester is preferable. The carbon number of the alcohol moiety is preferably 1-30, more preferably 1-8, still more preferably 1-4, and most preferably 1.

  Examples of preferred fullerene derivatives include phenyl-C61-butyric acid methyl ester ([60] PCBM), phenyl-C61-butyric acid n-butyl ester ([60] PCBnB), phenyl-C61-butyric acid isobutyl ester ([60] PCBiB). Phenyl-C61-butyric acid n-hexyl ester ([60] PCBH), phenyl-C61-butyric acid n-octyl ester ([60] PCBO), diphenyl-C62-bis (butyric acid methyl ester) (bis [60] PCBM) , Phenyl-C71-butyric acid methyl ester ([70] PCBM), phenyl-C85-butyric acid methyl ester ([84] PCBM), thienyl-C61-butyric acid methyl ester ([60] ThCBM), C60 pyrrolidine tris acid, C60 pyrrolidine Tris acid ethyl ester, -Methylfulleropyrrolidine (MP-C60), (1,2-methanofullerene C60) -61-carboxylic acid, (1,2-methanofullerene C60) -61-carboxylic acid t-butyl ester, JP2008-130889 And metallocene fullerenes such as US Pat. No. 7,329,709 and fullerenes having a cyclic ether group.

1.2 Anode (II), cathode (VI)
The anode (II) and the cathode (VI) have a function of collecting holes and electrons generated by light absorption. Therefore, it is preferable to use an electrode (VI) (cathode) suitable for collecting electrons and an electrode (II) (anode) suitable for collecting holes for the pair of electrodes. One of the pair of electrodes (preferably the anode (II)) may be translucent, and both may be translucent. Translucency means that sunlight passes through 40% or more. Moreover, it is preferable that the translucent transparent electrode has a sunlight transmittance of 70% or more in order to allow light to reach the active layer (IV) through the transparent electrode. The light transmittance can be measured with a normal spectrophotometer.

  The cathode (VI) is preferably an electrode made of a conductive material having a work function smaller than that of the anode and having a function of smoothly extracting electrons generated in the active layer (IV).

  Examples of the material of the cathode (VI) include platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, sodium, potassium, cesium, calcium or magnesium, and alloys thereof; Inorganic salts such as lithium fluoride and cesium fluoride; metal oxides such as nickel oxide, aluminum oxide, lithium oxide, and cesium oxide. These materials are preferable because they are materials having a small work function. When an n-type semiconductor compound such as zinc oxide having conductivity is used as the material for the electron transport layer (V), a material having a large work function suitable for an anode such as indium tin oxide (ITO) is used. It can also be used as a material for the cathode (VI). From the viewpoint of electrode protection, the cathode (VI) is preferably a metal electrode formed from a metal such as platinum, gold, silver, copper, iron, tin, aluminum, calcium or indium and an alloy using these metals.

  The film thickness of the cathode (VI) is usually 10 nm or more, preferably 20 nm or more, more preferably 50 nm or more, and usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. As the cathode (VI) film thickness is moderately increased, sheet resistance is suppressed, and the cathode (VI) film thickness is moderately thin, so that light can be efficiently converted to electricity without lowering the light transmittance. Can do. When the cathode (VI) is used as a transparent electrode, it is necessary to select a film thickness that achieves both light transmittance and sheet resistance.

  The sheet resistance of the cathode (VI) is usually 1000Ω / sq or less, preferably 500Ω / sq or less, more preferably 100Ω / sq or less. The lower limit is usually preferably 1 Ω / sq or more.

  As a method for forming the cathode (VI), there are a vacuum film forming method such as a vapor deposition method or a sputtering method, or a wet coating method in which an ink containing nanoparticles or a precursor is applied to form a film.

  The anode (II) is an electrode generally made of a conductive material having a work function larger than that of the cathode and having a function of smoothly extracting holes generated in the active layer (IV).

  Examples of the material of the anode (II) include conductive metal oxidation such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium-zirconium oxide (IZO), titanium oxide, indium oxide, or zinc oxide. A metal such as gold, platinum, silver, chromium or cobalt, or an alloy thereof. These substances are preferable because they have a large work function, and moreover, a conductive polymer material represented by PEDOT-PSS in which a polythiophene derivative is doped with polystyrene sulfonic acid can be stacked. When laminating such a conductive polymer, the work function of this conductive polymer material is large, so it is suitable for cathodes such as aluminum and magnesium, even if it is not a material with a large work function as described above. Metals can also be widely used.

  Further, PEDOT-PSS in which a polythiophene derivative is doped with polystyrene sulfonic acid, or a conductive polymer material in which polypyrrole, polyaniline, or the like is doped with iodine or the like can also be used as an anode material.

  When the anode (II) is a transparent electrode, it is preferable to use a light-transmitting conductive metal oxide such as ITO, zinc oxide or tin oxide, and it is particularly preferable to use ITO.

  The film thickness of the anode (II) is usually 10 nm or more, preferably 20 nm or more, more preferably 50 nm or more, and usually 10 μm or less, preferably 1 μm or less, more preferably 500 nm or less. When the anode (II) film thickness is moderately large, sheet resistance is suppressed, and when the anode (II) film thickness is moderately thin, light is efficiently converted to electricity without reducing light transmittance. be able to. When the anode (II) is a transparent electrode, it is necessary to select a film thickness that can achieve both light transmittance and sheet resistance.

  The sheet resistance of the anode (II) is usually preferably 1 Ω / sq or more, usually 1000 Ω / sq or less, preferably 500 Ω / sq or less, more preferably 100 Ω / sq or less.

  Examples of the method for forming the anode (II) include a vacuum film forming method such as an evaporation method or a sputtering method, or a wet coating method in which an ink containing nanoparticles or a precursor is applied to form a film.

  Further, the cathode (VI) and the anode (II) may have a laminated structure of two or more layers. Further, the characteristics (electrical characteristics, wetting characteristics, etc.) may be improved by performing a surface treatment on the cathode (VI) and the anode (II).

1.3 Substrate (I)
A photoelectric conversion element (VII) has the base material (I) which becomes a support body normally. That is, the electrodes (II) and (VI) and the active layer (IV) are formed on the substrate.

  The material for the substrate (I) is not particularly limited as long as the effects of the present invention are not significantly impaired. Preferable examples of the material of the substrate (I) include inorganic materials such as quartz, glass, sapphire and titania; polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol Organic materials such as copolymers, fluororesin films, polyolefins such as vinyl chloride or polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, or epoxy resins; paper or synthetic paper Paper materials; composite materials such as those obtained by coating or laminating a surface of a metal such as stainless steel, titanium, or aluminum to provide insulation;

  Examples of the glass include soda glass, blue plate glass, and non-alkali glass. Among these, alkali-free glass is preferable in that there are few eluted ions from the glass.

  As a shape of base material (I), things, such as plate shape, a film form, or a sheet form, can be used, for example. The thickness of the substrate (I) is usually 5 μm or more, preferably 20 μm or more, and is usually 20 mm or less, preferably 10 mm or less. It is preferable that the thickness of the base material (I) is appropriately thick because the possibility that the strength of the photoelectric conversion element is insufficient is reduced. When the film thickness of the substrate (I) is moderately thin, it is preferable because the cost is suppressed and the weight does not increase. The film thickness when the material of the substrate (I) is glass is usually 0.01 mm or more, preferably 0.1 mm or more, and usually 1 cm or less, preferably 0.5 cm or less. When the film thickness of the glass substrate (I) is appropriately thick, the mechanical strength is increased and it is difficult to break, which is preferable. Moreover, it is preferable for the glass substrate (I) to have a suitably thin film thickness because the weight does not increase.

1.4 Buffer layer (III, V)
The photoelectric conversion element (VII) includes an active layer (IV), an anode (II) (hereinafter also referred to as “electrode (II)”), and a cathode (VI) (hereinafter also referred to as “electrode (VI)”). It is preferable to have buffer layers (III) and (V) between them. The buffer layer can be classified into an electron transport layer (V) and a hole transport layer (III). By providing the buffer layer, electrons or holes can be easily transferred between the active layer (IV) and the anode (II) or the cathode (VI), and a short circuit between the electrodes can be prevented. However, in the present invention, the buffer layers (III) and (V) may not exist.

  The electron transport layer (V) and the hole transport layer (III) are arranged so that the active layer (IV) is sandwiched between the pair of electrodes (II) and (VI). That is, when the photoelectric conversion element (VII) according to the present invention includes both the electron transport layer (V) and the hole transport layer (III), the cathode (VI), the electron transport layer (V), and the active layer (IV) , Hole transport layer (III), and anode (II) are arranged in this order. When the photoelectric conversion element (VII) according to the present invention includes the electron transport layer (V) and does not include the hole transport layer (III), the cathode (VI), the electron transport layer (V), the active layer (IV), and The anode (II) is arranged in this order.

1.4.1 Electron transport layer (V)
The electron transport layer (V) is a layer that extracts electrons from the active layer (IV) to the cathode (VI), and the material constituting the electron transport layer (V) is an electron transport property that improves the efficiency of electron extraction. These materials are preferable, and an organic compound or an inorganic compound may be used, but an inorganic compound is preferable.

  Preferable examples of the inorganic compound material include a salt of an alkali metal such as lithium, sodium, potassium or cesium, a salt of an alkaline earth metal such as calcium, or a metal oxide. Among them, the alkali metal salt is preferably a fluoride salt such as lithium fluoride, sodium fluoride, potassium fluoride or cesium fluoride, and the metal oxide is titanium oxide (TiOx) or zinc oxide (ZnO). A metal oxide having n-type semiconductor characteristics such as More preferable as the material of the inorganic compound is a metal oxide having n-type semiconductor properties such as titanium oxide (TiOx) or zinc oxide (ZnO). Particularly preferred is titanium oxide (TiOx). The operation mechanism of such a material is unknown, but when combined with the cathode (VI), it is conceivable to reduce the work function and increase the voltage applied to the inside of the solar cell element.

  The LUMO energy level of the material of the electron transport layer (V) is usually −4.0 eV or more, preferably −3.9 eV or more, and usually −1.9 eV or less, preferably −2.0 eV or less. It is preferable that the LUMO energy level of the material of the electron transport layer (V) is appropriately suppressed in that charge transfer can be promoted. It is preferable that the LUMO energy level of the material of the electron transport layer (V) is appropriately increased in that reverse electron transfer to the n-type semiconductor compound can be prevented.

  The HOMO energy level of the material of the electron transport layer (V) is usually −9.0 eV or more, preferably −8.0 eV or more, and usually −5.0 eV or less, preferably −5.5 eV or less. When the HOMO energy level of the material of the electron transport layer (V) is appropriately suppressed, it is preferable in that the movement of holes can be prevented. As a method for calculating the LUMO energy level and the HOMO energy level of the material of the electron transport layer (V), a cyclic voltammogram measurement method may be mentioned.

  The film thickness of the electron transport layer (V) is usually 0.1 nm or more, preferably 0.5 nm or more, more preferably 1.0 nm or more, usually 100 nm or less, preferably 70 nm or less, more preferably 40 nm or less, particularly Preferably it is 20 nm or less. When the thickness of the electron transport layer (V) is moderately large, it functions as a buffer material, and when the thickness of the electron transport layer (V) is moderately thin, electrons can be easily taken out and photoelectric conversion is performed. Efficiency can be improved.

1.4.2 Hole transport layer (III)
The hole transport layer (III) is a layer that extracts holes from the active layer (IV) to the anode (II), and any material that can improve the hole extraction efficiency can be used. There is no particular limitation. Specifically, a conductive polymer in which polythiophene, polypyrrole, polyacetylene, triphenylenediamine, polyaniline or the like is doped with sulfonic acid and / or iodine, a polythiophene derivative having a sulfonyl group as a substituent, or a conductive organic material such as arylamine. Examples include compounds, metal oxides having p-type semiconductor properties such as molybdenum trioxide, vanadium pentoxide, or nickel oxide, and the above-described p-type semiconductor compounds. Among them, a conductive polymer doped with sulfonic acid is preferable, and poly (3,4-ethylenedioxythiophene) poly (styrenesulfonic acid) (PEDOT-PSS) in which a polythiophene derivative is doped with polystyrene sulfonic acid is more preferable. . A thin film of metal such as gold, indium, silver or palladium can also be used. A thin film of metal or the like may be formed alone or in combination with the above organic material.

  The film thickness of the hole transport layer (III) is usually 0.2 nm or more, preferably 0.5 nm or more, more preferably 1.0 nm or more, usually 400 nm or less, preferably 200 nm or less, more preferably 100 nm or less, particularly Preferably it is 70 nm or less. When the film thickness of the hole transport layer 104 is moderately large, it will serve as a buffer material. When the film thickness of the hole transport layer (III) is moderately thin, holes can be easily taken out, and the photoelectric conversion efficiency Can be improved.

  There is no restriction | limiting in the formation method of an electron carrying layer (V) and a hole carrying layer (III). For example, when a material having sublimation property is used, it can be formed by a vacuum deposition method or the like. Further, for example, when a material soluble in a solvent is used, it can be formed by a wet coating method such as spin coating or inkjet. When a semiconductor compound is used for the hole transport layer (III), the precursor may be converted into a semiconductor compound after forming a layer containing a semiconductor compound precursor, as in the active layer (IV).

1.5 Manufacturing Method of Photoelectric Conversion Element The photoelectric conversion element (VII) is formed, for example, according to the following method, using a substrate (I), an anode (II), a hole transport layer (III), an active layer (IV), an electron transport layer. It can be produced by sequentially stacking (V) and cathode (VI). For example, an indium tin oxide (ITO) transparent conductive film (anode) patterned glass substrate (manufactured by Geomatic) is ultrasonically cleaned with acetone, then ultrasonically cleaned with ethanol, and then dried with nitrogen blow. Ozonation is performed to make a substrate with an anode. Next, PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid))) aqueous dispersion used as a hole transport layer was applied with a spin coater (5000 rpm for 50 seconds) and then at 200 ° C. A hole transport layer can be formed by annealing for 10 minutes. Later, the active layer can be formed by carrying it in a glove box, spin-coating a mixed solution of p-type semiconductor compound and n-type semiconductor compound in an inert gas atmosphere, and performing annealing treatment or drying under reduced pressure on a hot plate. . Next, an electron transport layer in which tetraisopropyl orthotitanate in ethanol (about 0.3 v%) is spin-coated in the atmosphere and converted into titanium oxide by moisture in the atmosphere can be produced. Finally, aluminum as an electrode is vapor-deposited to form a cathode, and a photoelectric conversion element can be obtained.
In addition, photoelectric conversion elements having different configurations, for example, a photoelectric conversion element that does not have at least one of the hole transport layer (III) and the electron transport layer (V) can be manufactured by a similar method.

1.6 Photoelectric conversion characteristics The photoelectric conversion characteristics of the photoelectric conversion element (VII) can be obtained as follows. The photoelectric conversion element (VII) is irradiated with AM1.5G light with a solar simulator at an irradiation intensity of 100 mW / cm ² to measure current-voltage characteristics. From the obtained current-voltage curve, photoelectric conversion characteristics such as photoelectric conversion efficiency (PCE), short circuit current density (Jsc), open circuit voltage (Voc), fill factor (FF), series resistance, and shunt resistance can be obtained.

2. Organic thin film solar cell according to the present invention The photoelectric conversion element (VII) according to the present invention is preferably used as a solar cell, in particular, a solar cell element of an organic thin film solar cell, and is provided with a photoelectric conversion element (VII). Thin film solar cells are also included in the technical scope of the present invention.

  The organic thin film solar cell according to the present invention can be used for any application. Examples of fields to which the organic thin film solar cell according to the present invention can be applied include building material solar cells, automotive solar cells, interior solar cells, railway solar cells, marine solar cells, airplane solar cells, and spacecrafts. Solar cells for home appliances, solar cells for home appliances, solar cells for mobile phones, solar cells for toys, and the like.

  The organic thin film solar cell according to the present invention may be used as it is, or may be used as a solar cell module by installing a solar cell on the substrate (I). If a specific example is given, when using the board | plate material for building materials as a base material, a solar cell panel can be produced as a solar cell module by providing a thin film solar cell on the surface of this board | plate material.

  This application claims the benefit of priority based on Japanese Patent Application No. 2015-022034 filed on Feb. 6, 2015. The entire contents of the specification of Japanese Patent Application No. 2015-022034 filed on February 6, 2015 are incorporated herein by reference.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.
The measuring method used in the synthesis example is as follows.

NMR spectrum measurement About the benzobis thiazole compound, NMR spectrum measurement was performed using the NMR spectrum measuring device (Agilent (formerly Varian), "400MR", and Bruker, "AVANCE500").

  An example of the synthesis of the polymer compound (1) used in this patent is shown below. The polymer compound (1) used in the present invention is not limited by the following synthesis examples, and the synthesis method itself may be synthesized with appropriate modifications within a range that can meet the purpose described above and below. Of course it is possible. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Synthesis example 1
Synthesis of 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-HDTH)

In a 300 mL flask, 2,6-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DI, 5.2 g, 11.7 mmol), tributyl [5- (2-hexyldecyl) thiophene- 2-yl] stannane (HDT-Sn, 23.2 g, 38.6 mmol), tris (2-furyl) phosphine (443 mg, 1.87 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct ( 490 mg, 0.47 mol) and N, N-dimethylformamide (115 mL) were added and reacted at 120 ° C. for 23 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl. ] 5.52 g of benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-HDTH) was obtained as a pale yellow solid (yield 60%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

Synthesis Examples 2-6
As in Synthesis Example 1, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-DMOTH (Synthesis Example 2), 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-EHTH) (synthesis) Example 3), 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-BOTH) (Synthesis Example 4) ), 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-TDTH) (Synthesis Example 5) 2,6-bis (5-triisopropylsilanylthiophene-2- Was obtained; [4,5-d '1,2-d] bisthiazole the (DBTH-TIPSTH) (Synthesis Example 6) - Le) benzo. The yield was 38-51%.

Synthesis example 7
Of 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-HDTH) Composition

In a 100 mL flask was 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-HDTH, 4 g, 4.97 mmol). ) And tetrahydrofuran (80 mL) were added and cooled to −40 ° C., then lithium diisopropylamide (2M solution, 5.5 mL, 10.9 mmol) was added dropwise and stirred for 30 minutes. Next, iodine (3.8 g, 14.9 mol) was added, followed by reaction at room temperature for 2 hours. After completion of the reaction, 10% sodium bisulfite was added and the mixture was extracted with chloroform. The obtained organic layer was washed with saturated aqueous sodium hydrogen carbonate and then with saturated brine and dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1/1) to obtain 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl. ] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH-HDTH) was obtained as a yellow solid (yield 51%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

Synthesis Examples 8-12
As in Synthesis Example 7, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bis Thiazole (DI-DBTH-DMOTH) (Synthesis Example 8), 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; d ′] bisthiazole (DI-DBTH-EHTH) (Synthesis Example 9), 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d 4,5-d ′] bisthiazole (DI-DBTH-BOTH) (Synthesis Example 10), 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-diiodobenzo; [1,2-d; 4,5-d ′] bisthiazole (DI DBTH-TDTH) (Synthesis Example 11), 4,8-diiodo-2,6-bis- (5-triisopropylsilanylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′ Bisthiazole (DI-DBTH-TIPSTH) (Synthesis Example 12) was obtained. The yield was 36-70%.

Synthesis Example 13
2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH -DBTH-HDTH)

In a 50 mL flask was 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH- HDTH, 1.1 g, 1.04 mmol), tributylthiophen-2-yl-stannane (830 μL, 2.60 mmol), tris (2-furyl) phosphine (40 mg, 0.17 mmol), tris (dibenzylideneacetone) dipalladium (0) -Chloroform adduct (45 mg, 0.04 mmol) and N, N-dimethylformamide (22 mL) were added and reacted at 80 ° C. for 19 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration was purified by column chromatography (silica gel, chloroform / hexane = 1 / 1-chloroform) to obtain 2,6-bis [5- (2-hexyldecyl) thiophene-2. -Yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH) was obtained as a yellow solid (1.01 g). Yield 100%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

Synthesis Examples 14-17
As in Synthesis Example 13, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 5-d ′] bisthiazole (DTH-DBTH-DMOTH) (Synthesis Example 14), 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4,8-dithiophen-2-yl- Benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-EHTH) (Synthesis Example 15), 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-BOTH) (Synthesis Example 16), 2,6-bis [5- ( 2-decyltetradecyl) thiophen-2-yl] -4,8 Was obtained; [4,5-d '1,2-d] bisthiazole the (DTH-DBTH-TDTH) (Synthesis Example 17) - dithiophen-2-yl benzo. The yield was 45 to 99%.

Synthesis Example 18
2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bisthiazol-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole ( Synthesis of DTHA-DBTH-HDTH)

In a 30 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d ′] bisthiazole (DI-DBTH— HDTH, 800 mg, 0.76 mmol), 2-tributylstannanylthiazole (708 mg, 1.89 mmol), tris (2-furyl) phosphine (29 mg, 0.12 mmol), tris (dibenzylideneacetone) dipalladium (0)- Chloroform adduct (32 mg, 30 μmol) and N, N-dimethylformamide (5 mL) were added and reacted at 80 ° C. for 17 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, and the mixture was extracted twice with chloroform. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Next, the crude product obtained by filtration and concentration is purified by column chromatography (silica gel, chloroform), whereby 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8- 684 mg of bisthiazol-2-yl-benzo [1,2-d; 4,5-d ′] bisthiazole (DTHA-DBTH-HDTH) was obtained as a yellow solid (yield 94%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

Synthesis Example 19
As in Synthesis Example 18, 4,8-bis- (thiazol-2-yl) -2,6-bis- (5-triisopropylsilanylthiophen-2-yl) -benzo [1,2-d; , 5-d ′] bisthiazole (DBTH-TIPSTH-THA) was obtained. The yield was 45%.

Synthesis Example 20
2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [1,2-d; 4,5 -D '] bisthiazole (DTH-DBTH-HDTH-DSB)

2,6-Bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d ′] bis in a 50 mL flask Add thiazole (DTH-DBTH-HDTH, 602 mg, 0.62 mmol) and tetrahydrofuran (18 mL), cool to −40 ° C., add lithium diisopropylamide (2M solution, 0.65 mL, 1.30 mmol) dropwise and stir for 30 minutes. did. Thereafter, tributyltin chloride (352 μL, 1.30 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours. After completion of the reaction, water was added and extracted twice with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by filtration and concentration was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform), whereby 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl]- 634 mg of 4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSB), light brown oil (Yield 66%).
It was confirmed by ¹ H-NMR measurement that the target compound was produced.

Synthesis Example 21
As in Synthesis Example 20, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [ 1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-DMOTH-DSB) was obtained. The yield was 49 to 63%.

Synthesis Examples 22-25
Similar to Synthesis Example 20, 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4,8-bis (5-trimethylstanne) was obtained by using trimethyltin chloride instead of tributyltin chloride. Nylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-EHTH-DSM) (Synthesis Example 22), 2,6-bis [5- (2 -Butyloctyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH -BOTH-DSM) (Synthesis Example 23), 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl)- Be Zo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM) (Synthesis Example 24), 2,6-bis [5- (2-decyltetradecyl) thiophene-2 -Yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM) (synthesis) Example 25) was obtained. The yield was 27-67%.

Synthesis Examples 26 and 27
Similar to Synthesis Example 19, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiazol-2-yl) -benzo [1, 2-d; 4,5-d ′] bisthiazole (DTHA-DBTH-HDTH-DSB) (Synthesis Example 26), 4,8-bis (5-tributylstannylthiazol-2-yl) -2,6- Bis (5-triisopropylsilanylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DBTH-TIPSTH-THA-DSB) (Synthesis Example 27) was obtained. The yield was 49%.

Synthesis Example 28
Synthesis of P-THDT-DBTH-EH-IMTH

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [1,2-d. ; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSB, 150 mg, 0.10 mmol), 1,3-dibromo-5- (2-ethylhexyl) thieno [3,4-c] pyrrolo-4; , 6-dione (EH-IMTH-DB, 41 mg, 0.10 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.9 μmol), tris (o-tolyl) phosphine (5 mg 15.5 μmol) and chlorobenzene (12 mL) were added and reacted at 120 ° C. for 22 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequently, extraction with Soxhlet (chloroform) gave 109 mg (91%) of P-THDT-DBTH-EH-IMTH as a black solid.

Synthesis Example 29
Synthesis of P-THDT-DBTH-O-IMTH

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM, 90 mg, 0.07 mmol), 1,3-dibromo-5-octylthieno [3,4-c] pyrrolo-4,6-dione ( O-IMTH-DB, 30 mg, 0.07 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.8 μmol), tris (2-methoxyphenyl) phosphine (4 mg, 11.1 μmol) ) And chlorobenzene (7 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (50 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 74 mg (87%) of P-THDT-DBTH-O-IMTH as a black solid.

Synthesis Example 30
Synthesis of P-THDT-DBTH-DMO-IMTH

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM, 80 mg, 0.06 mmol), 1,3-dibromo-5- (3.7-dimethyloctyl) thieno [3,4, -c Pyrolo-4,6-dione (DMO-IMTH-DB, 28 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.4 μmol), tris (2-methoxy) Phenyl) phosphine (4 mg, 9.6 μmol) and chlorobenzene (3.2 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 68 mg (87%) of P-THDT-DBTH-DMO-IMTH as a black solid.

Synthesis Example 31
Synthesis of P-THDT-DBTH-H-IMTH

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d. ; 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM, 100 mg, 0.08 mmol), 1,3-dibromo-5-hexylthieno [3,4, -c] pyrrolo-4,6-dione; (H-IMTH-DB, 31 mg, 0.08 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 3.2 μmol), tris (2-methoxyphenyl) phosphine (4 mg, 12. 8 μmol) and chlorobenzene (8 mL) were added and reacted at 120 ° C. for 22 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 40 mg (44%) of P-THDT-DBTH-H-IMTH as a black solid.

Synthesis Example 32
Synthesis of P-TEHT-DBTH-HD-IMTH

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-EHTH-DSM, 100 mg, 0.09 mmol), 1,3-dibromo-5- (2-hexyldecyl) thieno [3,4-c] pyrrolo-; 4,6-dione (HD-IMTH-DB, 50 mg, 0.09 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.7 μmol), tris (2-methoxyphenyl) phosphine (6 mg, 14.9 μmol) and chlorobenzene (7 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 39 mg (37%) of P-TEHT-DBTH-HD-IMTH as a black solid.

Synthesis Example 33
Synthesis of P-TEHT-DBTH-ODD-IMTH

  In a 20 mL flask, 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-EHTH-DSM, 100 mg, 0.09 mmol), 1,3-dibromo-5- (2-octyldodecyl) thieno [3,4, -c] pyrrolo- 4,6-dione (ODD-IMTH-DB, 55 mg, 0.09 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.7 μmol), tris (2-methoxyphenyl) phosphine (6 mg, 14.9 μmol) and chlorobenzene (7 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) gave 91 mg (76%) of P-TEHT-DBTH-ODD-IMTH as a black solid.

Synthesis Example 34
Synthesis of P-TEHT-DBTH-TD-IMTH

  In a 20 mL flask, 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d ′] bisthiazole (DTH-DBTH-EHTH-DSM, 70 mg, 0.07 mmol), 1,3-dibromo-5- (2-decyltetradecyl) thieno [3,4, -c] pyrrolo -4,6-dione (TD-IMTH-DB, 43 mg, 0.07 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.8 μmol), tris (2-methoxyphenyl) Phosphine (4 mg, 11.2 μmol) and chlorobenzene (2.8 mL) were added and reacted at 120 ° C. for 25 hours. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, by Soxhlet extraction (chloroform), 62 mg (77%) of P-TEHT-DBTH-TD-IMTH was obtained as a black solid.

Synthesis Example 35
Synthesis of P-TBOT-DBTH-DMO-IMTH

  In a 20 mL flask, 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d 4,5-d ′] bisthiazole (DTH-DBTH-BOTH-DSM, 100 mg, 0.09 mmol), 1,3-dibromo-5- (3,7-dimethyloctyl) thieno [3,4, -c ] Pyrrolo-4,6-dione (DMO-IMTH-DB, 38 mg, 0.09 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.6 μmol), tris (2-methoxy) Phenyl) phosphine (5 mg, 14.4 μmol) and chlorobenzene (8 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-TBOT-DBTH-DMO-IMTH was obtained as a black solid at 26 mg (27%) by Soxhlet extraction (chloroform).

Synthesis Example 36
Synthesis of P-TBOT-DBTH-HD-IMTH

  In a 20 mL flask, 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d ; 4,5-d '] bisthiazole (DTH-DBTH-BOTH-DSM, 70 mg, 0.06 mmol), 1,3-dibromo-5- (2-hexyldecyl) thieno [3,4, -c] pyrrolo; -4,6-dione (HD-IMTH-DB, 32 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (2 mg, 2.4 μmol), tris (2-methoxyphenyl) Phosphine (4 mg, 9.6 μmol) and chlorobenzene (6 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequent Soxhlet extraction (chloroform) yielded 57 mg (78%) of P-TBOT-DBTH-HD-IMTH as a black solid.

Synthesis Example 37
Synthesis of P-TTDT-DBTH-B-IMTH

  In a 20 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2- d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM, 70 mg, 0.05 mmol), 1,3-dibromo-5-butylthieno [3,4, -c] pyrrolo-4,6- Dione (B-IMTH-DB, 17 mg, 0.05 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (2 mg, 2.0 μmol), tris (2-methoxyphenyl) phosphine (3 mg, 8 0.0 μmol) and chlorobenzene (3 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-TTDT-DBTH-B-IMTH was obtained as a black solid at 33 mg (52%) by Soxhlet extraction (chloroform).

Synthesis Example 38
Synthesis of P-TDMOT-DBTH-TDZ

  In a 20 mL flask, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [1,2 -D; 4,5-d '] bisthiazole (DTH-DBTH-DMOTH-DSB, 122 mg, 0.09 mmol), 4,7-dibromobenzo [1,2,5] thiadiazole (TDZ-DB, 26 mg, 0 0.09 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.5 μmol), tris (o-tolyl) phosphine (4 mg, 14.0 μmol), and chlorobenzene (10 mL) were added at 120 ° C. For 24 hours. After completion of the reaction, the reaction solution was added to methanol (50 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-TDMOT-DBTH-TDZ was obtained as a black solid at 31 mg (38%) by Soxhlet extraction (chloroform).

Synthesis Example 39
Synthesis of P-THDT-DBTH-FFTDZ

To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSB, 122 mg, 0.08 mmol), 4,7-dibromo-5,6-difluorobenzo [1,2,5] thiadiazole (FFTDZ-DB); , 28 mg, 0.08 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.4 μmol), tris (o-tolyl) phosphine (4 mg, 13.4 μmol) and chlorobenzene (10 mL) And reacted at 120 ° C. for 23 hours. After completion of the reaction, the reaction solution was added to methanol (50 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-THDT-DBTH-FFTDZ was obtained as a black solid at 27 mg (29%) by Soxhlet extraction (chloroform).

Synthesis Example 40
Synthesis of P-TTDT-DBTH-FFTDZ

  In a 20 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2- d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM, 90 mg, 0.06 mmol), 4,7-dibromo-5,6-difluorobenzo [1,2,5] thiadiazole (FFTDZ- DB, 20 mg, 0.06 mmol), tetrakis (triphenylphosphine) palladium (2 mg, 1.8 μmol), toluene (4 mL), and N, N-dimethylformamide (0.3 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-TTDT-DBTH-FFTDZ was obtained as a black solid at 70 mg (87%) by Soxhlet extraction (chloroform).

Synthesis Example 41
Synthesis of P-TTDT-DBTH-FTDZ

  In a 20 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2- d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM, 90 mg, 0.06 mmol), 4,7-dibromo-5-fluorobenzo [1,2,5] thiadiazole (FTDZ-DB, 19 mg, 0.06 mmol), tetrakis (triphenylphosphine) palladium (2 mg, 1.8 μmol), toluene (3 mL) and N, N-dimethylformamide (0.3 mL) were added and reacted at 120 ° C. for 23 hours. After completion of the reaction, the reaction mixture was added to methanol (25 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone). Subsequently, P-TTDT-DBTH-FTDZ was obtained as a black solid at 68 mg (85%) by Soxhlet extraction (chloroform).

Synthesis Example 42
Synthesis of P-THDT-DBTH-OO-TDZ

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM, 70 mg, 0.05 mmol), 4,7-dibromo-5,6-bisoctyloxybenzo [1,2,5] thiadiazole (OO); -TDZ-DB, 30 mg, 0.05 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (2 mg, 2.0 μmol), tris (2-methoxyphenyl) phosphine (3 mg, 8.0 μmol) And chlorobenzene (3 mL) was added and it reacted at 120 degreeC for 26 hours. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-THDT-DBTH-OO-TDZ was obtained as a black solid at 53 mg (73%) by Soxhlet extraction (chloroform).

Synthesis Example 43
Synthesis of P-TTDT-DBTH-NTDZ

  In a 20 mL flask, 2,6-bis [5- (2-decyltetradecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2- d; 4,5-d ′] bisthiazole (DTH-DBTH-TDTH-DSM, 80 mg, 0.05 mmol), 5,10-dibromonaphtho [1,2-c: 5,6-c ′] bis [1 , 2,5] thiadiazole (NTDZ-DB, 21 mg, 0.05 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (2 mg, 2.0 μmol), tris (2-methoxyphenyl) phosphine ( 3 mg, 8.0 μmol) and chlorobenzene (6 mL) were added and reacted at 120 ° C. for 28 hours. After completion of the reaction, the reaction mixture was added to methanol (30 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-TTDT-DBTH-NTDZ was obtained as a black solid at 63 mg (84%) by Soxhlet extraction (chloroform).

Synthesis Example 44
Synthesis of P-THDT-DBTH-DMO-DPP

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSB, 100 mg, 0.06 mmol), 3,6-bis (5-bromothiophen-2-yl) -2,5- (3,7 -Dimethyloctyl) -2,5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (DMO-DPP-DB, 49 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (0) -Addition of chloroform adduct (3 mg, 2.6 μmol), tris (o-tolyl) phosphine (3 mg, 10.4 μmol) and chlorobenzene (10 mL) Reacted for hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequently, P-THDT-DBTH-DMO-DPP was obtained as a black solid at 26 mg (26%) by Soxhlet extraction (chloroform).

Synthesis example 45
Synthesis of P-THDT-DBTH-EH-OFTT

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTH-DBTH-HDTH-DSM, 90 mg, 0.07 mmol), 4,6-dibromo-3-fluorothieno [3,4-b] thiophene-2-carboxylic acid ( 2-ethylhexyl) ester (EH-OFTT-DB, 33 mg, 0.07 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.1 μmol), tris (2-methoxyphenyl) phosphine (4 mg, 8.4 μmol) and chlorobenzene (7 mL) were added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (40 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-THDT-DBTH-EH-OFTT was obtained as a black solid at 80 mg (87%) by Soxhlet extraction (chloroform).

Synthesis Example 46
Synthesis of P-THHDT-DBTH-HTT

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiazol-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTHA-DBTH-HDTH-DSB, 120 mg, 0.08 mmol), 5,5′-dibromo-3-hexyl [2,2 ′] bithiophenyl (HTT-DB, 32 mg, 0.08 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 3.1 μmol), tris (o-tolyl) phosphine (4 mg, 12.3 μmol) and chlorobenzene (10 mL) were added. The reaction was carried out at 24 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 72 mg (77%) of P-THHDT-DBTH-HTT as a black solid.

Synthesis Example 47
Synthesis of P-THHDT-DBTH-EH-BDT

  To a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributylstannylthiazol-2-yl) -benzo [1,2-d. 4,5-d ′] bisthiazole (DTHA-DBTH-HDTH-DSB, 120 mg, 0.08 mmol), 2,6-dibromo-4,8-bis (2-ethylhexyloxy) -1,5-dithia; -S-indenecene (EH-BDT-DB, 47 mg, 0.08 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 3.1 μmol), tris (o-tolyl) phosphine (4 mg , 12.3 μmol) and chlorobenzene (10 mL) were added and reacted at 120 ° C. for 25 hours. After completion of the reaction, the reaction solution was added to methanol (50 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, extraction with Soxhlet (chloroform) gave 70 mg (64%) of P-THHDT-DBTH-EH-BDT as a dark red solid.

Synthesis Example 48
Synthesis of P-THTIPSTH-DBTH-O-IMTH

  In a 20 mL flask, 4,8-bis (5-tributylstannylthiazol-2-yl) -2,6-bis (5-triisopropylsilanylthiophen-2-yl) -benzo [1,2-d; , 5-d ′] bisthiazole (DBTH-TIPSTH-THA-DSB, 88 mg, 0.06 mmol), 1,3-dibromo-5-octylthieno [3,4-c] pyrrolo-4,6-dione (O— IMTH-DB, 26 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.5 μmol), tris (o-tolyl) phosphine (4 mg, 10 μmol) and chlorobenzene (8 mL) ) Was added and reacted at 120 ° C. for 24 hours. After completion of the reaction, the reaction solution was added to methanol (50 mL), the precipitated solid was collected by filtration, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Subsequently, P-THTIPSTH-DBTH-O-IMTH was obtained as a black solid at 34 mg (50%) by Soxhlet extraction (chloroform).

Evaluation Method for Photoelectric Conversion Element A 0.055027 mm square metal mask is attached to the photoelectric conversion element, a solar simulator (CEP2000, AM1.5G filter, radiation intensity 100 mW / cm ² , manufactured by Spectrometer) is used as an irradiation light source, and a source meter ( The current-voltage characteristics between the ITO electrode and the aluminum electrode were measured by Keisley (Model 2400). From this measurement result, open circuit voltage Voc (V), short circuit current density Jsc (mA / cm ² ), fill factor FF, and photoelectric conversion efficiency PCE (%) were calculated.

Here, the open circuit voltage Voc is a voltage value at a current value = 0 (mA / cm ² ), and the short circuit current density Jsc is a current density at a voltage value = 0 (V). The curve factor FF is a factor representing the internal resistance, and is represented by the following expression when the maximum output is Pmax.
FF = Pmax / (Voc × Jsc)
Further, the photoelectric conversion efficiency PCE is given by the following equation when the incident energy is Pin.
PCE = (Pmax / Pin) × 100
= (Voc x Jsc x FF / Pin) x 100

Example 1

Preparation of mixed solution of p-type semiconductor compound and n-type semiconductor compound As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-EH-IMTH (Synthesis Example 28) was used.
PCBM (C61) (phenyl C61 butyric acid methyl ester, manufactured by Frontier Carbon Corporation, NS-E100H) as an n-type semiconductor compound, p-type semiconductor compound: n-type semiconductor compound in a mass ratio of 1: 2, (total concentration 2.4 mass) %) And 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene. This solution was stirred and mixed for 2 hours or more at a temperature of 100 ° C. on a hot stirrer. The solution after stirring and mixing was filtered through a 0.45 μm filter to obtain a mixed solution of a p-type semiconductor compound and an n-type semiconductor compound.

Production of photoelectric conversion element A glass substrate (manufactured by Geomatic) with a patterned indium tin oxide (ITO) transparent conductive film (anode) was ultrasonically cleaned with acetone, then ultrasonically cleaned with ethanol, and then dried with nitrogen blow. It was.

  After the UV-ozone treatment, a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion used as a hole transport layer was applied with a spin coater (5000 rpm for 60 seconds) ) And annealed at 200 ° C. for 10 minutes.

  It was carried into a glove box, a mixed solution of p-type semiconductor compound / n-type semiconductor compound was spin-coated in an inert gas atmosphere, and annealing treatment or vacuum drying was performed on a hot plate.

  In the air, a film in which tetraisopropyl orthotitanate in ethanol (about 0.3 v%) was spin-coated and converted into titanium oxide by moisture in the atmosphere was created. Then, aluminum which is an electrode was vapor-deposited to make a device. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 2

As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-O-IMTH (Synthesis Example 29) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 3

A high molecular compound having a structure of P-THDT-DBTH-DMO-IMTH (Synthesis Example 30) was used as the p-type semiconductor compound.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 4

As the p-type semiconductor compound, a polymer compound having the structure of P-THDT-DBTH-H-IMTH (Synthesis Example 31) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 5

As the p-type semiconductor compound, a polymer compound having a structure of P-TEHT-DBTH-HD-IMTH (Synthesis Example 32) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 6

As the p-type semiconductor compound, a polymer compound having a structure of P-TEHT-DBTH-ODD-IMTH (Synthesis Example 33) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 7

As the p-type semiconductor compound, a polymer compound having a structure of P-TEHT-DBTH-TD-IMTH (Synthesis Example 34) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 8

As the p-type semiconductor compound, a polymer compound having a structure of P-TBOT-DBTH-DMO-IMTH (Synthesis Example 35) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 9

As the p-type semiconductor compound, a polymer compound having a structure of P-TBOT-DBTH-HD-IMTH (Synthesis Example 36) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 10

As the p-type semiconductor compound, a polymer compound having a structure of P-TTDT-DBTH-B-IMTH (Synthesis Example 37) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 11

As the p-type semiconductor compound, a polymer compound having a structure of P-TDMOT-DBTH-TDZ (Synthesis Example 38) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 12

As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-FFTDZ (Synthesis Example 39) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 13

As the p-type semiconductor compound, a polymer compound having a structure of P-THTDT-DBTH-FFTDZ (Synthesis Example 40) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 14

As the p-type semiconductor compound, a polymer compound having a structure of P-TTDT-DBTH-FTDZ (Synthesis Example 41) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 15

As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-OO-TDZ (Synthesis Example 42) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 16

As the p-type semiconductor compound, a polymer compound having a structure of P-TTDT-DBTH-NTDZ (Synthesis Example 43) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 17

As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-DMO-DPP (Synthesis Example 44) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in orthodichlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 18

As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-OFTT (Synthesis Example 45) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 19

As the p-type semiconductor compound, a polymer compound having the structure of P-THHDT-DBTH-HTT (Synthesis Example 46) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 2 (total concentration 2.4 mass%), and 1,8-diiodooctane (0.03 mL). / ML) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution. Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 20

As the p-type semiconductor compound, a polymer compound having the structure of P-THHDT-DBTH-EH-BDT (Synthesis Example 47) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound in a mass ratio of 1: 2 (total concentration of 3.0% by mass) and 1,8-diiodooctane (0.03 mL) / ML) was dissolved in orthodichlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution.
Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 21

As the p-type semiconductor compound, a polymer compound having a structure of P-THTIPSTH-DBTH-O-IMTH (Synthesis Example 48) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound has a mass ratio of 1: 1.5 (total concentration 2.0 mass%), and 1,8-diiodooctane (0 .03 mL / mL) was dissolved in chlorobenzene and passed through a 0.45 μm filter to obtain a mixed solution.
Using the obtained mixed solution, a device was produced in the same manner as in Example 1. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

Example 22

Preparation of mixed solution of p-type semiconductor compound and n-type semiconductor compound As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-EH-IMTH (Synthesis Example 28) was used.
Using PCBM (C61) as an n-type semiconductor compound, a p-type semiconductor compound: n-type semiconductor compound = 1: 1.5 (mass), dissolved in chlorobenzene at a total concentration of 2.0 mass%, a 0.45 μm filter To obtain a mixed solution of a p-type semiconductor compound and an n-type semiconductor compound.

Production of photoelectric conversion element A glass substrate (manufactured by Geomatek Co., Ltd.) patterned with indium tin oxide (ITO) transparent conductive film (cathode) was ultrasonically cleaned with acetone, then ultrasonically cleaned with ethanol, and then dried with nitrogen blow. It was.

  After the UV-ozone treatment, PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) used as a hole transport layer was applied with a spin coater (5000 rpm for 60 seconds). Annealed at 200 ° C. for 10 minutes.

  The mixture was carried into a glove box, and a mixed solution of a p-type semiconductor compound and an n-type semiconductor compound was spin-coated in an inert gas atmosphere and dried under reduced pressure.

  Lithium fluoride as an electron transfer layer was vapor-deposited with a vapor deposition machine, and then aluminum as an electrode was vapor-deposited to obtain a device. The obtained device evaluated the said photoelectric conversion element. The results are shown in Table 1.

  As described above, the photoelectric conversion element manufactured using the polymer compound used in the present invention can obtain both a high open-circuit voltage (Voc) and a short-circuit current density (Jsc), thereby obtaining a high photoelectric conversion efficiency η. It is possible. Moreover, according to the production method of the present invention, various substituents can be introduced as substituents, and the characteristics (crystallinity, film-forming property, absorption wavelength) of the material can be controlled.

(VII) Photoelectric conversion element (VI) Cathode (V) Electron transport layer
(IV) Active layer (III) Hole transport layer (II) Anode (I) Base material

Claims (11)

A photoelectric conversion element having a structure in which a base material, an anode, an active layer, and a cathode are arranged in this order, wherein the active layer has a benzobisthiazole structural unit represented by formula (1) A photoelectric conversion element comprising a molecular compound.

[In Formula (1),
T ¹ and T ² are each independently a thiophene ring which may be substituted with an alkoxy group, a thioalkoxy group, a hydrocarbon group or an organosilyl group, a thiazole which may be substituted with a hydrocarbon group or an organosilyl group A ring, or a phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, or a trifluoromethyl group is represented.
B ¹ and B ² represent a thiophene ring that may be substituted with a hydrocarbon group, a thiazole ring that may be substituted with a hydrocarbon group, or an ethynylene group. ] ^{2. The} photoelectric conversion element according to claim 1, wherein T ¹ and T ² of the polymer compound are groups represented by any of the following formulas (t1) to (t5), respectively.

Wherein (t1) ~ (t5), R 13 ~R 14 each independently represent a hydrocarbon group having 6 to 30 carbon atoms. R ¹⁵ to R ¹⁶ are each independently a hydrocarbon group having 6 to 30 carbon atoms, ^{or,, * - Si (R 18} ) a group represented by _3. R ^{15 ′} represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by * —Si (R ¹⁸ ) ₃ . R ¹⁷ represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, * —O—R ¹⁹ , * —S—R ²⁰ , * —Si (R ¹⁸ ) ₃ , or * —CF ₃ . R ¹⁸ each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a plurality of R ¹⁸ may be the same or different. R ^{19 to} R ²⁰ represent a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond bonded to the thiazole ring of benzobisthiazole. ] The photoelectric conversion element according to claim ¹ , wherein B ¹ and B ² are groups represented by any of the following formulas (b1) to (b3), respectively.

[In the formulas (b1) to (b3), R ²¹ , R ²² and R ^{21 ′} represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. * Represents a bond, and in particular, * on the left side represents a bond bonded to the benzene ring of the benzobisthiazole compound. ]   The photoelectric conversion element according to claim 1, wherein the polymer compound is a donor-acceptor type semiconductor polymer.   The photoelectric conversion element according to claim 1, further comprising an n-type organic semiconductor compound in the active layer.   The photoelectric conversion element according to claim 5, wherein the n-type organic semiconductor compound is fullerene or a derivative thereof.   The photoelectric conversion device according to claim 1, further comprising a hole transport layer between the anode and the active layer.   The photoelectric conversion element according to claim 1, further comprising an electron transport layer between the cathode and the active layer.   The photoelectric conversion element according to claim 1, wherein the anode is a transparent electrode.   The photoelectric conversion element according to claim 1, wherein the cathode is a metal electrode.   An organic thin film solar cell comprising the photoelectric conversion element according to claim 1.