TWI665232B - Photoelectric conversion element and organic semiconductor compound used in the photoelectric conversion element - Google Patents

Abstract

The present invention provides a photoelectric conversion element that exhibits a high open circuit voltage by using a polymer compound capable of introducing a variety of skeletons and substituents. The photoelectric conversion element has a structure in which a substrate, an anode, an active layer, and a cathode are sequentially arranged, and the active layer contains a polymer compound having a benzobisthiazole structural unit represented by formula (1).

In the formula (1), T ¹ and T ² each independently represent an alkoxy group, a thioalkoxy group, a thiophene ring which may be substituted with a hydrocarbon group or an organosiliconyl group, a thiazole ring which may be substituted with a hydrocarbon group or an organosiliconyl group, or A phenyl group which may be substituted by a hydrocarbon group, an alkoxy group, a thioalkoxy group, a silicone group, a halogen atom or a trifluoromethyl group; and B ¹ and B ² represent a thiophene ring which may be substituted by a hydrocarbon group, and may be substituted by a hydrocarbon group Thiazolyl ring, or ethynyl.

Description

Photoelectric conversion element and organic semiconductor compound used in the photoelectric conversion element

The invention relates to a photoelectric conversion element, which has a structure in which a substrate, an anode, an active layer, and a cathode are sequentially arranged, and contains a polymer compound having a specific benzobisthiazole structural unit.

Organic semiconductor compounds are one of the most important materials in the field of organic electronics, and can be classified into p-type organic semiconductor compounds that have electron-emitting properties and n-type organic semiconductor compounds that have electron-withdrawing properties. By appropriately combining a p-type organic semiconductor compound and an n-type organic semiconductor compound, various elements can be manufactured, and such elements are used, for example, by the action of an exciton formed by the recombination of electrons and holes. Luminous organic electroluminescence, or organic thin-film solar cells that convert light into electricity, and organic thin-film transistors that control the amount of current or voltage.

Among them, organic thin-film solar cells are effective for environmental protection because they do not release carbon dioxide into the atmosphere, and they have a simple structure and are easy to manufacture, so demand is high. However, the photoelectric conversion efficiency of organic thin film solar cells is not sufficient. Photoelectric conversion efficiency η uses the product of short circuit current density (Jsc), open circuit voltage (Voc), and fill factor (FF) "η = open circuit The voltage (Voc) × short-circuit current density (Jsc) × fill factor (FF) ”is calculated. In order to improve the photoelectric conversion efficiency, in addition to increasing the open-circuit voltage (Voc), the short-circuit current density (Jsc) Factor (FF).

Open circuit voltage (Voc) and HOMO (Highest Occupied Molecular Orbital) energy level of p-type organic semiconductor compounds and LUMO (Lowest Unoccupied Molecular Orbital energy level) of n-type organic semiconductor compounds The energy difference is directly proportional. Therefore, in order to increase the open circuit voltage (Voc), the HOMO level of the p-type organic semiconductor needs to be deepened (reduced).

In addition, the short-circuit current density (Jsc) is related to the amount of energy received by the organic semiconductor compound. In order to increase the short-circuit current density (Jsc) of the organic semiconductor compound, it is necessary to absorb light in a wide wavelength range from the visible region to the near-infrared region. Among the light that the organic semiconductor compound can absorb, the wavelength of the light with the lowest energy (the longest wavelength) is the absorption end wavelength, and the energy corresponding to this wavelength corresponds to the energy of the energy gap. Therefore, in order to absorb light in a wider wavelength range, it is necessary to make the energy gap (the energy difference between the HOMO level and the LUMO level of a p-type semiconductor) small.

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

[Prior technical literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2007-238530.

An object of the present invention is to provide a photoelectric conversion element exhibiting a high open circuit voltage. In addition, since the capability of a photoelectric conversion element depends on the type and combination of organic semiconductor compounds, and the HOMO in the organic semiconductor compound is closely related to the open circuit voltage, the object of the present invention is to provide a method for introducing more types of skeletons and substituents. Photoelectric conversion element of polymer compound.

In order to improve the conversion efficiency, that is, increase the open circuit voltage (Voc) and increase the short-circuit current density (Jsc), the inventors found that it is effective to moderately deepen the HOMO level while absorbing p-type organic semiconductors in a wide wavelength range. Furthermore, research was conducted focusing on the relationship between the conversion efficiency and the chemical structure of the p-type organic semiconductor compound, and it was found that by using an organic semiconductor polymer having a specific structure, a wide range of light absorption can be achieved in the visible light region as a whole. Since the HOMO level and LUMO level are adjusted to appropriate ranges, the open circuit voltage (Voc) and the short circuit current density (Jsc) can be increased. Further, it was found that if such an organic semiconductor polymer is used, it is easy to cause charge separation between the p-type organic semiconductor and the n-type organic semiconductor, and the present invention has been completed.

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 sequentially arranged, and the active layer contains a specific benzobisthiazole skeleton represented by formula (1). A polymer compound of a structural unit (hereinafter may be referred to as a "polymer compound (1)").

[In formula (1), T ¹ and T ² each independently represent an alkoxy group, a thioalkoxy group, a thiophene ring which may be substituted with a hydrocarbon group or an organosiliconyl group, a thiazole ring which may be substituted with a hydrocarbon group or an organosiliconyl group, Or a phenyl group which may be substituted by a hydrocarbyl group, an alkoxy group, a thioalkoxy group, a silicone group, a halogen atom or a trifluoromethyl group; and B ¹ and B ² represent a thiophene ring which may be substituted by a hydrocarbon group, Substituted thiazole ring, or ethynyl]

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

[Chemical Formula 2]

[In the formulae (t1) to (t5), R ¹³ to R ¹⁴ each independently represent a hydrocarbon group having 6 to 30 carbon atoms; R ¹⁵ to R ¹⁶ each independently represent a hydrocarbon group having 6 to 30 carbon atoms or * -Si (R group ¹⁸⁾ ₃ represented by the; R ^{15 'represents} a hydrogen atom, hydrocarbon group having 6 to ^{30's, * - Si (R 18)} 3 represented by the group; R ¹⁷ represents a halogen atom, a C1-2 hydrocarbon group having 6 to 30, the * -OR ¹⁹ , * -SR ²⁰ , * -Si (R ¹⁸ ) ₃ or * -CF ₃ ; R ¹⁸ 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 bonding bond to a thiazole ring bonded to benzobisthiazole]

Further, in the formula (1), B ¹ and B ² are each preferably a base represented by any one of the following formulae (b1) to (b3).

[In the formulae (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 bonding bond, and in particular, * on the left side represents a bond to a benzo Bond of benzene ring of bisthiazole compound]

The polymer compound (1) contained in the photoelectric conversion element of the present invention is preferably an acceptor-acceptor 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. In addition, 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 utilizing the intramolecular SN interaction. As a result, since the π conjugate is expanded in the planar cross-shaped skeleton, it shows multi-band light absorption due to a complex π-π ^* transition, and can absorb a wide range of light from the visible region to the near-infrared region. Thereby, both a high open circuit voltage (Voc) and a short circuit current density (Jsc) can be obtained, and a high photoelectric conversion efficiency η can be obtained. In addition, various substituents can be introduced as substituents in the benzobisthiazole skeleton constituting the polymer compound (1) used in the present invention, so that the characteristics (crystallinity) of materials that have various effects on the characteristics of the photoelectric conversion element can be controlled. , Film formation, absorption wavelength).

(VII) ‧‧‧Photoelectric conversion element

(VI) ‧‧‧ cathode

(V) ‧‧‧Electronic transmission layer

(IV) ‧‧‧active layer

(III) ‧‧‧hole transmission layer

(II) ‧‧‧Anode

(I) ‧‧‧ Substrate

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

Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.

Photoelectric conversion element

The photoelectric conversion element of the present invention has a structure in which a substrate, an anode, an active layer, and a cathode are sequentially arranged, and the active layer contains a polymer compound having a benzobisthiazole structural unit represented by formula (1).

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

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 sequentially arranged. The photoelectric conversion element (VII) preferably further includes a buffer layer (hole transport layer) (III) and a buffer layer (electron transport layer) (V). That is, the photoelectric conversion element (VII) preferably has a substrate (I), an anode (II), a buffer layer (hole transport layer) (III), an active layer (IV), and a buffer layer (electron transmission) arranged in this order. Layer) (V) and cathode (VI) structure. However, the photoelectric conversion element of the present invention may not include the hole transport layer (III) and the electron transport layer (V). These sections will be described below.

1.1 Active layer (IV)

The active layer (IV) refers to a layer that performs photoelectric conversion, and usually includes a single or plural p-type semiconductor compound and a single or plural n-type semiconductor compound. Specific examples of the p-type semiconductor compound include a polymer compound (1) and an organic semiconductor compound (11) described later, but they are not limited thereto. In the present invention, it is necessary to use at least the polymer compound (1) as the p-type semiconductor compound. After the photoelectric conversion element (VII) receives light, the light is absorbed by the active layer (IV), and electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is removed from the anode (II) and the cathode (VI) extract. In the present invention, the polymer compound (1) is used as a p-type semiconductor compound.

The film thickness of the active layer (IV) is preferably 70 nm or more, more preferably 90 nm or more, and also 100 nm or more, and preferably 1000 nm or less, more It is preferably at most 750 nm, more preferably at most 500 nm.

If the film thickness of the active layer (IV) is moderately thick, the conversion efficiency of the photoelectric conversion element (VII) can be expected to be improved. Further, if the film thickness of the active layer (IV) is moderately thick, it is also preferable in terms of preventing punch-through short circuits in the film. If the thickness of the active layer (IV) is moderately thin, the internal resistance will be small, and the distance between the electrode (II) and the electrode (VI) will not be too far, and the diffusion of the charge will be good, so it is preferable. In addition, if the film thickness of the active layer (IV) is within the above range, it is preferable in terms of improving the reproducibility in the process of producing the active layer (IV).

Generally speaking, the thicker the active layer, the greater the distance traveled by the charges generated in the active layer to the electrode, or the electron transport layer or hole transport layer, which will hinder the transfer of charge to the electrode. As described above, when the active layer (IV) is thicker, although the area where light can be absorbed increases, it is difficult to transfer the electric charges generated by light absorption, so the photoelectric conversion efficiency decreases. Therefore, in terms of securing the voltage and improving the conversion efficiency, it is also preferable to set the film thickness of the active layer (IV) to the above range.

1.1.1 Layer structure of the active layer

Examples of the layer structure of the active layer (IV) include a thin film laminated type in which a p-type semiconductor compound and an n-type semiconductor compound are laminated, or a block heterojunction having a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed. Type and so on. Among them, in terms of the photoelectric conversion efficiency that can be further improved, a bulk heterojunction (Bulk Heterojunction) type is preferred Active layer.

Active layer with heterogeneous interface of bulk material

The bulk heterojunction type active layer has a layer (i-layer) formed by mixing a p-type semiconductor compound and an n-type semiconductor compound. 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 transmitted to the electrode.

Among the p-type semiconductor compounds contained in the i-layer, the polymer compound (1) having the benzobisthiazole structural unit represented by the formula (1) (preferably the benzobisthiazole structural unit represented by the formula (1) The ratio with the polymer compound (1-1) formed by the copolymerization component (2) described later is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass of the p-type semiconductor compound. Above mass%. Since the polymer compound (1) has properties suitable as a p-type semiconductor compound, it is particularly preferred that the polymer compound (1) is included only in the p-type semiconductor compound.

Regarding 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), from the viewpoint of improving the photoelectric conversion efficiency by obtaining a good phase separation structure, It is preferably 0.5 or more, more preferably 1 or more, and preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less.

The i-layer may be any one of a coating method and a vapor deposition method (for example, a co-evaporation method). It is preferably formed by any method, and if the coating method is used, the i-layer can be formed more easily. Since the polymer compound (1) of the present invention has solubility in a solvent, it is preferable in terms of excellent coating film forming properties. When the i-layer is produced by a coating method, a coating liquid containing a p-type semiconductor compound and an n-type semiconductor compound may be prepared, and the coating liquid may be applied. A coating solution containing a p-type semiconductor compound and an n-type semiconductor compound can be prepared by mixing a solution containing a p-type semiconductor compound and a solution containing an n-type semiconductor compound and mixing them, or dissolving the p-type semiconductor compound in a solvent described later and n-type semiconductor compound.

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 with respect to the entire coating solution in terms of forming an active layer having a sufficient film thickness. From the viewpoint that the semiconductor compound is sufficiently dissolved, it is preferably 4.0% by mass or less with respect to the entire coating liquid.

Examples of the coating method include a spin coating method, an inkjet method, a doctor blade method, a drip casting method, a reverse roll coating method, a gravure coating method, a contact coating method, a roller brush coating method, a spray coating method, and an air coating method. A knife coating method, a wire rod coating method, a tubular blade coating method, an impregnation coating method or a curtain coating method, a flexible board coating method, and the like. After the application of the coating liquid, drying may be performed by heating or the like.

As a solvent of the coating liquid, it is preferable that the p-type semiconductor compound and the n-type semiconductor compound can be uniformly dissolved, and examples thereof include hexane, heptane, Aliphatic hydrocarbons such as octane, isooctane, nonane or decane; aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, chlorobenzene or o-dichlorobenzene; cyclopentane, cyclohexane Alicyclic hydrocarbons such as alkane, methylcyclohexane, cycloheptane, cyclooctane, tetrahydronaphthalene or decalin; lower alcohols such as methanol, ethanol or propanol, anisole; acetone, methyl ethyl Aliphatic ketones such as methyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone or cyclohexanone; aromatic ketones such as acetophenone or phenylacetone; ethyl acetate, isopropyl acetate , Esters such as butyl acetate or methyl lactate; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, trichloroethane, or trichloroethylene; ether, tetrahydrofuran, cyclopentyl methyl ether, dibutyl Ethers such as ether, diphenyl ether or dioxane; or dimethylformamide, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolinone (1,3-dimethyl-2-imidazolidinone, DMI) or amines such as dimethylacetamide.

Among them, aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, chlorobenzene or o-dichlorobenzene are preferred; cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclo Alicyclic hydrocarbons such as octane, tetrahydronaphthalene or decalin; ketones such as acetone, methyl ethyl ketone, cyclopentanone or cyclohexanone; or ethers such as diethyl ether, tetrahydrofuran or dioxane.

When an active layer of a bulk heterojunction type is formed by a coating method, an additive may be further added to a coating liquid containing a p-type semiconductor compound and an n-type semiconductor compound. The phase separation structure of the p-type semiconductor compound and the n-type semiconductor compound in the active layer of the bulk heterojunction type will absorb light. The influence of the ionization, the diffusion of the exciton, the departure of the exciton (carrier separation), and the carrier transmission affects the photoelectric conversion efficiency by optimizing the phase separation structure. By containing an additive having a high affinity with the p-type semiconductor compound or the n-type semiconductor compound in the coating solution, an active layer having a better phase separation structure can be obtained, so that the photoelectric conversion efficiency can be improved.

In view of the fact that the additive does not easily disappear from the active layer (IV), the additive is preferably a solid or a high boiling point.

Specifically, when the additive is a solid, the melting point (atmospheric pressure) of the additive is usually 35 ° C or higher, preferably 50 ° C or higher, more preferably 80 ° C or higher, even more preferably 150 ° C or higher, particularly preferably 200 ° C. Above, and preferably 400 ° C or lower, more preferably 350 ° C or lower, even more preferably 300 ° C or lower.

When the additive is a liquid, its boiling point (atmospheric pressure) is 80 ° C or higher, more preferably 100 ° C or higher, particularly 150 ° C or higher, and preferably 300 ° C or lower, more preferably 250 ° C or lower, and even more preferably 200 ° C or lower. the following.

As examples of the additive, if it is a solid, an aliphatic hydrocarbon compound having a carbon number of 10 or more and 20 or less and an aromatic compound having a carbon number of 10 or more and 20 or less may be mentioned. Carbon is preferred. An aromatic compound having a number of 10 or more and 20 or less. Specific examples include naphthalene compounds, and particularly preferred is the conversion of one to eight substituents on the naphthalene 组合。 The compound. Examples of the substituent bonded to naphthalene include a halogen atom, a hydroxyl group, a cyano group, an amine group, amidino group, a carbonyloxy group, a carboxy group, a carbonyl group, an oxycarbonyl group, a silicon group, Alkenyl, alkynyl, alkoxy, aryloxy, alkylthio, arylthio or aromatic.

When the additive is a liquid, an aliphatic hydrocarbon compound having a carbon number of 8 to 9 or less and an aromatic compound having a carbon number of 8 to 9 or less may be mentioned. Specific examples include dihalogenated hydrocarbon compounds, and particularly preferred are compounds in which one or more substituents are bonded to octane. Examples of the substituent bonded to octane include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, an amine group, a carbamoyl group, a carbonyloxy group, a carboxyl group, a carbonyl group, or an aromatic group. Preferred are fluorine and chlorine , Bromine, iodine and other halogen atoms. As another example of the additive, a benzene compound having 4 to 6 halogen atoms bonded thereto may be mentioned.

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

1.1.2 p-type semiconductor compounds

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

Polymer Compound (1)

The polymer compound (hereinafter referred to as "polymer compound (1)") used in the photoelectric conversion element of the present invention is one of p-type semiconductor compounds and has a benzobisthiazole structure represented by formula (1) Unit (hereinafter may be referred to as a "structural unit represented by formula (1)").

[In formula (1), T ¹ and T ² each independently represent an alkoxy group, a thioalkoxy group, a thiophene ring which may be substituted with a hydrocarbon group or an organosiliconyl group, a thiazole ring which may be substituted with a hydrocarbon group or an organosiliconyl group, Or a phenyl group which may be substituted by a hydrocarbyl group, an alkoxy group, a thioalkoxy group, a silicone group, a halogen atom or a trifluoromethyl group; and B ¹ and B ² represent a thiophene ring which may be substituted by a hydrocarbon group, Substituted thiazole ring, or ethynyl]

Since the polymer compound used in the present invention has the benzobisthiazole structural unit represented by the formula (1), it can deepen the HOMO energy level and reduce the energy gap, which is beneficial for improving the photoelectric conversion efficiency. Polymer Compound (1) The donor-acceptor type semiconductor polymer obtained by copolymerizing a structural unit represented by the formula (1) and a copolymerization component (2) described later is preferable. Donor-receptor semiconductor polymer refers to a high molecular compound in which the donor unit and the acceptor unit are alternately arranged. Donor unit refers to the structural unit of electron pushing, and acceptor unit refers to the structural unit of electron withdrawing. The donor-acceptor semiconductor polymer is preferably a polymer compound in which a structural unit represented by formula (1) and a copolymerization component (2) described later are alternately arranged. With such a structure, it can be suitably used as a p-type semiconductor compound.

In addition, in the present specification, the organosiliconyl group means a monovalent group substituted with one or more hydrocarbon groups on the Si atom, and the number of the hydrocarbon groups substituted on the Si atom is preferably 2 or more and 3 or less, more preferably 3 Each.

In the benzobisthiazole structural unit represented by the formula (1), T ¹ and T ² may be the same as or different from each other, but are preferably the same from the viewpoint of easy production.

In the benzobisthiazole structural unit represented by formula (1), T ¹ and T ² are each preferably a group represented by the following formulae (t1) to (t5). Specifically, the alkoxy group as T ¹ and T ² is preferably a group represented by the following formula (t1), the thioalkoxy group is preferably a group represented by the following formula (t2), and The thiophene ring substituted with a hydrocarbon group or an organosiliconyl group is preferably a group represented by the following formula (t3), and the thiazole ring which may be substituted with a hydrocarbon group or an organosiliconyl group is preferably a group represented by the following formula (t4) The phenyl group which may be substituted with a hydrocarbon group, an alkoxy group, a thioalkoxy group, a silicone group, a halogen atom or a trifluoromethyl group is preferably a group represented by the following formula (t5). If T ¹ and T ² are the bases represented by the following formulae (t1) to (t5), short-wavelength light can be absorbed and high planarity can be obtained. Therefore, π-π stacking can be formed efficiently. Further improve the photoelectric conversion efficiency.

[In the formulae (t1) to (t5), R ¹³ to R ¹⁴ each independently represent a hydrocarbon group having 6 to 30 carbon atoms; R ¹⁵ to R ¹⁶ each independently represent a hydrocarbon group having 6 to 30 carbon atoms or * -Si (R group ¹⁸⁾ ₃ represented by the; R ^{15 'represents} a hydrogen atom, hydrocarbon group having 6 to ^{30's, * - Si (R 18)} 3 represented by the group; R ¹⁷ represents a halogen atom, a C1-2 hydrocarbon group having 6 to 30, the * -OR ¹⁹ , * -SR ²⁰ , * -Si (R ¹⁸ ) ₃ or * -CF ₃ ; R ¹⁸ 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 bonding bond to a thiazole ring bonded to benzobisthiazole]

In the above formulae (t1) to (t5), 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 branched hydrocarbon group is preferable, and a branched chain is more preferable. Saturated hydrocarbyl. ^Since the hydrocarbon groups of R ¹³ to R ¹⁷ , R ¹⁹ to R ²⁰ , and R ^{15 ′} have branches, the solubility in an organic solvent can be improved, and the polymer compound of the present invention can obtain moderate crystallinity. The larger the carbon number of the hydrocarbon groups of R ¹³ to R ¹⁷ , R ¹⁹ to R ²⁰ , and R ^{15 ′} , the higher the solubility in the organic solvent, but if it becomes too large, the reactivity of the coupling reaction described below will decrease, Therefore, the synthesis of polymer compounds becomes difficult. Therefore, the carbon number of the hydrocarbon group of R ¹³ to R ¹⁷ , R ¹⁹ to R ²⁰ , and R ^{15 ′} is preferably 8 to 25, more preferably 8 to 20, and even more preferably 8 to 16.

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 C ₆ alkyl groups such as n-hexyl; C ₇ alkyl groups such as n-heptyl; n-octyl Base, 1-n-butylbutyl, 1-n-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-methylheptyl, 2 -C ₈ alkyl such as methylheptyl, 6-methylheptyl, 2,4,4-trimethylpentyl, 2,5-dimethylhexyl; n-nonyl, 1-n-propylhexyl, 2-n-propylhexyl, 1-ethylheptyl, 2-ethylheptyl, 1-methyloctyl, 2-methyloctyl, 6-methyloctyl, 2,3,3,4- C ₉ alkyl such as tetramethylpentyl, 3,5,5-trimethylhexyl; n-decyl, 1-n-pentylpentyl, 1-n-butylhexyl, 2-n-butylhexyl, 1- C ₁₀ alkyl groups such as n-propylheptyl, 1-ethyloctyl, 2-ethyloctyl, 1-methylnonyl, 2-methylnonyl, 3,7-dimethyloctyl; n Undecyl, 1-n-butylheptyl, 2-n-butylheptyl, 1-n-propyloctyl, 2-n-propyloctyl, 1-ethylnonyl, 2-ethylnonyl and other C ₁₁ alkanes N-dodecyl, 1-n-pentylheptyl, 2-n-pentylheptyl, 1-n-butyloctyl, 2-n-butyloctyl , 1-n-propyl-nonyl, n-propyl-nonyl group C ₁₂ alkyl group; n-tridecyl, 1-n-octyl-pentyl, 2-pentyl n-octyl, 1-n-butyl-nonyl group, C ₁₃ alkyl such as 2-n-butylnonyl, 1-methyldodecyl, 2-methyldodecyl; n-tetradecyl, 1-n-heptylheptyl, 1-n-hexyl octyl, C ₁₄ alkyl such as 2-n-hexyloctyl, 1-n-pentylnonyl, 2-n-pentylnonyl; n-pentadecyl, 1-n-heptyloctyl, 1-n-hexylnonyl, - n-nonyl and the like C ₁₅ alkyl group; n-hexadecyl, 2-n-hexyl-decyl, 1-n-octyl-octyl, 1-n-heptyl-nonyl, 2-nonyl, n-heptyl and the like C ₁₆ Alkyl; C ₁₇ alkyl such as n-heptadecyl, 1-n-octyl nonyl; C ₁₈ alkyl such as n-octadecyl, 1-n-nonyl nonyl; C ₁₉ alkyl such as n-nonadecyl; C ₂₀ alkyl groups such as n-icosyl, 2-n-octyldodecyl; C ₂₁ alkyl groups such as n-doctanyl; C ₂₂ alkyl groups such as n-doctadecyl; n-coscosane Radicals such as C ₂₃ alkyl; C ₂₄ alkyls such as n-tetracosyl, 2-n-decyl tetradecyl and the like. C ₈ to C ₂₈ alkyl is preferred, C ₈ to C ₂₆ alkyl is more preferred, C ₈ to C ₂₆ branched alkyl is more preferred, and C ₈ to C ₂₄ branched alkyl is further more preferred. base. Especially preferred are 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl, 2-n-hexyldecyl, 2-n-octyldodecyl, 2-n-decyldeca Tetraalkyl. When R ¹³ to R ¹⁷ , R ¹⁹ to R ²⁰ , and R ^{15 ′} are the above-mentioned groups, the solubility of the polymer compound of the present invention in an organic solvent is improved, and it has moderate crystallinity.

Of the groups represented by * -Si (R ¹⁸ ) ₃ of R ¹⁵ to R ¹⁷ and R ^{15 ′} in the above formulae (t1) to (t5), the carbon number of the aliphatic hydrocarbon group of R ¹⁸ is preferably 1 to 18 , More preferably 1 ~ 8. Examples of the aliphatic hydrocarbon group of R ¹⁸ include alkyl groups such as methyl, ethyl, isopropyl, third butyl, isobutyl, octyl, and octadecyl. The carbon number of the aromatic hydrocarbon group of R ¹⁸ is preferably 6 to 8, more preferably 6 to 7, and even more preferably 6. Examples of the aromatic hydrocarbon group of R ¹⁸ include a phenyl group. Among them, as R ¹⁸ , an aliphatic hydrocarbon group is preferred, a branched aliphatic hydrocarbon group is more preferred, and an isopropyl group is particularly preferred. 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 groups represented by * -Si (R ¹⁸ ) ₃ , the solubility of the polymer compound of the present invention in an organic solvent is improved.

In the formulae (t1) to (t5), as the group represented by * -Si (R ¹⁸ ) ₃ of R ¹⁵ to R ¹⁷ and R ^{15 ′} , specifically, trimethylsilyl, triethyl Dimethylsilyl, isopropyldimethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, triethylsilyl, triisobutylsilyl, tripropylsilyl Alkylsilyl such as triphenylsilyl, tributylsilyl, dimethylphenylsilyl, methyldiphenylsilyl; arylsilyl such as triphenylsilyl, third butylchlorodiphenylsilyl Wait. Among them, alkylsilyl is preferred, and trimethylsilyl and triisopropylsilyl are particularly preferred.

When R ¹⁷ is a halogen atom in the formula (t5), 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 or a group that is the same as the hydrocarbon group having 6 to 30 carbon atoms or a group represented by * -Si (R ¹⁸ ) ₃ as R ¹⁵ and is preferably a hydrogen atom.

As the electron-withdrawing radicals of T ¹ and T ² , from the viewpoint that the overall flatness of the structural unit represented by the formula (1) is excellent, it is more preferably represented by the formulas (t1), (t3), and (t5). The base is more preferably a base represented by the formula (t3), and particularly preferably a base represented by the following formulae (t3-1) to (t3-16). In the formula, * represents a bonding bond.

As T ¹ and T ² , an electron-injecting or electron-extracting base can be used. Examples of the electron inferiority base include the bases represented by the formulae (t1) to (t3).

[In the formulae (t1) to (t3), * represents a bonding bond, R ¹³ to R ¹⁵ and R ^{15 '} represent the same bases as described above; * represents a bonding bond]

Examples of the electron-withdrawing base that can be used for T ¹ and T ² include the bases represented by the formulae (t4) to (t5).

[In formulae (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, * -OR ¹⁹ , * -SR ²⁰ , * -Si (R ¹⁸ ) ₃ or * -CF ₃ ; * indicates a bonding key]

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

[In the formulae (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 bonding bond, and in particular, * on the left side represents a bond to a benzo Bond of benzene ring of bisthiazole compound]

As the hydrocarbon group having 6 to 30 carbon atoms for R ²¹ , R ²² and R ^{21 ′} , a hydrocarbon group having 6 to 30 carbon atoms for R ¹³ to R ¹⁷ , R ¹⁹ to R ²⁰ , and R ^{15 ′} can be preferably used. The base.

If R ²¹ , R ²² , and R ^{21 ′} are hydrogen atoms, it is easy to form an acceptor-acceptor semiconductor polymer, which is preferable. In addition, if R ²¹ , R ²² , and R ^{21 ′} are hydrocarbon groups having 6 to 30 carbon atoms, there is a possibility that the photoelectric conversion efficiency can be further improved, so it is preferable.

In addition, among the benzobisthiazole structural units represented by the formula (1), the entire planarity of the structural unit represented by the formula (1) is excellent, and the planarity of the entire polymer compound obtained is also excellent. In other words, B ¹ and B ^{2 are more} preferably the bases represented by the formulae (b1) and (b2). When B ¹ and B ² are groups represented by the formulae (b1) and (b2), an interaction between the S atom and the N atom is generated in the benzobisthiazole structural unit (1), and the planarity is further improved. As B ¹ and B ² , specifically, a base represented by the following formula is preferable. However, * in the formula represents a bonding bond, and * on the left side is assumed to be bonded to a benzene ring of benzobisthiazole.

[Chemical Formula 12]

Examples of the structural unit represented by the formula (1) include the structural units represented by the following formulae (1-1) to (1-48).

[Chemical Formula 15]

[Chemical Formula 18]

It is preferable to use the copolymerization component (2) (donor unit, acceptor unit) of the donor-acceptor type semiconductor polymer in combination with the structural unit represented by formula (1). As the copolymerization component (2), a conventionally known structural unit can be used. Specifically, the following structural units are mentioned. Among them, the structural units represented by the formulae (c1), (c3) to (c5), (c7), (c9), (c12), (c21), (c27), (c37), and (c42) are preferred .

[Chemical Formula 19]

[Chemical Formula 20]

[In the formulae (c1) to (c43), R ³⁰ to R ⁷³ and R ⁷⁵ to R ⁷⁶ each independently represent a hydrocarbon group having 4 to 30 carbon atoms, and R ⁷⁴ represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms; A ³⁰ And A ³¹ independently represent the same base as T ¹ and T ² , and j represents an integer of 1 to 4; set to a bonding bond of B ¹ or B ^{2 that} is bonded to the structural unit represented by formula (1) ]

Examples of the hydrocarbon group having 4 to 30 carbon atoms represented by R ³⁰ to R ⁷⁶ include: C ₄ alkyl groups such as n-butyl; C ₅ alkyl groups such as n-pentyl; C ₆ alkyl groups such as n-hexyl; n-heptyl And other C ₇ alkyl groups; n-octyl, 1-n-butylbutyl, 1-n-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, C ₈ alkyl such as 1-methylheptyl, 2-methylheptyl, 6-methylheptyl, 2,4,4-trimethylpentyl, 2,5-dimethylhexyl; n-nonyl , 1-n-propylhexyl, 2-n-propylhexyl, 1-ethylheptyl, 2-ethylheptyl, 1-methyloctyl, 2-methyloctyl, 6-methyloctyl, C ₉ alkyl such as 2,3,3,4-tetramethylpentyl, 3,5,5-trimethylhexyl; n-decyl, 1-n-pentylpentyl, 1-n-butylhexyl, 2 -N-butylhexyl, 1-n-propylheptyl, 1-ethyloctyl, 2-ethyloctyl, 1-methylnonyl, 2-methylnonyl, 3,7-dimethyloctyl C ₁₀ alkyl groups such as n-undecyl, 1-n-butylheptyl, 2-n-butylheptyl, 1-n-propyloctyl, 2-n-propyloctyl, 1-ethylnonyl, 2- ethylnonyl C ₁₁ alkyl group and the like; n-dodecyl, 1-n-pentyl-heptyl group, 2-n-pentyl-heptyl, 1-n-butyl Octyl, 2-n-butyl-octyl, 1-n-propyl-nonyl, n-propyl-nonyl group C ₁₂ alkyl group; n-tridecyl, 1-n-octyl-pentyl, 2-n-pentyl C ₁₃ alkyl such as octyl, 1-n-butylnonyl, 2-n-butylnonyl, 1-methyldodecyl, 2-methyldodecyl; n-tetradecyl, 1-n-heptyl C ₁₄ alkyl such as heptyl, 1-n-hexyloctyl, 2-n-hexyloctyl, 1-n-pentylnonyl, 2-n-pentylnonyl; n-pentadecyl, 1-n-heptyloctyl C ₁₅ alkyl groups such as n-yl, 1-n-hexyl nonyl, 2-n-hexyl nonyl; n-hexadecyl, 2-n-hexyl decyl, 1-n-octyl octyl, 1-n-heptyl nonyl, C ₁₆ alkyl such as 2-n-heptyl nonyl; C ₁₇ alkyl such as n-heptyl, 1-n-octyl nonyl; C ₁₈ alkyl such as n-octadecyl, 1-n-nonyl nonyl; n C ₁₉ alkyl such as undecyl; C ₂₀ alkyl such as n-eicosyl, 2-n-octyl dodecyl; C ₂₁ alkyl such as n-decyl; n-docosadecyl C ₂₂ alkyl groups; C ₂₃ alkyl groups such as n-tricosane; C ₂₄ alkyl groups such as n-tetracosyl and 2-n-decyl tetradecyl. C ₈ to C ₂₈ alkyl is preferred, C ₈ to C ₂₆ alkyl is more preferred, C ₈ to C ₂₆ branched alkyl is more preferred, and C ₈ to C ₂₄ branched alkyl is further more preferred. Is particularly preferably 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl, 2-n-hexyldecyl, 2-n-octyldodecyl, 2-n-decyl Tetradecyl. When R ³⁰ to R ⁷³ and R ⁷⁵ to R ⁷⁶ are the above-mentioned groups, and R ⁷⁴ is a hydrogen atom or the above-mentioned group, the solubility of the polymer compound of the present invention in an organic solvent is improved, and it has moderate crystallinity.

The bases represented by the formulae (c1) to (c30) are bases that function as acceptor units, and the bases represented by the formulas (c32) to (c43) are bases that function as donor units. The base represented by the formula (c31) may function as an acceptor unit or may function as an 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, and more preferably 15 mol% or more. It is more preferably 30 mol% or more, and 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 copolymerization 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 even more preferably 30 mol. Ear mole%, and usually 99 mole% or less, preferably 95 mole% or less, more preferably 85 mole% or more It is more preferably 70 mol% or less.

The arrangement state of the structural unit and the copolymerization component (2) represented by the formula (1) of the repeating unit in the polymer compound (1) of the present invention may be any of alternating, block, and random. That is, the polymer compound (1) of the present invention may be any of an alternating copolymer, a block copolymer, and a random copolymer. It is preferably arranged alternately.

In the polymer compound (1), each of the structural unit and the copolymerization component (2) represented by the formula (1) may include only one kind. In addition, two or more kinds of structural units represented by formula (1) may be included, and two or more kinds of copolymerization components (2) may be included. The types of the structural unit and the copolymerization component (2) represented by the formula (1) are usually 8 or less, and preferably 5 or less. A polymer compound (1) containing one of the constituent units represented by the formula (1) and one of the copolymerization components (2) alternately is particularly preferred, and the structural unit represented by the formula (1) is alternately contained alternately. Polymer compound (1) with only one copolymerization component (2).

Preferred specific examples of the polymer compound (1) are shown below. However, the polymer compound (1) of the present invention is not limited to the following examples. In the following specific examples, R ^T represents n-octyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl, 2-n-hexyldecyl, 2-n-octyldeca Dialkyl, 2-n-decyltetradecyl, or triisopropylsilyl. R ³⁰ to R ⁷³ and R ⁷⁵ to R ⁷⁶ represent n-octyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl, or 2-n-hexyldecyl, and R ⁷⁴ Represents a hydrogen atom, or n-octyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl, 2-n-hexyldecyl, 2-n-octyldodecyl, 2-n-decyltetradecyl or triisopropylsilyl. When the polymer compound (1) contains plural kinds of repeating units, the ratio of the number of each repeating unit is arbitrary.

[Chemical Formula 23]

[Chemical Formula 24]

[Chemical Formula 25]

[Chemical Formula 26]

[Chemical Formula 27]

[Chemical Formula 28]

[Chemical Formula 29]

[Chemical Formula 30]

[Chemical Formula 31]

[Chemical Formula 32]

[Chemical Formula 33]

[Chemical Formula 34]

[Chemical Formula 35]

[Chemical Formula 36]

[Chemical Formula 37]

[Chemical Formula 38]

[Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

[Chemical Formula 42]

[Chemical Formula 43]

[Chemical Formula 44]

[Chemical Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

[Chemical Formula 48]

[Chemical Formula 49]

[Chemical Formula 50]

[Chemical Formula 51]

[Chemical Formula 52]

[Chemical Formula 53]

[Chemical Formula 54]

[Chemical Formula 55]

[Chemical Formula 56]

[Chemical Formula 57]

[Chemical Formula 58]

[Chemical Formula 59]

[Chemical Formula 60]

[Chemical Formula 61]

[Chemical Formula 62]

[Chemical Formula 63]

[Chemical Formula 64]

[Chemical Formula 65]

[Chemical Formula 66]

[Chemical Formula 67]

[Chemical Formula 68]

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). In addition, the photoelectric conversion element using the polymer compound (1) exhibits high openness. Circuit voltage (Voc) and shows high photoelectric conversion characteristics. When the polymer compound (1) is used as a p-type semiconductor compound and a fullerene compound is used as an n-type semiconductor compound, particularly high photoelectric conversion characteristics are exhibited. In addition, the polymer compound (1) of the present invention has the advantage that HOMO has a low energy level and is not easily oxidized.

In addition, since the polymer compound (1) shows high solubility in a solvent, it has an advantage of being easy to coat and form a film. In addition, when coating and forming a film, a wide range of solvents can be selected, so a solvent more suitable for film formation can be selected, and the film quality of the formed active layer can be improved. It is considered that this is also a factor that the photoelectric conversion element using the polymer compound (1) of the present invention exhibits high photoelectric conversion characteristics.

The weight average molecular weight and number average molecular weight of the polymer compound (1) of the present invention are generally preferably 2,000 to 500,000, and more preferably 3,000 to 200,000. 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 a gel permeation chromatography.

The polymer compound (1) of the present invention preferably has a light absorption maximum wavelength (λmax) of 400 nm or more, more preferably 450 nm or more, and usually 1200 nm or less, preferably 1000 nm or less, and more preferably 900 nm or less. Moreover, the half-value width is usually more than 10nm, which is It is preferably 20 nm or more, and usually 300 nm or less. In addition, the closer the absorption wavelength region of the polymer compound (1) of the present invention is to the absorption wavelength region of sunlight, the better.

The solubility of the polymer compound (1) of the present invention is preferably a solubility in chlorobenzene at 25 ° C of usually 0.1% by mass or more, more preferably 0.4% by mass or more, still more preferably 0.8% by mass or more, and usually It is 30% by mass or less, and preferably 20% by mass. The solubility is higher than that of a thicker active layer that can be formed into a film.

The polymer compound (1) of the present invention is preferably one having an interaction between molecules. In the present invention, the intermolecular interaction refers to the shortening of the distance between polymer chains by the interaction of π-π stacking between molecules of a polymer compound. The stronger the interaction, the more the polymer compound tends to exhibit high carrier mobility and / or crystallinity. That is, it is easy to cause an intermolecular charge transfer in a polymer compound that generates an interaction between the molecules. Therefore, it is considered that the p-type semiconductor compound (polymer compound (1)) and n that are located in the active layer (IV) can be efficiently transferred. Holes generated at the interface of the type semiconductor compound are transmitted to the anode (II).

Method for producing polymer compound (1)

The manufacturing method of the polymer compound (1) used in the present invention is, for example, manufactured by a manufacturing method selected from 2,6-diiodobenzo [1,2-d; 4,5-d '] One of the compounds in the group consisting of bisthiazole and 2,6-dibromobenzo [1,2-d; 4,5-d '] bisthiazole was used as a starting material and passed through the following compounds, namely, formula (3 ),

[In formula (3), T ¹ and T ² each independently represent an alkoxy group, a thioalkoxy group, a thiophene ring which may be substituted with a hydrocarbon group or an organosiliconyl group, a thiazole ring which may be substituted with a hydrocarbon group or an organosiliconyl group, Or phenyl substituted with hydrocarbyl, alkoxy, thioalkoxy, organosilicon, halogen atom or trifluoromethyl]

A compound represented by formula (4),

[In formula (4), T ¹ and T ² each represent the same group as above; X ¹ and X ^{2 each} represent chlorine, bromine, or iodine]

A compound represented by formula (5).

[In formula (5), T ¹ and T ² represent the same groups as 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 ethynyl]

The method for producing the polymer compound (1) used in the present invention is preferably a compound represented by formula (6).

[In formula (6), T ¹ and T ² represent the same bases as above; B ³ and B ⁴ represent the same bases as B ¹ and B ² ; R ¹ to R ⁴ each independently represent a carbon number of 1 to 6 Aliphatic hydrocarbon group, hydroxyl group, alkoxy group having 1 to 6 carbon atoms, or 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 also be M ¹ forms a ring together, and R ³ and R ⁴ can also form a ring with M ² ; m and n each represent an integer of 1 or 2; and when m and n are 2, a plurality of R ¹ and R ³ may each Same or different]

The compound of the formula (6) can be produced, for example, in the following manner.

First step: reacting a compound represented by formula (7) and / or formula (8) in the presence of 2,6-dihalobenzobisthiazole and a metal catalyst to obtain the compound represented by formula (3) The steps of the compound shown.

[Chemical Formula 73] T ¹ -R ⁵ (7) T ² -R ⁶ (8)

[In formulae (7) and (8), T ¹ and T ² each represent the same group as described above; R ⁵ and R ⁶ each independently represent a hydrogen atom or * -M ³ (R ⁷ ) _k R ⁸ ; R ⁷ And R ⁸ each independently represent 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 bonding bond; R ⁷ and R ⁸ may also form a ring with M ³ ; k represents an integer of 1 or 2; and when k is 2, a plurality of R ⁷ may be the same or different]

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).

By further including the following third step, fourth step, and fifth step, a compound represented by formula (6) can be obtained.

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

[In the formulae (9) and (10), B ¹ and B ² each represent the same base as above; R ⁹ to R ¹² each independently represent an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a hydroxyl group, and 1 to 6 carbon atoms. An alkoxy group, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms; M ⁴ and M ⁵ represent a boron atom, a tin atom, or a silicon atom; R ⁹ and R ¹⁰ may also be combined with M ⁴ Together form a ring, R ¹¹ and R ¹² can also form a ring with M ⁵ ; p represents an integer of 1 or 2; when p is 2, a plurality of R ⁹ may be the same or different]

Fourth step: a step of reacting a compound represented by the formula (5) with a base and a tin halide compound to obtain a compound represented by the formula (6).

In the present invention, B ¹ and B ² of the compound represented by the formula (5) are a thiophene ring (preferably a group represented by the formula (b1)) which may be substituted with a hydrocarbon group, or a thiazole which may be substituted with a hydrocarbon group In the case of a ring (preferably a base represented by formula (b2)), it is preferable to include a fourth step.

Coupling reaction

In addition, the polymer compound (1) can be manufactured as an acceptor-acceptor type polymer compound (acceptor-receptor polymer) by coupling the structural unit represented by formula (1) and the copolymerization component (2) in an alternating arrangement by a coupling reaction. -Acceptor type semiconductor polymer).

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

[Chemical Formula 75]

[Chemical Formula 76]

[In the formulae (C1) to (C43), R ³⁰ to R ⁷³ and R ⁷⁵ to R ⁷⁶ each independently represent a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms, and R ⁷⁴ represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms ; A ³⁰ and A ³¹ each independently represent the same base as T ¹ and T ² , X represents a halogen atom, and j represents an integer of 1 to 4]

Other p-type semiconductor compounds

The active layer (IV) contains at least the polymer compound (1) of the present invention as a p-type semiconductor compound. However, a p-type semiconductor compound different from the polymer compound (1) and the polymer compound (1) may be mixed and / or laminated and used in combination. Examples of other p-type semiconductor compounds that can be used in combination include 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 a high molecular organic semiconductor compound is preferred.

Organic semiconductor compounds (11)

Examples of the organic semiconductor compound (11) include conjugated copolymer semiconductor compounds such as polythiophene, polyfluorene, polyphenylacetylene, polythiopheneacetylene, polyacetylene, or polyaniline; oligomers substituted with alkyl groups or other substituents Copolymer semiconductor compounds such as thiophene. Further, a copolymer semiconductor compound in which two or more kinds of monomer units are copolymerized may be mentioned. For conjugated copolymers, for example, the third edition of the Handbook of Conducting Polymers (3rd Ed.) (2 volumes), 2007, Journal of Polymer Science A: Polymer Chemistry (J. Polym. Sci. Part A: Polym. Chem.) 2013, 51, 743-768, Journal of the American Chemical Society (J. Am. Chem. Soc.) 2009, 131, 13886-13887, International Edition of Applied Chemistry (Angew. Chem. Int. Ed.) 2013 , 52,8341-8344, Advanced Materials (Adv. Mater.) 2009, 21, 2093-2097 and other known copolymers or derivatives thereof, and copolymers that can be synthesized by combining the recorded monomers Thing. The organic semiconductor compound (11) may be a single compound or a mixture of a plurality of compounds. By using the organic semiconductor compound (11), an increase in the amount of light absorption and the like due to the addition of an absorption wavelength band can be expected.

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

[Chemical Formula 78]

HOMO (highest occupied molecular orbital) energy order of p-type semiconductor compound (polymer compound (1), or a mixture of polymer compound (1) and other p-type semiconductor compounds, preferably polymer compound (1)) It can be selected according to the type of the n-type semiconductor compound described later. Especially when a fullerene compound is used as the n-type semiconductor compound, the lower limit of the HOMO energy step of the p-type semiconductor compound is usually -7 eV or more, more preferably -6.5 eV or more, and even more preferably -6.2 eV or more. 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 even more preferably -5.1 eV or less. By moderately increasing the HOMO energy level of p-type semiconductor compounds, As the characteristics of the p-type semiconductor are improved, by appropriately suppressing the HOMO energy level of the p-type semiconductor compound, the stability of the p-type semiconductor compound is improved, and the open circuit voltage (Voc) is also increased.

The LUMO (lowest unoccupied molecular orbital) energy order of the p-type semiconductor compound can be selected according to the type of the n-type semiconductor compound described later. Especially when a fullerene compound is used as the 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 -2.7eV or less. By moderately suppressing the LUMO energy level of the p-type semiconductor, the energy gap is adjusted, which can effectively absorb light energy at long wavelengths, thereby increasing the short-circuit current density. By appropriately increasing the LUMO energy level of the p-type semiconductor compound, it is easy to cause electrons to move to the n-type semiconductor compound, thereby increasing the short-circuit current density.

The calculation method of the LUMO energy step and the HOMO energy step can be exemplified by a method of calculating in theory and a method of performing actual measurement. As a method of calculating a theoretical value, a semi-empirical molecular orbital method and an ab initio molecular orbital method can be cited. Examples of a method for performing the actual measurement include ultraviolet-visible absorption spectrometry, and measurement of free potential using an ultraviolet photoelectron analyzer ("AC-3" manufactured by Riken Keiki Co., Ltd.) at room temperature and pressure.

Among them, AC-3 measurement is preferred. In the present invention, AC-3 is used. Assay.

1.1.3 n-type semiconductor compounds

The n-type organic semiconductor compound is generally a π-electron conjugated compound having a lowest unoccupied molecular orbital domain (LUMO) energy level of 3.5eV to 4.5eV, and examples thereof include: fullerene or a derivative thereof; octaaza Porphyrins and other perfluorinated bodies in which hydrogen atoms of p-type organic semiconductor compounds are replaced by fluorine atoms (such as perfluoropentabenzene or perfluorophthalocyanin); including naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic acid difluorene Aromatic carboxylic anhydrides such as amines, fluorene tetracarboxylic anhydride, and fluorene dicarboxylic acid difluorene or their fluorinated imide compounds are used as backbone polymer compounds.

Among these n-type organic semiconductor compounds, fullerene or its derivative can perform charge separation with the p-type semiconductor compound (especially the polymer compound (1) having a specific constituent unit) of the present invention at high speed and efficiency, It is better.

Examples of fullerenes and derivatives include: C60 fullerene, C70 fullerene, C76 fullerene, C78 fullerene, C84 fullerene, C240 fullerene, C540 fullerene, mixed fuller Alkenes, fullerene nanotubes, and any of these are partially hydrogen, halogen, substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, ether , Thioether, amine, silicon and other substituted fullerene derivatives.

As the fullerene derivative, phenyl-C61-butyrate, diphenyl-C62-bis (butyrate), phenyl-C71-butyrate, phenyl-C85-butyrate or The thienyl-C61-butyrate, the preferred carbon number of the alcohol portion of the butyrate is 1 to 30, more preferably 1 to 8, even more preferably 1 to 4, and most preferably 1.

Examples of preferred fullerene derivatives include phenyl-C61-butyric acid methyl ester ([60] PCBM), phenyl-C61-n-butyl butyrate ([60] PCBnB), and phenyl- C61-isobutyl butyrate ([60] PCBiB), phenyl-C61-n-hexyl butyrate ([60] PCBH), phenyl-C61-n-octyl butyrate ([60] PCBO), diphenyl -C62-bis (methyl butyrate) (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 tricarboxylic acid ethyl ester, N-methylfullerene pyrrolidine (MP- C60), (1,2-methylene fullerene C60) -61-carboxylic acid, (1,2-methylene fullerene C60) -61-carboxylic acid third butyl ester, Japanese Patent Laid-Open No. 2008 -130889, metallocene fullerenes and the like, and US Pat. No. 7,329,709 fullerenes having a cyclic ether group.

1.2 Anode (II), cathode (VI)

The anode (II) and the cathode (VI) have a function of capturing holes and electrons generated by light absorption. Therefore, the pair of electrodes is preferably an electrode (VI) (cathode) suitable for capturing electrons and an electrode (II) (anode) suitable for capturing holes. Either one of the pair of electrodes (preferably the anode (II)) may be translucent, or both may be translucent. Translucent refers to the transmission of sunlight by more than 40%. In addition, in order to allow light to pass through the transparent electrode and reach the active layer (IV), The solar light transmittance of the optical transparent electrode is preferably 70% or more. The light transmittance can be measured by a general spectrophotometer.

The cathode (VI) is preferably an electrode composed of a conductive material having a smaller work function than 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, and magnesium, and alloys thereof. ; Inorganic salts such as lithium fluoride or cesium fluoride; metal oxides such as nickel oxide, aluminum oxide, lithium oxide, or cesium oxide. These materials are preferred because they have a smaller work function. In addition, when an n-type semiconductor compound such as zinc oxide is used as a material for the electron transport layer (V), a material suitable for the anode such as indium tin oxide (ITO) can also be used. A material with a larger work function is used as a material of the cathode (VI). From the viewpoint of electrode protection, the cathode (VI) is preferably a metal electrode formed of 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, and more preferably 500 nm or less. The more moderate the thickness of the cathode (VI) film, the more the sheet resistance can be suppressed. By appropriately reducing the thickness of the cathode (VI) film, the light can be efficiently converted into electricity without lowering the light transmittance. Cathode (VI) When used as a transparent electrode, it is necessary to select a film thickness that has both light transmittance and sheet resistance.

The sheet resistance of the cathode (VI) is usually 1000 Ω / sq or less, preferably 500 Ω / sq or less, and more preferably 100 Ω / 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 nano particles and a precursor is applied to form a film.

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

Examples of the anode (II) include conductive materials such as nickel oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium zirconium oxide (IZO), titanium oxide, indium oxide, or zinc oxide. Metal oxides; metals such as gold, platinum, silver, chromium or cobalt, or alloys thereof. These substances are preferred because they have a large work function, and furthermore, they can be laminated due to the conductive polymer materials represented by PEDOT-PSS doped with polystyrene sulfonic acid in polythiophene derivatives. When laminating such conductive polymers, since the conductive polymer material has a large work function, it can be widely used even if it is not a material with a large work function as described above. Metals suitable for the cathode such as aluminum or magnesium are commonly used.

Moreover, PEDOT-PSS doped with polystyrene sulfonic acid in polythiophene derivatives, or conductive polymer materials doped with iodine or the like in polypyrrole or polyaniline may be used as the material of the anode.

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

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, and further preferably 500 nm or less. By making the film thickness of the anode (II) moderately thick, sheet resistance can be suppressed, and by making the film thickness of the anode (II) moderately thin, light can be efficiently converted into electricity without lowering light transmittance. When the anode (II) is a transparent electrode, it is necessary to select a film thickness that can have both light transmittance and sheet resistance.

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

Examples of a method for forming the anode (II) include a vacuum film-forming method such as a vapor deposition method or a sputtering method, or applying an ink containing nano particles and a precursor. A film-forming wet coating method was performed.

In addition, the cathode (VI) and the anode (II) may have a laminated structure of two or more layers. Moreover, the surface characteristics of the cathode (VI) and the anode (II) can be improved to improve the characteristics (electrical characteristics, wetting characteristics, etc.).

1.3 Substrate (I)

The photoelectric conversion element (VII) usually has a base material (I) as a support. That is, an electrode (II), an electrode (VI), and an active layer (IV) are formed on a substrate.

The material of the substrate (I) is not particularly limited as long as the effect of the present invention is not significantly impaired. Examples of suitable materials for the substrate (I) include inorganic materials such as quartz, glass, sapphire, and titanium oxide; polyethylene terephthalate, polyethylene naphthalate, polyether fluorene, Polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, fluororesin film, polyolefins such as vinyl chloride or polyethylene, cellulose, polyvinylidene chloride, aromatic polyamine, Organic materials such as polyphenylene sulfide, polyurethane, polycarbonate, polyarylate, polynorbornene, or epoxy resin; paper materials such as paper or synthetic paper; performed on the surface of metals such as stainless steel, titanium, or aluminum Composite materials such as those coated or laminated to provide insulation.

Examples of the glass include soda glass, blue plate glass, and alkali-free glass. Among them, alkali-free glass is preferred in terms of less eluted ions from the glass.

As the shape of the substrate (I), for example, a plate shape, a film shape, or a sheet shape can be used. The film thickness of the substrate (I) is usually 5 μm or more, preferably 20 μm or more, and usually 20 mm or less, and preferably 10 mm or less. If the film thickness of the base material (I) is moderately thick, the possibility of insufficient strength of the photoelectric conversion element is reduced, which is preferable. If the film thickness of the base material (I) is moderately thin, costs can be suppressed and the weight does not become heavy, so it is preferable. When the material of the substrate (I) is glass, the film thickness is usually 0.01 mm or more, preferably 0.1 mm or more, and usually 1 cm or less, and preferably 0.5 cm or less. If the film thickness of the glass substrate (I) is moderately thick, the mechanical strength is increased and it is difficult to break, so it is preferable. In addition, if the film thickness of the glass substrate (I) is moderately thin, the weight does not become heavy, so it is preferable.

1.4 buffer layer (III, V)

The photoelectric conversion element (VII) is preferably located on the active layer (IV) and the anode (II) (hereinafter, also referred to as "electrode (II)") and the cathode (VI) (hereinafter, also referred to as "electrode (VI)" ) Has a buffer layer (III) and a buffer layer (V). The buffer layer can be classified into an electron transport layer (V) and a hole transport layer (III). By providing a buffer layer, electrons or holes can easily move between the active layer (IV) and the anode (II) or the cathode (VI), and in addition, a short circuit between the electrodes can be prevented. However, the buffer layer (III) and the buffer layer (V) may not be present in the present invention.

The electron transport layer (V) and the hole transport layer (III) are arranged between a pair of electrodes (II) and electrodes (VI) so as to sandwich an active layer (IV). That is, the photoelectric conversion element (VII) in the present invention includes an electron transport layer (V) and a hole transport layer In both cases (III), the cathode (VI), the electron transport layer (V), the active layer (IV), the hole transport layer (III), and the anode (II) are arranged in this order. When the photoelectric conversion element (VII) of the present invention includes an electron transport layer (V) and does not include a hole transport layer (III), the cathode (VI), the electron transport layer (V), the active layer (IV), And anode (II).

1.4.1 Electron transport layer (V)

The electron transport layer (V) is a layer for extracting electrons from the active layer (IV) to the cathode (VI). The material constituting the electron transport layer (V) is preferably a material having an electron transport property that improves the efficiency of electron extraction. The organic compound may be an inorganic compound, but an inorganic compound is preferred.

Preferred examples of the material of the inorganic compound include salts of alkali metals such as lithium, sodium, potassium, and cesium, salts of alkaline earth metals such as calcium, and metal oxides. 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 preferably titanium oxide (TiOx) or zinc oxide ( A metal oxide having n-type semiconductor characteristics such as ZnO). As the material of the inorganic compound, a metal oxide having n-type semiconductor characteristics such as titanium oxide (TiOx) or zinc oxide (ZnO) is more preferable. Especially preferred is titanium oxide (TiOx). The action mechanism of this material is unknown, but it is believed that when combined with the cathode (VI), the work function will be reduced and the voltage applied to the interior of the solar cell element will be increased.

The LUMO energy level of the material of the electron transport layer (V) is usually -4.0eV The above is preferably -3.9 eV or more, and is usually -1.9 eV or less, and preferably -2.0 eV or less. If the LUMO energy level of the material of the electron transport layer (V) is moderately suppressed, it is better in terms of promoting charge transfer. If the LUMO energy level of the material of the electron transport layer (V) is increased moderately, it is preferable in terms of preventing reverse electron movement to the n-type semiconductor compound.

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. If the HOMO energy level of the material of the electron transport layer (V) is moderately suppressed, it is better in that the hole movement can be prevented. As a calculation method of the LUMO energy level and the HOMO energy level of the material of the electron transport layer (V), a cyclic voltammetry method can be cited.

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, and usually 100 nm or less, preferably 70 nm or less, more preferably 40 nm or less, particularly preferably Below 20nm. By making the film thickness of the electron transport layer (V) moderately thick, it functions as a buffer material. By making the film thickness of the electron transport layer (V) moderately thin, it becomes easy to extract electrons, and the photoelectric conversion efficiency can be improved.

1.4.2 Hole Transmission Layer (III)

The hole transporting layer (III) is a layer for extracting holes from the active layer (IV) to the anode (II), and is not particularly limited as long as it is a hole transporting material that can improve the efficiency of hole extraction. Specific examples include polythiophene, Conductive polymers doped with sulfonic acid and / or iodine in polypyrrole, polyacetylene, triphenylenediamine, polyaniline, etc .; polythiophene derivatives with sulfonyl groups as substituents, and arylamine conductive properties Organic compounds; metal oxides with p-type semiconductor characteristics such as molybdenum trioxide, vanadium pentoxide or nickel oxide; the aforementioned p-type semiconductor compounds and the like. Among them, a conductive polymer doped with a sulfonic acid is preferable, and a poly (3,4-ethylenedioxythiophene) -poly doped with a polystyrenesulfonic acid in a polythiophene derivative is more preferable. (Styrenesulfonic acid) (PEDOT-PSS). In addition, a thin film of a metal such as gold, indium, silver, or palladium may be used. A thin film of a metal or the like may be formed alone, or may be used in combination with the above-mentioned 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, and usually 400 nm or less, preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably It is 70 nm or less. By making the film thickness of the hole transport layer 104 moderately thick, it functions as a buffer material. By making the film thickness of the hole transport layer (III) moderately thin, it becomes easy to extract holes, and the photoelectric conversion efficiency can be improved. .

The method for forming the electron transport layer (V) and the hole transport layer (III) is not limited. For example, when a material having sublimation properties is used, it can be formed by a vacuum evaporation method or the like. In addition, for example, when a solvent-soluble material 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 after forming a layer containing the semiconductor compound precursor in the same manner as the active layer (IV). 组合。 The compound.

1.5 Manufacturing method of photoelectric conversion element

The photoelectric conversion element (VII) can be laminated in order, for example, by the following method: And cathode (VI). For example, an indium tin oxide (ITO) transparent conductive film (anode) is patterned on a glass substrate (manufactured by Geomatics) using acetone for ultrasonic cleaning, and then using ethanol for ultrasonic cleaning, followed by nitrogen flow The substrate is dried and subjected to UV (ultraviolet) -ozone treatment to form a substrate with an anode. Then, a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion used as a hole transporting layer was coated with a spin coater (5000 rpm, 50 seconds), and then annealed at 200 ° C for 10 minutes to form a hole transport layer. After that, it is moved into a glove box, and a mixed solution of the p-type semiconductor compound and the n-type semiconductor compound is spin-coated under an inert gas environment, and an annealing process or drying under reduced pressure is performed on a hot plate to form an active layer. Then, an ethanol solution (about 0.3v%) of tetraisopropyl orthotitanate is spin-coated in the atmosphere, and an electron transport layer can be produced by converting moisture in the environment into titanium oxide. Finally, aluminum, which is vapor-deposited as an electrode, is set as a cathode, so that a photoelectric conversion element can be obtained.

In addition, photoelectric conversion elements having different structures, for example, photoelectric conversion elements that do not have at least one of a hole transport layer (III) and an electron transport layer (V) can also be manufactured by the same method.

1.6 photoelectric conversion characteristics

The photoelectric conversion characteristics of the photoelectric conversion element (VII) were obtained as follows. The photoelectric conversion element (VII) was irradiated with light of AM1.5G condition at an irradiation intensity of 100 mW / cm ² using a solar simulator, and the current-voltage characteristics were measured. Based on the obtained current-voltage curve, photoelectric conversion characteristics (PCE), short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF), series resistance, and parallel resistance can be obtained.

2. Organic thin film solar cell of the present invention

The photoelectric conversion element (VII) of the present invention is used as a solar cell, and among them, it is preferably used as a solar cell element of an organic thin film solar cell. An organic thin film solar cell having the photoelectric conversion element (VII) is also included in the technical scope of the present invention Inside.

The organic thin film solar cell of the present invention can be used in any application. Examples of the fields in which the organic thin-film solar cells to which the present invention can be applied are solar cells for building materials, solar cells for automobiles, solar cells for interior decoration, solar cells for railways, solar cells for ships, solar cells for aircraft, and the universe. Solar cells for aircraft, solar cells for home appliances, solar cells for mobile phones, or solar cells for toys.

The organic thin film solar cell of the present invention can be used directly, or a solar cell can be provided on the substrate (I) and used as a solar cell module. If specific examples are listed, when using a building material plate as a base material, A thin-film solar cell is installed on the surface, and the solar cell panel can be manufactured as a solar cell module.

This case is based on Japanese Patent Application No. 2015-022034 filed on February 6, 2015 and claiming priority. The entire contents of the specification of Japanese Patent Application No. 2015-022034 filed on February 6, 2015 are incorporated herein by reference.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Of course, the present invention can be appropriately modified and implemented within a range suitable for the above-mentioned and later-mentioned gist, and All are included in the technical scope of the present invention.

In addition, unless otherwise specified in the following, "part" means "mass part" and "%" means "mass%".

The measurement methods used in the synthesis examples are as follows.

NMR Spectroscopy

The benzobisthiazole compound was subjected to NMR spectrum measurement using an NMR spectrometer ("400MR" manufactured by Agilent (formerly Varian) and "AVANCE500" manufactured by Bruker).

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 of course not affected by the following The synthesis examples are limited, and of course, the synthesis method itself may be appropriately changed and synthesized within a range suitable for the above-mentioned and later-mentioned purposes. In addition, unless otherwise specified in the following, "part" means "mass part" and "%" means "mass%".

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) thiophen-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) and reacted at 120 ° C for 23 hours. After the reaction was completed, the 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. Then, filtration and concentration were performed, and the obtained crude product was purified by a column chromatography (silica gel, chloroform / hexane = 1/1), thereby obtaining 5.62 g of 2,6-bis [5 as a pale yellow solid. -(2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-HDTH) (60% yield).

It was confirmed by ¹ H-NMR measurement that the target compound was formed.

Synthesis Examples 2 to 6

In the same manner as in Synthesis Example 1, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] Bithiazole (DBTH-DMOTH) (Synthesis Example 2), 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] Bithiazole (DBTH-EHTH) (Synthesis Example 3), 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] benzo [1,2-d; 4,5-d ' ] Bithiazole (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-triisopropylsilylthiophen-2-yl) -benzo [1,2-d; 4,5 -d '] bisthiazole (DBTH-TIPSTH) (Synthesis Example 6). The yield is 38% to 51%.

Synthesis Example 7

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

In a 100 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-HDTH, 4g , 4.97 mmol) and tetrahydrofuran (80 mL) and cooled to -40 ° C, lithium diisopropylamidamine (2M solution, 5.5 mL, 10.9 mmol) was added dropwise and stirred for 30 minutes. Of course Then, iodine (3.8 g, 14.9 mol) was added, and the mixture was reacted at room temperature for 2 hours. After the reaction was completed, 10% sodium bisulfite was added and extraction was performed with chloroform. The obtained organic layer was washed with a saturated sodium bicarbonate aqueous solution, and then washed with saturated brine, and then dried over anhydrous magnesium sulfate. Then, filtration and concentration were performed, and the obtained crude product was purified by a column chromatography (silica gel, chloroform / hexane = 1/1), thereby obtaining 2.66 g of 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-HDTH) (51% yield ).

It was confirmed by ¹ H-NMR measurement that the target compound was formed.

Synthesis Examples 8 ~ 12

In the same manner as in Synthesis Example 7, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-DMOTH) (Synthesis Example 8), 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4,8-diiodo Benzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-EHTH) (Synthesis Example 9), 2,6-bis [5- (2-butyloctyl) thiophene-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-triisopropylsilylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DI-DBTH-TIPSTH) (Synthesis Example 12). The yield is 36% ~ 70%.

Synthesis Example 13

2,6-bis [5- (2-hexyldecyl) thien-2-yl] -4,8-dithien-2-yl-benzo [1,2-d; 4,5-d '] bis Synthesis of thiazole (DTH-DBTH-HDTH)

In a 50 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-diiodobenzo [1,2-d; 4,5-d '] bis Thiazole (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) and reacted at 80 ° C. for 19 hours. After the reaction was completed, the 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. Then, filtration and concentration were performed, and the obtained crude product was purified by column chromatography (silica gel, chloroform / hexane = 1/1 to chloroform), thereby obtaining 1.01 g of 2,6-bis [as a yellow solid. 5- (2-hexyldecyl) thien-2-yl] -4,8-dithien-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH- HDTH) (100% yield).

It was confirmed by ¹ H-NMR measurement that the target compound was formed.

Synthesis Examples 14 to 17

In the same manner as in Synthesis Example 13, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-dithiophen-2-yl-benzo [1 , 2-d; 4,5-d '] bisthiazole (DTH-DBTH-DMOTH) (Synthesis Example 14), 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4 , 8-dithien-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-dithiophen-2-yl-benzo [1,2-d ; 4,5-d '] bisthiazole (DTH-DBTH-TDTH) (Synthesis Example 17). The yield is 45% ~ 99%.

Synthesis Example 18

2,6-bis [5- (2-hexyldecyl) thien-2-yl] -4,8-bisthiazol-2-yl-benzo [1,2-d; 4,5-d '] Synthesis of thiazole (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 '] bis Thiazole (DI-DBTH-HDTH, 800mg, 0.76mmol), 2-tributyltinalkylthiazole (708mg, 1.89mmol), tris (2-furyl) phosphine (29mg, 0.12mmol), tris (dibenzylideneacetone) ) Dipalladium (0) -chloroform adduct (32 mg, 30 μmol) and N, N-dimethylformamide (5 mL) and reacted at 80 ° C. for 17 hours. End of reaction Then, it cooled to room temperature, water was added, it extracted with chloroform twice, and the organic layer was washed with water and dried with anhydrous magnesium sulfate. Then, filtration and concentration were performed, and the obtained crude product was purified by a column chromatography (silica gel, chloroform) to obtain 684 mg of 2,6-bis [5- (2-hexyldecyl) thiophene as a yellow solid. 2-yl] -4,8-bisthiazole-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTHA-DBTH-HDTH) (94% yield).

It was confirmed by ¹ H-NMR measurement that the target compound was formed.

Synthesis Example 19

In the same manner as in Synthesis Example 18, 4,8-bis- (thiazol-2-yl) -2,6-bis- (5-triisopropylsilylthiophen-2-yl) -benzo [1, 2-d; 4,5-d '] bisthiazole (DBTH-TIPSTH-THA). The yield was 45%.

Synthesis Example 20

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

In a 50 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophene-2- Group] -4,8-dithiophen-2-yl-benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-HDTH, 602 mg, 0.62 mmol) and tetrahydrofuran (18 mL) and After cooling to -40 ° C, lithium diisopropylamidamine (2M solution, 0.65 mL, 1.30 mmol) was added dropwise and stirred for 30 minutes. After that, tributyltin chloride (352 μL, 1.30 mmol) was added, and the temperature was raised to room temperature and stirred for 2 hours. After the reaction was completed, water was added, extraction was performed twice with toluene, and the organic layer was washed with water, and then dried over anhydrous magnesium sulfate. Then, filtration and concentration were performed, and the obtained crude product was purified by GPC-HPLC (JAIGEL-1H, 2H, chloroform) to obtain 634 mg of 2,6-bis [5- (2-hexyldecane) as a light brown oil. Yl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH -HDTH-DSB) (yield 66%).

It was confirmed by ¹ H-NMR measurement that the target compound was formed.

Synthesis Example 21

In the same manner as in Synthesis Example 20, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-bis (5-tributyltin alkylthiophene-2) was obtained. -Yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-DMOTH-DSB). The yield is 49% ~ 63%.

Synthesis Examples 22 to 25

In the same manner as in Synthesis Example 20 and by using trimethyltin chloride instead of tributyltin chloride, 2,6-bis [5- (2-ethylhexyl) thiophen-2-yl] -4, 8-bis (5-trimethylstannylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] Bithiazole (DTH-DBTH-EHTH-DSM) (Synthesis Example 22), 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-bis (5-trimethyl Stannylthiophene-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) -benzo [1,2-d; 4,5- d '] bisthiazole (DTH-DBTH-HDTH-DSM) (Synthesis Example 24), 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) (Synthesis Example 25). The yield is 27% ~ 67%.

Synthesis Examples 26, 27

In the same manner as in Synthesis Example 19, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiazol-2-yl)- Benzo [1,2-d; 4,5-d '] bisthiazole (DTHA-DBTH-HDTH-DSB) (Synthesis Example 26), 4,8-bis (5-tributyltin alkylthiazol-2-yl ) -2,6-bis (5-triisopropylsilylthiophen-2-yl) -benzo [1,2-d; 4,5-d '] bisthiazole (DBTH-TIPSTH-THA-DSB) (Synthesis example 27). The yield was 49%.

Synthesis Example 28

Synthesis of P-THDT-DBTH-EH-IMTH

[Chemical Formula 84]

In a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiophen-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] pyrrole-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 reacted at 120 ° C. for 22 hours. After the reaction, the reaction solution was added to methanol (60 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet washing (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 109 mg (91%) of P-THDT-DBTH-EH-IMTH was obtained as a black solid.

Synthesis Example 29

Synthesis of P-THDT-DBTH-O-IMTH

[Chemical Formula 85]

In 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, 90mg, 0.07mmol), 1,3-dibromo-5-octylthieno [3,4-c ] Pyrrole-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) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (50 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 74 mg (87%) of P-THDT-DBTH-O-IMTH as a black solid.

Synthesis Example 30

Synthesis of P-THDT-DBTH-DMO-IMTH

[Chemical Formula 86]

In 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) thiophene [3,4-c] pyrrole-4,6-dione (DMO-IMTH-DB, 28 mg, 0.06 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.4 μmol), tris (2-methoxyphenyl) phosphine (4 mg, 9.6 μmol) and chlorobenzene (3.2 mL) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 68 mg (87%) of P-THDT-DBTH-DMO-IMTH was obtained as a black solid.

Synthesis Example 31

Synthesis of P-THDT-DBTH-H-IMTH

[Chemical Formula 87]

In 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] Pyrrole-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 reacted at 120 ° C. for 22 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 40 mg (44%) of P-THDT-DBTH-H-IMTH as a black solid.

Synthesis Example 32

Synthesis of P-TEHT-DBTH-HD-IMTH

[Chemical Formula 88]

In 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] pyrrole-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) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 39 mg (37%) of P-TEHT-DBTH-HD-IMTH as a black solid.

Synthesis Example 33

Synthesis of P-TEHT-DBTH-ODD-IMTH

[Chemical Formula 89]

In a 20 mL flask, add 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] pyrrole-4,6-dione (ODD-IMTH-DB, 55mg, 0.09mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4mg 3.7 μmol), tris (2-methoxyphenyl) phosphine (6 mg, 14.9 μmol) and chlorobenzene (7 mL) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 91 mg (76%) of P-TEHT-DBTH-ODD-IMTH was obtained as a black solid.

Synthesis Example 34

Synthesis of P-TEHT-DBTH-TD-IMTH

[Chemical Formula 90]

In a 20 mL flask, add 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] pyrrole-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) and reacted at 120 ° C. for 25 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 62 mg (77%) of P-TEHT-DBTH-TD-IMTH as a black solid.

Synthesis Example 35

Synthesis of P-TBOT-DBTH-DMO-IMTH

[Chemical Formula 91]

In a 20 mL flask, add 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzene 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] pyrrole-4,6-dione (DMO-IMTH-DB, 38 mg, 0.09 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (4 mg, 3.6 μmol), tris (2-methoxyphenyl) phosphine (5 mg, 14.4 μmol) and chlorobenzene (8 mL) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 26 mg (27%) of P-TBOT-DBTH-DMO-IMTH as a black solid.

Synthesis Example 36

Synthesis of P-TBOT-DBTH-HD-IMTH

[Chemical Formula 92]

In a 20 mL flask, add 2,6-bis [5- (2-butyloctyl) thiophen-2-yl] -4,8-bis (5-trimethylstannylthiophen-2-yl) -benzene [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] Pyrrole-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) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 57 mg (78%) of P-TBOT-DBTH-HD-IMTH was obtained as a black solid.

Synthesis Example 37

Synthesis of P-TTDT-DBTH-B-IMTH

[Chemical Formula 93]

In a 20 mL flask, add 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] pyrrole-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 μmol) and chlorobenzene (3 mL) were reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 33 mg (52%) of P-TTDT-DBTH-B-IMTH as a black solid.

Synthesis Example 38

Synthesis of P-TDMOT-DBTH-TDZ

[Chemical Formula 94]

In a 20 mL flask, 2,6-bis [5- (3,7-dimethyloctyl) thiophen-2-yl] -4,8-bis (5-tributyltin alkylthiophen-2-yl)- Benzo [1,2-d; 4,5-d '] bisthiazole (DTH-DBTH-DMOTH-DSB, 122mg, 0.09mmol), 4,7-dibromobenzo [1,2,5] thiadi Azole (TDZ-DB, 26 mg, 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) and reacted at 120 ° C for 24 hours. After the reaction was completed, the reaction solution was added to methanol (50 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 31 mg (38%) of P-TDMOT-DBTH-TDZ was obtained as a black solid.

Synthesis Example 39

Synthesis of P-THDT-DBTH-FFTDZ

[Chemical Formula 95]

In a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiophen-2-yl) -benzo [1 , 2-d; 4,5-d '] bisthiazole (DTH-DBTH-HDTH-DSB, 122mg, 0.08mmol), 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 the reaction was completed, the reaction solution was added to methanol (50 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 27 mg (29%) of P-THDT-DBTH-FFTDZ as a black solid.

Synthesis Example 40

Synthesis of P-TTDT-DBTH-FFTDZ

[Chemical Formula 96]

In a 20 mL flask, add 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, 90mg, 0.06mmol), 4,7-dibromo-5,6-difluorobenzo [ 1,2,5] thiadiazole (FFTDZ-DB, 20mg, 0.06mmol), tetrakis (triphenylphosphine) palladium (2mg, 1.8μmol), toluene (4mL), and N, N-dimethylformamidine Amine (0.3 mL) and reacted at 120 ° C for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 70 mg (87%) of P-TTDT-DBTH-FFTDZ was obtained as a black solid.

Synthesis Example 41

Synthesis of P-TTDT-DBTH-FTDZ

[Chemical Formula 97]

In a 20 mL flask, add 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, 90mg, 0.06mmol), 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) and reacted at 120 ° C for 23 hours. After the reaction was completed, the reaction solution was added to methanol (25 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone). Then, Soxhlet extraction (chloroform) was performed, whereby 68 mg (85%) of P-TTDT-DBTH-FTDZ was obtained as a black solid.

Synthesis Example 42

Synthesis of P-THDT-DBTH-OO-TDZ

[Chemical Formula 98]

In 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, 70mg, 0.05mmol), 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) were reacted at 120 ° C. for 26 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 53 mg (73%) of P-THDT-DBTH-OO-TDZ was obtained as a black solid.

Synthesis Example 43

Synthesis of P-TTDT-DBTH-NTDZ

[Chemical Formula 99]

In a 20 mL flask, add 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, 80mg, 0.05mmol), 5,10-dibromonaphtho [1,2-c: 5 , 6-c '] bis [1,2,5] thiadiazole (NTDZ-DB, 21mg, 0.05mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (2mg, 2.0 μmol), tris (2-methoxyphenyl) phosphine (3 mg, 8.0 μmol) and chlorobenzene (6 mL) and reacted at 120 ° C. for 28 hours. After the reaction was completed, the reaction solution was added to methanol (30 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 63 mg (84%) of P-TTDT-DBTH-NTDZ as a black solid.

Synthesis Example 44

Synthesis of P-THDT-DBTH-DMO-DPP

[Chemical Formula 100]

In a 20 mL flask, add 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiophen-2-yl) -benzo [1 , 2-d; 4,5-d '] bisthiazole (DTH-DBTH-HDTH-DSB, 100 mg, 0.06 mmol), 3,6-bis (5-bromothien-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 (di Benzylideneacetone) dipalladium (0) -chloroform adduct (3 mg, 2.6 μmol), tris (o-tolyl) phosphine (3 mg, 10.4 μmol) and chlorobenzene (10 mL) and reacted at 120 ° C. for 23 hours. After the reaction was completed, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 26 mg (26%) of P-THDT-DBTH-DMO-DPP as a black solid.

Synthesis Example 45

Synthesis of P-THDT-DBTH-EH-OFTT

[Chemical Formula 101]

In 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) and reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (40 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 80 mg (87%) of P-THDT-DBTH-EH-OFTT was obtained as a black solid.

Synthesis Example 46

Synthesis of P-THHDT-DBTH-HTT

[Chemical Formula 102]

In a 20 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiazol-2-yl) -benzo [1 , 2-d; 4,5-d '] bisthiazole (DTHA-DBTH-HDTH-DSB, 120mg, 0.08mmol), 5,5'-dibromo-3-hexyl [2,2'] bithiophene (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) and reacted at 120 ° C for 24 hours. After the reaction was completed, the reaction solution was added to methanol (60 mL), the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 72 mg (77%) of P-THHDT-DBTH-HTT was obtained as a black solid.

Synthesis Example 47

Synthesis of P-THHDT-DBTH-EH-BDT

[Chemical Formula 103]

In a 20 mL flask, 2,6-bis [5- (2-hexyldecyl) thiophen-2-yl] -4,8-bis (5-tributyltinalkylthiazol-2-yl) -benzo [1 , 2-d; 4,5-d '] bisthiazole (DTHA-DBTH-HDTH-DSB, 120mg, 0.08mmol), 2,6-dibromo-4,8-bis (2-ethylhexyloxy) -1,5-Dithiadicyclopentadiene s (indacene) (EH-BDT-DB, 47 mg, 0.08 mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform addition (3 mg, 3.1 μmol), tris (o-tolyl) phosphine (4 mg, 12.3 μmol) and chlorobenzene (10 mL) and reacted at 120 ° C. for 25 hours. After the reaction was completed, the reaction solution was added to methanol (50 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, whereby 70 mg (64%) of P-THHDT-DBTH-EH-BDT was obtained as a dark red solid.

Synthesis Example 48

Synthesis of P-THTIPSTH-DBTH-O-IMTH

[Chemical Formula 104]

In a 20 mL flask, 4,8-bis (5-tributyltinalkylthiazol-2-yl) -2,6-bis (5-triisopropylsilylthiophen-2-yl) -benzo [1, 2-d; 4,5-d '] bisthiazole (DBTH-TIPSTH-THA-DSB, 88 mg, 0.06 mmol), 1,3-dibromo-5-octylthieno [3,4-c] pyrrole- 4,6-dione (O-IMTH-DB, 26mg, 0.06mmol), tris (dibenzylideneacetone) dipalladium (0) -chloroform adduct (3mg, 2.5μmol), tris (o-tolyl) Phosphine (4 mg, 10 μmol) and chlorobenzene (8 mL) were reacted at 120 ° C. for 24 hours. After the reaction was completed, the reaction solution was added to methanol (50 mL), and the precipitated solid was collected by filtration, and the obtained solid was subjected to Soxhlet cleaning (methanol, acetone, and hexane). Then, Soxhlet extraction (chloroform) was performed, thereby obtaining 34 mg (50%) of P-THTIPSTH-DBTH-O-IMTH as a black solid.

Evaluation method of photoelectric conversion element

A 0.05027mm square metal mask was installed on the photoelectric conversion element. A solar simulator (CEP2000, AM1.5G filter, radiation intensity 100mW / cm ² , manufactured by a spectrometer) was used as the light source, and a solar instrument (Keithley ( Keithley), Model 2400). The current-voltage characteristics between the ITO electrode and the aluminum electrode were measured. Based on the measurement results, an open-circuit voltage Voc (V), a short-circuit current density Jsc (mA / cm ² ), a fill factor FF, and a photoelectric conversion efficiency PCE (%) were calculated.

Here, the open circuit voltage Voc is a voltage value when the current value = 0 (mA / cm ² ), and the short-circuit current density Jsc is a current density when the voltage value is 0 (V). The fill factor FF is a factor representing the internal resistance. If the maximum output is set to Pmax, it is expressed by the following formula.

FF = Pmax / (Voc × Jsc)

The photoelectric conversion efficiency PCE is provided by the following formula when the incident energy is set to Pin.

PCE = (Pmax / Pin) × 100 = (Voc × Jsc × FF / Pin) × 100

Example 1

p-type semiconductor compounds. Preparation of mixed solution of n-type semiconductor compound

Use a structure with P-THDT-DBTH-EH-IMTH (synthesis example 28) The polymer compound is referred to as a p-type semiconductor compound.

PCBM (C61) (phenyl C61 methyl butyrate, Frontier Carbon, NS-E100H) was used as the n-type semiconductor compound, and a p-type semiconductor compound and an n-type semiconductor compound with a mass ratio of 1: 2 (total concentration of 2.4 mass) %), And 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene. The solution was stirred and mixed on a hot stirrer at a temperature of 100 ° C for 2 hours or more. The stirred and mixed solution was filtered through a 0.45 μm filter, thereby obtaining a p-type semiconductor compound. A mixed solution of n-type semiconductor compounds.

Production of photoelectric conversion elements

An indium tin oxide (ITO) transparent conductive film (anode) patterned glass substrate (manufactured by Geomatics) was ultrasonically cleaned with acetone, and then ultrasonically cleaned with ethanol, and then dried with a nitrogen stream.

After the UV-ozone treatment, a PEDOT-PSS ([poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) aqueous dispersion used as a hole transporting layer was subjected to a spin coater. After coating (5000 rpm, 60 seconds), annealing was performed at 200 ° C for 10 minutes.

Carry it into the glove box and spin-coat the p-type semiconductor compound in an inert gas environment. The mixed solution of the n-type semiconductor compound is annealed or dried under reduced pressure on a hot plate.

In the atmosphere, a solution of tetraisopropyl orthotitanate in ethanol (about 0.3v%) was spin-coated to produce a film that converts moisture in the environment into titanium oxide. After that, aluminum as an electrode was vapor-deposited to prepare a device. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 3

As a p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-DMO-IMTH (Synthesis Example 30) was used.

Using PCBM (C61) as the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 4

As the p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-H-IMTH (Synthesis Example 31) was used.

Using PCBM (C61) as the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) Dissolved in chlorobenzene In this case, a 0.45 μm filter was used to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Use the income The solution was mixed, and a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 11

[Chemical Formula 115]

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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 12

As a p-type semiconductor compound, a polymer compound having a structure of P-THDT-DBTH-FFTDZ (Synthesis Example 39) was used.

Using PCBM (C61) as the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) Dissolved in chlorobenzene In this case, a 0.45 μm filter was used to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 16

[Chemical Formula 120]

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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in o-dichlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned 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 the n-type semiconductor compound, the p-type semiconductor compound and the n-type semiconductor compound in a mass ratio of 1: 2 (total concentration 2.4% by mass) and 1,8-diiodooctane (0.03 mL / mL) were dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 19

As the p-type semiconductor compound, a polymer compound having a structure of P-THHDT-DBTH-HTT (Synthesis Example 46) was used.

Using PCBM (C61) as the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound (total concentration of 2.4% by mass) with a mass ratio of 1: 2 and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution. Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 20

As the p-type semiconductor compound, a polymer compound having a structure of P-THHDT-DBTH-EH-BDT (Synthesis Example 47) was used.

Using PCBM (C61) as the n-type semiconductor compound, a p-type semiconductor compound and an n-type semiconductor compound with a mass ratio of 1: 2 (total concentration 3.0% by mass), and 1,8-diiodooctane (0.03mL / mL) It was dissolved in o-dichlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution.

Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 21

[Chemical Formula 125]

As a p-type semiconductor compound, a polymer compound having a structure of P-THTIPSTH-DBTH-O-IMTH (Synthesis Example 48) was used.

PCBM (C61) was used as the n-type semiconductor compound, and a p-type semiconductor compound and an n-type semiconductor compound with a mass ratio of 1: 1.5 (total concentration of 2.0% by mass) and 1,8-diiodooctane (0.03mL / mL) It was dissolved in chlorobenzene and passed through a 0.45 μm filter to prepare a mixed solution.

Using the obtained mixed solution, a device was fabricated in the same manner as in Example 1. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Example 22

p-type semiconductor compounds. Preparation of mixed solution of 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 the n-type semiconductor compound, 1: 1.5 (mass) of the p-type semiconductor compound and the n-type semiconductor compound were dissolved in chlorobenzene at a total concentration of 2.0% by mass, and p was obtained through a 0.45 μm filter. Type semiconductor compound. A mixed solution of n-type semiconductor compounds.

Production of photoelectric conversion elements

An indium tin oxide (ITO) transparent conductive film (anode) patterned glass substrate (manufactured by Geomatics) was ultrasonically cleaned with acetone, and then ultrasonically cleaned with ethanol, and then dried with a nitrogen stream.

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

Carry it into the glove box and spin-coat the p-type semiconductor compound in an inert gas environment. The mixed solution of the n-type semiconductor compound is dried under reduced pressure.

Lithium fluoride as an electron moving layer was vapor-deposited by a vapor deposition machine, and thereafter, The device is plated with aluminum as an electrode. The obtained device was evaluated for the above-mentioned photoelectric conversion element. The results are shown in Table 1.

Jsc = Short circuit current density

Voc = Open circuit voltage

FF = Fill factor

PCE = Power conversion efficiency

As described above, the photoelectric conversion element produced 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), and a high photoelectric conversion efficiency η can be obtained. In addition, according to the production method of the present invention, various substituents can be introduced as a substituent, so that the characteristics (crystallinity, film-forming property, and absorption wavelength) of the material can be controlled.

Claims (11)

A photoelectric conversion element has a structure in which a substrate, an anode, an active layer, and a cathode are sequentially arranged, and the foregoing active layer contains a polymer compound having a benzobisthiazole structural unit represented by formula (1): In the formula (1), T ¹ and T ² each independently represent an alkoxy group, a thioalkoxy group, a thiophene ring which may be substituted with a hydrocarbon group or an organosiliconyl group, a thiazole ring which may be substituted with a hydrocarbon group or an organosiliconyl group, or A phenyl group which may be substituted by a hydrocarbon group, an alkoxy group, a thioalkoxy group, a silicone group, a halogen atom or a trifluoromethyl group; and B ¹ and B ² represent a thiophene ring which may be substituted by a hydrocarbon group, and may be substituted by a hydrocarbon group Thiazolyl ring, or ethynyl. The photoelectric conversion element according to claim 1, wherein T ¹ and T ^{2 of the} polymer compound are each a base represented by any one of the following formulae (t1) to (t5): [Chemical formula 2] In the formulae (t1) to (t5), R ¹³ to R ¹⁴ each independently represent a hydrocarbon group having 6 to 30 carbon atoms; R ¹⁵ to R ¹⁶ each independently represent a hydrocarbon group having 6 to 30 carbon atoms or * -Si (R ¹⁸ ) ₃ ; R ^{15 ′} represents a hydrogen atom, a hydrocarbon group having 6 to 30 carbon atoms, * -Si (R ¹⁸ ) ₃ ; R ¹⁷ represents a halogen atom, a hydrocarbon group having 6 to 30 carbon atoms, * -OR ¹⁹ , * -SR 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 bonding bond to a thiazole ring of benzobisthiazole. The photoelectric conversion element according to claim 1 or 2, wherein B ¹ and B ² are each a base represented by any one of the following formulae (b1) to (b3): In the formulae (b1) to (b3), R ²¹ , R ²² , and R ^{21 ′} represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms; * indicates a bonding bond, especially the left side * is set to indicate bonding to benzobis Bonding bond of benzene ring of thiazole compound. The photoelectric conversion element according to claim 1 or 2, wherein the polymer compound is an donor-acceptor semiconductor polymer. The photoelectric conversion element according to claim 1 or 2, wherein the active layer further contains an n-type organic semiconductor compound. The photoelectric conversion element according to claim 5, wherein the n-type organic semiconductor compound is fullerene or a derivative thereof. The photoelectric conversion element according to claim 1 or 2, further comprising a hole transport layer between the anode and the active layer. The photoelectric conversion element according to claim 1 or 2, further comprising an electron transport layer between the cathode and the active layer. The photoelectric conversion element according to claim 1 or 2, wherein the anode is a transparent electrode. The photoelectric conversion element according to claim 1 or 2, wherein the cathode is a metal electrode. An organic thin-film solar cell including the photoelectric conversion element according to any one of claims 1 to 10.