Polymer compound, composition, organic semiconductor material, and organic electronic device

Abstract

Provided is an organic electronic device that has high photoelectric conversion efficiency η as a result of increasing the short circuit current density Jsc and the open circuit voltage Voc of the organic electronic device. Also provided is an organic semiconductor material that can be suitably used when manufacturing such an organic electronic device. Further provided is a polymer compound that can be suitably used as a raw material for such an organic semiconductor material.　The polymer compound has donor units and acceptor units that are alternately arranged, and satisfies UV characteristics indicated in the following (1) and (2). (1) When the ultraviolet-visible absorption spectrum of a film solely containing the polymer compound is measured, one maximum peak exists within 500-800 nm. (2) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound and [60]PCBM at a mass ratio of 1:1 is measured, two maximum peaks exist within 500-800 nm.

Description

Polymer compounds, compositions, organic semiconductor materials, organic electronic devices

[0001] This disclosure relates to polymer compounds that can be suitably used as materials for organic electronic devices, organic semiconductor materials containing the polymer compounds, and electronic devices containing the organic semiconductor materials.

[0002] Organic semiconductor materials are among the most important materials in the field of organic electronics and can be classified into electron-donating p-type organic semiconductor materials and electron-accepting n-type organic semiconductor materials. Examples of organic semiconductor materials include those disclosed in Patent Documents 1 and 2.

[0003] By appropriately combining p-type and n-type organic semiconductor materials, various semiconductor devices can be manufactured. Such devices are applied to, for example, organic electroluminescence, which emits light through the action of excitons formed by the recombination of electrons and holes; organic thin-film solar cells, which convert light into electricity; and organic thin-film transistors, which control current and voltage. Among these, organic thin-film solar cells are particularly useful for environmental protection because they do not release carbon dioxide into the atmosphere, and their simple structure makes them easy to manufacture, leading to increasing demand.

[0004] Patent No. 6500786, Patent No. 6658727

[0005] The photoelectric conversion efficiency η of organic thin-film solar cells is still insufficient. Photoelectric conversion efficiency η is calculated as the product of the short-circuit current density Jsc, the open-circuit voltage Voc, and the curve factor FF. To increase photoelectric conversion efficiency η, it is necessary to improve the short-circuit current density Jsc and the open-circuit voltage Voc, in addition to improving the curve factor FF. Photoelectric conversion efficiency η = Short-circuit current density Jsc × Open-circuit voltage Voc × Curve factor FF

[0006] The problem to be solved by this disclosure is to provide an organic electronic device with high photoelectric conversion efficiency η by increasing the short-circuit current density Jsc and open-circuit voltage Voc of the organic electronic device. Another problem to be solved by this disclosure is to provide an organic semiconductor material that can be suitably used when manufacturing such an organic electronic device. Another problem to be solved by this disclosure is to provide a polymer compound that can be suitably used as a raw material for such an organic semiconductor material, and a composition containing the polymer compound.

[0007] The disclosure is as follows: [1] A polymer compound having alternating donor units and acceptor units, satisfying the UV characteristics shown in (1) and (2) below. (1) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound alone is measured, it shows one maximum peak between 500 nm and 800 nm. (2) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound and

[60] PCBM in a mass ratio of 1:1 is measured, it shows two maximum peaks between 500 nm and 800 nm. [2] The polymer compound according to [1], wherein the donor units have structural units represented by the following formula (1). [In formula (1), T １ , T ２ Each of these independently represents: a hydrogen atom; an alkoxy group; a thioalkoxy group; a thiophene ring which may be substituted with a hydrocarbon group or an organosilyl group; a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group; or a benzene ring which may be substituted with one or more selected from hydrocarbon groups, alkoxy groups, thioalkoxy groups, organosilyl groups, halogen atoms, and trifluoromethyl groups. １ , B ２ This represents an ethynylene group, which may be a single bond; a thiophene ring that may be substituted with a hydrocarbon group; a thiazole ring that may be substituted with a hydrocarbon group. * represents a bond. ] [3] The above T １ , T ２ However, each group is independently represented by one of the following formulas (t1) to (t5) in the polymer compound described in [2]. [In formulas (t1) to (t5), R １３ , R １４ each independently represents a hydrocarbon group having 6 to 30 carbon atoms. R １５ , R １６ each independently represents a hydrocarbon group having 6 to 30 carbon atoms, or a group represented by *-Si(R １８ ). R １７ each independently represents a hydrocarbon group having 6 to 30 carbon atoms, *-Si(R １８ ), *-O-R １９ , *-S-R ２０ , a halogen atom, or *-CF ３ . n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 2, n3 represents an integer of 0 to 5, respectively, and a plurality of R １５ may be the same or different, a plurality of R １６ may be the same or different, and a plurality of R １７ may be the same or different. 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 , R ２０ each independently represents a hydrocarbon group having 6 to 30 carbon atoms. * represents a bond.]. [4] The polymer compound according to [2] or [3], wherein the B １ , B ２ are each independently a group represented by any one of the following formulas (b1) to (b3). [In formulas (b1) to (b3), R ２１ , R ２２ represent a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. n4 represents an integer of 0 to 2. * represents a bond.]. [5] The polymer compound according to any one of [1] to [4], wherein the acceptor unit has a structural unit represented by the following formula (2). [In formula (2), R １ ​​​​∫ represents a hydrogen atom; a hydrocarbon group; or an alkoxy group. * represents a bond. ] [6] A composition comprising the polymer compound described in any of [1] to [5]. [7] The composition according to [6], further comprising a fullerene compound. [8] An organic electronic device comprising the composition according to [6]. [9] The organic electronic device according to [8], wherein the composition further comprises a fullerene compound.

[10] An organic semiconductor material comprising the polymer compound described in any of [1] to [5].

[11] The organic semiconductor material according to

[10] , further comprising a fullerene compound.

[12] The organic semiconductor material according to

[11] , wherein the fullerene compound comprises C60.

[13] The fullerene compound further comprises an aromatic ring and carboxyC １－１０ The organic semiconductor material according to

[11] or

[12] , which is a fullerene compound having an alkyl group as a substituent.

[14] An organic electronic device comprising the organic semiconductor material according to

[10] .

[15] The organic electronic device according to

[14] , wherein the organic semiconductor material further comprises a fullerene compound.

[16] The organic electronic device according to

[15] , wherein the fullerene compound comprises C60.

[17] The fullerene compound further comprises an aromatic ring and a carboxyl C １－１０ The organic electronic device according to

[15] or

[16] , which is a fullerene compound having an alkyl group as a substituent.

[0008] This disclosure provides an organic electronic device with a high short-circuit current density Jsc and open-circuit voltage Voc, and a high photoelectric conversion efficiency η. Furthermore, this disclosure provides an organic semiconductor material that can be suitably used in manufacturing such an organic electronic device. This disclosure also provides a polymer compound that can be suitably used as a raw material for such an organic semiconductor material, and a composition containing the polymer compound.

[0009] Figure 1 shows the ultraviolet-visible absorption spectrum of a film containing P-THDT-DBTH-DMO-IMTH alone, obtained in Example 1. Figure 2 shows the ultraviolet-visible absorption spectrum of a film containing P-THDT-DBTH-DMO-IMTH alone, obtained in Comparative Example 1. Figure 3 shows the ultraviolet-visible absorption spectrum of a film obtained using mixed solution 1 containing P-THDT-DBTH-DMO-IMTH obtained in Example 1. Figure 4 shows the ultraviolet-visible absorption spectrum of a film obtained using mixed solution 2 containing P-THDT-DBTH-DMO-IMTH obtained in Comparative Example 1.

[0010] In the embodiment, the polymer compound has donor units and acceptor units arranged alternately, and satisfies the UV characteristics shown in (1) and (2) below. (1) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound alone is measured, it shows one maximum peak between 500 nm and 800 nm. (2) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound and

[60] PCBM in a mass ratio of 1:1 is measured, it shows two maximum peaks between 500 nm and 800 nm.

[0011] By using polymer compounds that satisfy these UV characteristics, for example, as organic semiconductor materials, it is possible to improve the characteristics of organic electronic devices, particularly the short-circuit current density Jsc and the open-circuit voltage Voc. As a result, the photoelectric conversion efficiency η of organic electronic devices can be increased. By utilizing ultraviolet-visible absorption spectra, it is possible to evaluate the microscopic crystallinity of materials with low crystallinity where peaks are hardly detectable by X-ray crystallography (XRD), and the correlation between ultraviolet-visible absorption spectra and the performance of organic electronic devices has been clarified.

[0012] When measuring the ultraviolet-visible absorption spectrum of a film containing a polymer compound alone (hereinafter sometimes referred to as a single film), a polymer compound that shows one maximum peak between 500 nm and 800 nm shows two maximum peaks between 500 nm and 800 nm when measuring the ultraviolet-visible absorption spectrum of a film containing the same polymer compound and

[60] PCBM in a mass ratio of 1:1 (hereinafter sometimes referred to as a mixed film). This suggests that the single film has less regularly arranged polymers and lower crystallinity than the mixed film. This low crystallinity is thought to be due to the low amount of homocoupling of acceptor units in the polymer. In other words, homocouplings of acceptor units tend to have high planarity, so crystallinity increases as the content of homocouplings of acceptor units increases. However, because the amount of homocouplings of acceptor units is low, the crystallinity is considered to be low. Because there are few homocoupling groups of acceptor units and regions with low crystallinity, the conjugation length is relatively difficult to extend, which is thought to increase the HOMO-LUMO band gap and deepen the HOMO level. The open-circuit voltage Voc of organic electronic devices is correlated with the difference between the HOMO level of the donor material and the LUMO level of the acceptor material. Therefore, it is thought that as the HOMO level of the donor material deepens and drops, the open-circuit voltage Voc of the organic electronic device increases. In addition, as can be seen from the two maximum peaks in the bulk heterojunction as a whole between 500 nm and 800 nm, there are also regions with high crystallinity, so carrier (electron and hole) transfer can be carried out without problems. Polymer compounds will be explained below.

[0013] (Donor Units) Examples of donor units include thiophenes such as thienothiophene, ethylenedioxythiophene, bithiophene, benzodithiophene, cyclopentadichithiophene, silolodithiophene, germolodithiophene, dithienothiophene, benzothiophene, dibenzothiophene, and polythiophene; thiazoles such as cyclopentadithiazole, silolodithiazole, benzothiazole, and benzobisthiazole; thiadiazoles; benzodioxazoles; and benzoxazoles. Examples of units include oxazoles; imidazoles; furans such as furans, bifurans, benzodifurans, dithienofrans, dibenzofurans, and benzofurans; selenophenes such as selenoselenophenes, bicerenofenes, benzodiserenofen, and benzoselenophenes; pyrroles such as thienopyrroles, dithienopyrroles, benzopyrroles, and dibenzopyrroles; dithienopyrans; fluorenes such as silafluorenes; dibenzogermols; and triphenylamines. These units may be used individually or in combination of two or more. Thiazoles are preferred, and benzobisthiazoles are more preferred.

[0014] If the donor unit is a benzobisthiazole unit, the benzobisthiazole donor unit may have a structural unit represented by, for example, the following formula (1). In formula (1), T １ , T ２ Each of these independently represents: a hydrogen atom; an alkoxy group; a thioalkoxy group; a thiophene ring which may be substituted with a hydrocarbon group or an organosilyl group; a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group; or a benzene ring which may be substituted with one or more selected from hydrocarbon groups, alkoxy groups, thioalkoxy groups, organosilyl groups, halogen atoms, and trifluoromethyl groups. １ , B ２This represents an ethynylene group, which can be a single bond; a thiophene ring that may be substituted with a hydrocarbon group; or a thiazole ring that may be substituted with a hydrocarbon group. * represents a bond with an acceptor unit.

[0015]

[0016] T 1 , T 2 Each of these independently represents a hydrogen atom, an alkoxy group, a thioalkoxy group, a thiophene ring, a thiazole ring, or a benzene ring. The thiophene ring may be substituted with a hydrocarbon group or an organosilyl group. The thiazole ring may be substituted with a hydrocarbon group or an organosilyl group. The benzene ring may be substituted with one or more selected from a hydrocarbon group, an alkoxy group, a thioalkoxy group, an organosilyl group, a halogen atom, and a trifluoromethyl group.

[0017] An alkoxy group is a group in which a linear alkyl group, a branched alkyl group, or a cyclic alkyl group is bonded to an oxygen atom.

[0018] A thioalkoxy group is a group in which a linear alkyl group, a branched alkyl group, or a cyclic alkyl group is bonded to a sulfur atom.

[0019] The number of carbon atoms in the hydrocarbon group may be, for example, 6 to 30, preferably 8 to 24, more preferably 8 to 20, and even more preferably 8 to 16. A larger number of carbon atoms in the hydrocarbon group improves solubility in organic solvents, but if it becomes too large, the reactivity in the coupling reaction decreases.

[0020] The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, but a branched aliphatic hydrocarbon group is preferred. The branching of the aliphatic hydrocarbon group can increase the solubility of the coupling compound in organic solvents. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred.

[0021] Preferably, the hydrocarbon group is an alkyl group, specifically a C6 alkyl group such as n-hexyl; a C7 alkyl group such as n-heptyl; a C8 alkyl group such as n-octyl, 1-n-butylbutyl, 1-n-propylpentyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 1-methylheptyl, 2-methylheptyl, 6-methylheptyl, 2,4,4-trimethylpentyl, 2,5-dimethylhexyl; n-nonyl, 1-n-propylpentyl C9 alkyl groups such as pyruhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2,3,3,4-tetramethylpentyl group, 3,5,5-trimethylhexyl group; n-decyl group, 1-n-pentylpentyl group, 1-n-butylhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-ethyloctyl group, 2-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3,7-di C10 alkyl groups such as methyloctyl group; C11 alkyl groups such as n-undecyl group, 1-n-butylheptyl group, 2-n-butylheptyl group, 1-n-propyloctyl group, 2-n-propyloctyl group, 1-ethylnonyl group, 2-ethylnonyl group; C12 alkyl groups such as n-dodecyl group, 1-n-pentylheptyl group, 2-n-pentylheptyl group, 1-n-butyloctyl group, 2-n-butyloctyl group, 1-n-propylnonyl group, 2-n-propylnonyl group; n-tridecyl group, 1-n-pentyl C13 alkyl groups such as tyloctyl group, 2-n-pentyloctyl group, 1-n-butylnonyl group, 2-n-butylnonyl group, 1-methyldodecyl group, 2-methyldodecyl group; C14 alkyl groups such as n-tetradecyl group, 1-n-heptylheptyl group, 1-n-hexyloctyl group, 2-n-hexyloctyl group, 1-n-pentylnonyl group, 2-n-pentylnonyl group; C15 alkyl groups such as n-pentadecyl group, 1-n-heptyloctyl group, 1-n-hexylnonyl group, 2-n-hexylnonyl group;Examples include C16 alkyl groups such as n-hexadecyl group, 2-n-hexyldecyl group, 1-n-octyloctyl group, 1-n-heptylnonyl group, and 2-n-heptylnonyl group; C17 alkyl groups such as n-heptadecyl group and 1-n-octylnonyl group; C18 alkyl groups such as n-octadecyl group and 1-n-nonylnonyl group; C19 alkyl groups such as n-nonadecyl group; C20 alkyl groups such as n-eicosyl group and 2-n-octyldodecyl group; C21 alkyl groups such as n-heneicosyl group; C22 alkyl groups such as n-docosyl group; C23 alkyl groups such as n-tricosyl group; and C24 alkyl groups such as n-tetracosyl group and 2-n-decyltetradecyl group. In particular, the alkyl group may have 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms. Among these, the group may be 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl, n-hexadecyl, 2-n-hexyldecyl, 1-n-octyloctyl, 1-n-heptylnonyl, 2-n-heptylnonyl, 2-n-octyldodecyl, or 2-n-decyltetradecyl, preferably n-hexadecyl, 2-n-hexyldecyl, 1-n-octyloctyl, 1-n-heptylnonyl, 2-n-heptylnonyl, and more preferably 2-n-hexyldecyl. When the hydrocarbon group is one of the above groups, the solubility of the coupling compound in organic solvents improves, and it acquires appropriate crystallinity.

[0022] The hydrocarbon group is preferably a branched saturated hydrocarbon group, and more preferably a branched alkyl group having 8 to 16 carbon atoms.

[0023] The organosilyl group is a monovalent group in which one or more hydrocarbon groups are substituted on a Si atom, and the number of hydrocarbon groups substituted on the Si atom is preferably two or more, and more preferably three.

[0024] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0025] T １ , T ２Each of these is preferably a thiophene ring which may be substituted with a hydrocarbon group. １ , T ２ These may be identical or different, but from the viewpoint of ease of manufacture, they are preferably identical.

[0026] T １ , T ２ Each of these groups is preferably independently represented by one of the following formulas (t1) to (t5). That is, T １ , T ２ The alkoxy group represented by is preferably the group represented by the following formula (t1), T １ , T ２ The thioalkoxy group represented by is preferably the group represented by the following formula (t2), T １ , T ２ The thiophene ring represented by is preferably the group represented by the following formula (t3), T １ , T ２ The thiazole ring represented by the following formula (t4) is preferred, T １ , T ２ The benzene ring represented by the following formula (t5) is preferred. １ , T ２ If the group is represented by any of the following equations (t1) to (t5), it can absorb short-wavelength light and, due to its high planarity, efficiently forms π-π stacking, thereby further increasing the energy conversion efficiency PCE. １ , T ２ Each of these groups is independently more preferably represented by the following formula (t3). In formulas (t1) to (t5), * represents a bond that attaches to the thiazole ring of the benzobisthiazole compound that constitutes the structural unit represented by formula (1).

[0027]

[0028] In formulas (t1) to (t5), R １３ , R １４ Each of these independently represents a hydrocarbon group having 6 to 30 carbon atoms. １５ , R １６Each of these independently comprises a hydrocarbon group having 6 to 30 carbon atoms, or *-Si(R １８ ) ３ Represents the group represented by R. １７ Each of these independently consists of a hydrocarbon group having 6 to 30 carbon atoms, *-Si(R １８ ) ３ , *-O-R １９ , *-S-R ２０ , halogen atom, or *-CF ３ This represents n1 an integer from 0 to 3, n2 an integer from 0 to 2, and n3 an integer from 0 to 5, and multiple R １５ They may be the same or different, and there may be multiple R １６ They may be the same or different, and there may be multiple R １７ They may be the same or different. １８ Each of these independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and multiple R １８ They may be the same or different. １９ , R ２０ Each of these independently represents a hydrocarbon group with 6 to 30 carbon atoms. * represents a bonding bond.

[0029] R １３ ~R １７ The hydrocarbon group having 6 to 30 carbon atoms represented by may be a linear hydrocarbon group or a branched hydrocarbon group, but a branched hydrocarbon group is preferred, and more preferably a branched saturated hydrocarbon group. １３ ~R １７ The branching of the hydrocarbon group with 6 to 30 carbon atoms represented by R increases the solubility in organic solvents, allowing the coupling compound to obtain appropriate crystallinity. １３ ~R １７ The number of carbon atoms in the hydrocarbon group represented by R increases with increasing carbon number, which improves solubility in organic solvents. However, if it becomes too large, the reactivity in the coupling reaction described later decreases, making it difficult to synthesize the desired compound. Therefore, R １３ ~R １７ The number of carbon atoms in the hydrocarbon group represented is preferably 6 to 30, more preferably 8 to 25, even more preferably 8 to 20, and particularly preferably 8 to 16. １３ ~R１７ Specific examples of the hydrocarbon group having 6 to 30 carbon atoms represented by the above T 1 , T 2 can be referred to the description of the hydrocarbon group in １３ ~R １７ The hydrocarbon group having 6 to 30 carbon atoms represented by is preferably a branched alkyl group having 8 to 16 carbon atoms.

[0030] In the formulas (t3) to (t5), R １５ ~R １７ In the group of *-Si(R １８ ), R ３ 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. When R １８ ~R １５ ~R １７ is a group represented by *-Si(R １８ ), the solubility of the coupling compound in an organic solvent is improved. ３ <0S000427>

[0031] Examples of the halogen atom represented by R １７ include, for example, fluorine, chlorine, bromine, and iodine.

[0032] The number of carbon atoms of the aliphatic hydrocarbon group represented by R １８ is preferably 1 to 18, more preferably 1 to 8. Examples of the aliphatic hydrocarbon group represented by R １８ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, isobutyl group, n-pentyl group, tert-pentyl group, isopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 2-octylbutyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, 2-hexadecyl group, n-heptadecyl group, octadecyl group, etc. The number of carbon atoms of the aromatic hydrocarbon group represented by R １８ is preferably 6 to 8, more preferably 6 or 7, and particularly preferably 6. １８Examples of aromatic hydrocarbon groups represented by include the phenyl group. Among them, R １８ Preferably, the aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, more preferably a branched aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferred, and particularly preferably an isopropyl group. Multiple R １８ They may be the same or different, but it is preferable that they be the same.

[0033] In equations (t3) to (t5), R １５ ~R １７ *-Si(R １８ ) ３ Examples of the groups include alkylsilyl groups such as trimethylsilyl group, ethyldimethylsilyl group, isopropyldimethylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, triethylsilyl group, triisobutylsilyl group, tripropylsilyl group, tributylsilyl group, dimethylphenylsilyl group, and methyldiphenylsilyl group; and arylsilyl groups such as triphenylsilyl group and tert-butylchlorodiphenylsilyl group. Among these, alkylsilyl groups are preferred, and trimethylsilyl group or triisopropylsilyl group are particularly preferred.

[0034] In equation (t5), R １７ *-O-R １９ or *-S-R ２０ R under the basis １９ or R ２０ Each of these independently represents a hydrocarbon group having 6 to 30 carbon atoms, and as a hydrocarbon group having 6 to 30 carbon atoms, the above R １３ ~R １７ The groups exemplified as hydrocarbon groups having 6 to 30 carbon atoms, represented by [the formula], can preferably be used.

[0035] In equation (t3), multiple R １５ These may be the same or different, but it is preferable that they be the same. n1 is preferably 1 or 2, and more preferably 1. Formula (t3) is preferably the following formula (t3-1).

[0036]

[0037] In equation (t4), multiple R １６ These may be the same or different, but it is preferable that they be the same. n2 is preferably 1. Formula (t4) is preferably the following formula (t4-1).

[0038]

[0039] In equation (t5), multiple R １７ These may be the same or different, but it is preferable that they be the same. n3 is preferably an integer between 1 and 3, more preferably 1 or 2, and even more preferably 1.

[0040] B １ , B ２ Each of these independently represents a single bond, a thiophene ring, a thiazole ring, or an ethynylene group. The thiophene ring may be substituted with a hydrocarbon group. The thiazole ring may be substituted with a hydrocarbon group.

[0041] The number of carbon atoms in the hydrocarbon group may be, for example, 6 to 30, preferably 8 to 24, more preferably 8 to 20, and particularly preferably 8 to 16. A larger number of carbon atoms in the hydrocarbon group improves solubility in organic solvents, but if it becomes too large, the reactivity in the coupling reaction decreases. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. Branching of the aliphatic hydrocarbon group can increase solubility in organic solvents. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specific examples of hydrocarbon groups are shown in the above T. 1 , T 2 You can refer to the description of hydrocarbon groups in [the relevant section].

[0042] B １ , B ２ Each of these is preferably a thiophene ring substituted with a hydrocarbon group. １ , B ２ These may be identical or different, but from the viewpoint of ease of manufacture, they are preferably identical.

[0043] B １ , B ２ Each of these is preferably a group represented independently by one of the following formulas (b1) to (b3). That is, B １ , B ２ The thiophene ring represented by is preferably the group represented by the following formula (b1), B １ , B ２ The thiazole ring represented by is preferably the group represented by the following formula (b2), B １ , B ２ The ethynylene group represented by the following formula (b3) is preferred. １ , B ２ If the group is represented by any of the following formulas (b1) to (b3), the planarity of the resulting coupling compound will be good, and the photoelectric conversion efficiency will be further improved.

[0044] B １ , B ２ Each of these groups is more preferably represented by the following formula (b1).

[0045]

[0046] In formulas (b1) to (b3), R ２１ , R ２２ n represents a hydrogen atom or a hydrocarbon group having 6 to 30 carbon atoms. n4 represents an integer from 0 to 2. * represents a bond. In particular, the * on the left represents a bond attached to the benzene ring of the benzobisthiazole compound that constitutes the structural unit represented by formula (1).

[0047] R ２１ , R ２２ Specific examples of hydrocarbon groups having 6 to 30 carbon atoms, as represented by the above T, are 1 , T 2 You can refer to the description of hydrocarbon groups in R. ２１ , R ２２ It is preferable that the atom is a hydrogen atom because it facilitates the formation of a donor-acceptor type semiconductor polymer. ２１ , R ２２ It is preferable that n4 is a hydrocarbon group having 6 to 30 carbon atoms, as this may further increase the photoelectric conversion efficiency. It is preferable that n4 is 0.

[0048] Formula (b1) is preferably the following formula (b1-1).

[0049]

[0050] Formula (b2) is preferably the following formula (b2-1).

[0051]

[0052] (Acceptor Units) Examples of acceptor units include structural units represented by the following formulas (c1) to (c18). These units may be used individually or in combination of two or more types. Homocoupling bodies of these units exhibit high planarity.

[0053]

[0054] In formula (c1), R １ This represents a hydrogen atom, a hydrocarbon group, or an alkoxy group.

[0055] R １ The number of carbon atoms in the hydrocarbon group represented by R may be, for example, 6 to 30, preferably 8 to 24, more preferably 8 to 20, and particularly preferably 8 to 16. A larger number of carbon atoms in the hydrocarbon group improves solubility in organic solvents, but if it becomes too large, the reactivity in the coupling reaction decreases. １ The hydrocarbon group represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, but a branched aliphatic hydrocarbon group is preferred. By having a branched aliphatic hydrocarbon group, the solubility of the coupling compound in organic solvents can be increased. R １ The hydrocarbon group represented may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. Specific examples of hydrocarbon groups are shown in the above T. 1 , T 2 You can refer to the description of hydrocarbon groups in R. １The hydrocarbon group represented is preferably a branched saturated hydrocarbon group, and more preferably a branched alkyl group having 8 to 16 carbon atoms. １ It is preferable that it be a hydrocarbon group.

[0056] R １ The alkoxy group represented by may be, for example, a linear alkyl group, a branched alkyl group, or a cyclic alkyl group bonded to an oxygen atom. The number of carbon atoms in the alkyl group bonded to the oxygen atom may be, for example, 6 to 30.

[0057] In formulas (c2) to (c18), R ３０ * represents a hydrocarbon group with 6 to 30 carbon atoms. j represents an integer from 0 to 2, and k represents an integer from 0 to 4. * represents a bond with an acceptor unit.

[0058] R ３０ The number of carbon atoms in the hydrocarbon group represented by is preferably 8 to 24, more preferably 8 to 20, and particularly preferably 8 to 16. A larger number of carbon atoms in the hydrocarbon group improves solubility in organic solvents, but if it becomes too large, the reactivity in the coupling reaction decreases. ３０ The hydrocarbon group represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group, but a branched aliphatic hydrocarbon group is preferred. By having a branched aliphatic hydrocarbon group, the solubility of the coupling compound in organic solvents can be increased. R ３０ The hydrocarbon group represented may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred. Specific examples of hydrocarbon groups are shown in the above T. 1 , T 2 You can refer to the description of hydrocarbon groups in R. ３０ The hydrocarbon group represented is preferably a branched saturated hydrocarbon group, and more preferably a branched alkyl group having 8 to 16 carbon atoms.

[0059] j can be an integer between 0 and 1, or it can be 0, independently of the others. k can be an integer between 0 and 1, or it can be 0.

[0060] If the acceptor unit is any of the structural units represented by formulas (c1) to (c18) above, the acceptor unit is preferably a unit represented by formula (c1) or formula (c2), and more preferably a unit represented by formula (c1). That is, the acceptor unit may have, for example, a structural unit represented by the following formula (2). In formula (2), R １ * represents a hydrogen atom, a hydrocarbon group, or an alkoxy group. * represents a bond with an acceptor unit.

[0061]

[0062] (UV properties) The polymer compound satisfies the UV properties shown in (1) and (2) below. (1) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound alone is measured, it shows one maximum peak between 500 nm and 800 nm. (2) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound and

[60] PCBM in a mass ratio of 1:1 is measured, it shows two maximum peaks between 500 nm and 800 nm.

[0063] By using polymer compounds that satisfy these UV characteristics as organic semiconductor materials, the short-circuit current density Jsc and open-circuit voltage Voc of the resulting organic electronic device are increased, and the photoelectric conversion efficiency η is improved. For measuring the ultraviolet-visible absorption spectrum of a film containing the polymer compound alone, and for measuring the ultraviolet-visible absorption spectrum of a film containing the polymer compound and

[60] PCBM in a mass ratio of 1:1, chlorobenzene can be used as the solvent. The specific measurement procedure will be described in detail in the examples.

[0064] Polymeric compounds consist of alternating donor and acceptor units. Such polymeric compounds can be produced by coupling a compound that serves as a raw material for the donor units (hereinafter sometimes referred to as compound A) with a compound that serves as a raw material for the acceptor units (hereinafter sometimes referred to as compound B). Examples of coupling reactions include the Yamamoto reaction, Sonogashira reaction, Suzuki coupling reaction, Still reaction, and C-H activation reaction.

[0065] Specific coupling reactions include: Method 1, in which a halogenated compound that serves as a raw material for the donor unit is reacted with a compound that serves as a raw material for the acceptor unit; Method 2, in which a halogenated compound that serves as a raw material for the donor unit is reacted with a compound that serves as a raw material for the acceptor unit; Method 3, in which a tin compound that serves as a raw material for the donor unit is reacted with a compound that serves as a raw material for the acceptor unit; and Method 4, in which a compound that serves as a raw material for the donor unit is reacted with a tin compound that serves as a raw material for the acceptor unit. Method 1 or Method 2 is preferred, and Method 1 is more preferred.

[0066] When the coupling reaction is carried out by method 1 or method 2 above, it is preferable that the halogenated compound (or compound) that serves as the raw material for the donor unit and the halogenated compound (or compound) that serves as the raw material for the acceptor unit are coupled in the presence of at least one compound selected from monoarylphosphine, bis(monoarylphosphine), diarylphosphine, and bis(diarylphosphine); a salt thereof; or a complex thereof (hereinafter, these may be collectively referred to as phosphine compounds).

[0067] The phosphine compound present in the coupling reaction step may be at least one compound selected from monoarylphosphine, bis(monoarylphosphine), diarylphosphine, or bis(diarylphosphine); a salt thereof; or a complex thereof; and two or more may be used in combination. Hereafter, even when monoarylphosphine, bis(monoarylphosphine), diarylphosphine, or bis(diarylphosphine) are written, it means that a salt thereof or a complex thereof is included.

[0068] When using monoarylphosphine, bis(monoarylphosphine), diarylphosphine, or bis(diarylphosphine) individually, it is preferable to use diarylphosphine or bis(monoarylphosphine).

[0069] When using two or more monoarylphosphines, bis(monoarylphosphine), diarylphosphines, or bis(diarylphosphine) in combination, the combination of phosphine compounds used is not particularly limited. For example, two or more monoarylphosphines, two or more bis(monoarylphosphines), two or more diarylphosphines, or two or more bis(diarylphosphines) may be used in combination. Alternatively, two or more compounds selected from the group consisting of monoarylphosphine, bis(monoarylphosphine), diarylphosphine, and bis(diarylphosphine) may be used in combination, and the combination is not particularly limited. Examples include combinations of monoarylphosphine and diarylphosphine, monoarylphosphine and bis(monoarylphosphine), monoarylphosphine and bis(diarylphosphine), bis(monoarylphosphine) and diarylphosphine, bis(monoarylphosphine) and bis(diarylphosphine), and diarylphosphine and bis(diarylphosphine). Among these, combinations of monoarylphosphine and diarylphosphine, bis(monoarylphosphine) and diarylphosphine, bis(monoarylphosphine) and bis(diarylphosphine), and monoarylphosphine and bis(monoarylphosphine) are preferred.

[0070] A monoarylphosphine or diarylphosphine may be a compound represented by the following formula (3), a salt of the compound represented by the following formula (3), or a complex of the compound represented by the following formula (3). In formula (3), R ３１ is an alkyl or alkenyl group, p is 1 or 2, and R ３２ R is an aryl group, where q is 1 or 2, and p+q is 3. ３１ , R ３２ Each of these may independently have substituents. ３１ These may be the same or different. Multiple R ３２ They may be the same or they may be different.

[0071]

[0072] If the monoarylphosphine or diarylphosphine is a compound represented by formula (3) above, then R ３１ The number of carbon atoms in each alkyl group represented by R may be independently, for example, 1 to 10, preferably 2 to 8, and more preferably 2 to 6. ３１ The number of carbon atoms in each of the alkenyl groups represented by can be independently, for example, 2 to 10, preferably 2 to 8, and more preferably 2.

[0073] R ３１ Each alkyl group represented by R may independently be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, with cyclic alkyl groups being preferred. ３２ The number of carbon atoms in each aryl group represented by can be independently, for example, 6 to 20, preferably 6 to 16, and more preferably 6 to 12.

[0074] R ３２ Examples of aryl groups represented by include phenyl, naphthyl, indenyl, and biphenyl groups, with phenyl or biphenyl groups being preferred.

[0075] In formula (3), when p is 2 and q is 1, the compound represented by formula (3) is represented by the following formula (3-1). In formula (3), when p is 1 and q is 2, the compound represented by formula (3) is represented by the following formula (3-2). The compound represented by formula (3-1) is a monoarylphosphine, and the compound represented by formula (3-2) is a diarylphosphine.

[0076]

[0077] R ３１ Alkyl alkyl groups represented by R ３２ Each of the aryl groups represented by may independently have substituents.

[0078] R ３１ If there are multiple alkyl groups represented by R, one may be substituted, or both may be substituted.３１ The alkyl group represented by is preferably unsubstituted.

[0079] R ３２ If there are multiple aryl groups represented by R, one may be substituted, or both may be substituted. ３２ The aryl group represented by is preferably substituted.

[0080] When the alkyl group has substituents, the substituents are not particularly limited and include, for example, halogen atoms and alkoxy groups having 1 to 6 carbon atoms, with alkoxy groups having 1 carbon atom being preferred.

[0081] When the aryl group has substituents, the substituents are not particularly limited and include, for example, halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, etc., with C1-C3 alkyl groups and C1 alkoxy groups being preferred.

[0082] Examples of compounds represented by formula (3-1) include those represented by the following formulas (3-1-1) to (3-1-3). The compound represented by formula (3-1-1) is 2(dicyclohexylphosphino)biphenyl. The compound represented by formula (3-1-2) is 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, which may hereafter be written as Xphos. The compound represented by formula (3-1-3) is 2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl, which may hereafter be written as Brettphos.

[0083]

[0084] Examples of compounds represented by formula (3-2) include those represented by the following formulas (3-2-1) or (3-2-2).

[0085]

[0086] In formula (3-2-1), R ８１The number of carbon atoms in the alkyl group represented by is preferably 2 to 4, and more preferably 2. R82 and R83 each independently represent integers from 0 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0087] R ８２ , R ８３ The number of carbon atoms in each alkyl group represented by may be independently 1 to 6.

[0088] -OR bonded to the benzene ring ８２ , -OR ８３ The position is not particularly limited; each can be independently at the ortho position, the meta position, or the para position, or -OR ８２ and - OR ８３ The positions may be the same or different. -OR ８２ and - OR ８３ If the positions are the same, the compound represented by formula (3-2-1) above can be represented by the following formulas (3-2-1a) to (3-2-1c).

[0089]

[0090] Examples of compounds represented by formula (3-2-1) include those represented by the following formulas (3-2-1-1) to (3-2-1-4).

[0091]

[0092] In the compounds represented by formulas (3-2-1-1) to (3-2-1-4), R ８２ , R ８３ When the alkyl group represented by has 1 carbon atom, the compounds represented by formulas (3-2-1-1) to (3-2-1-4) are represented by the following formulas (3-2-1-1a) to (3-2-1-4a). The compound represented by the following formula (3-2-1-1a) is bis(2-methoxyphenyl)methylphosphine, and hereafter referred to as (anisyl). ２ PCH ３ It is sometimes written as follows. The compound name represented by the following formula (3-2-1-2a) is bis(2-methoxyphenyl)ethylphosphine, and hereafter referred to as (anisyl) ２ P(C) ２ H ５It is sometimes written as ). The compound name represented by the following formula (3-2-1-3a) is bis(2-methoxyphenyl)cyclohexylphosphine, and hereafter referred to as (anisyl) ２ It is sometimes written as PCy. The compound name represented by the following formula (3-2-1-4a) is bis(2,4-dimethoxyphenyl)cyclohexylphosphine, and hereafter referred to as (2,4-dimethoxyphenyl) ２ It is sometimes written as PCy.

[0093]

[0094] In formula (3-2-2), R ９１ , R ９２ The number of carbon atoms in each alkyl group represented by can be independently 1 to 6. r91 and r92 each independently represent integers from 0 to 5, preferably 1 or 2, and more preferably 1.

[0095] -OR bonded to the benzene ring ９１ , -OR ９２ The position is not particularly limited; each can be independently at the ortho position, the meta position, or the para position, or -OR ８２ and - OR ８３ The positions may be the same or different. -OR ８２ and - OR ８３ If the positions are the same, the compound represented by the above formula (3-2-2) can be represented by the following formulas (3-2-2a) to (3-2-2c).

[0096]

[0097] In the compound represented by formula (3-2-2a), R ９１ , R ９２ When the alkyl group represented by has 1 carbon atom, the compound represented by formula (3-2-2a) is represented by the following formula (3-2-2a-1). The compound represented by the following formula (3-2-2a-1) is bis(2-methoxyphenyl)vinylphosphine, and hereafter referred to as (anisyl). ２ P(C) ２ H ３ ) is sometimes written as .

[0098]

[0099] If the monoarylphosphine or diarylphosphine is a salt of the compound represented by formula (3) above, the salt may be, for example, BF ４ － , PF ６ － Salts such as BF ４ － A salt is preferred.

[0100] When the monoarylphosphine or diarylphosphine is a complex of the compound represented by formula (3) above, examples of complexes include those of a titanium atom, zirconium atom, vanadium atom, niobium atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom, nickel atom, and palladium atom, with palladium atom being preferred.

[0101] Bis(monoarylphosphine) or bis(diarylphosphine) may contain a compound represented by the following formula (4) or formula (5).

[0102] In formula (4) and formula (5), R ４１ａ , R ４１ｂ , R ４１ｃ Each of them is an alkyl group, R ５１ａ , R ５１ｂ , R ５１ｃ Each of these is an aryl group independently. In formula (4), ra is 0 or 1, sa is 1 or 2, and ra + sa is 2. In formula (5), ta is 1 or 2, ua is 0 or 1, and ta + ua is 2. R ４１ａ , R ４１ｂ , R ４１ｃ , R ５１ａ , R ５１ｂ , R ５１ｃ Each of these may independently have substituents. ４１ａ These may be the same or different. Multiple R ４１ｂ These may be the same or different. Multiple R ５１ａ These may be the same or different. Multiple R ５２ｂThese may be the same or different. For the compounds represented by formula (4) and formula (5), the type of optically active compound is not particularly limited and may be any of the (S,S) isomer, (R,R) isomer, (S,R) isomer, (R,S) isomer, or racemic mixture.

[0103]

[0104] R ４１ａ , R ４１ｂ , R ４１ｃ The number of carbon atoms in each alkyl group represented by can be independently, for example, 1 to 10, preferably 2 to 8, and more preferably 2 to 6.

[0105] R ４１ａ , R ４１ｂ , R ４１ｃ Each of the alkyl groups represented by may independently be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group.

[0106] R ４１ａ , R ４１ｂ Each of the alkyl groups represented is preferably a cyclic alkyl group.

[0107] R ４１ｃ The alkyl group represented is preferably a linear alkyl group.

[0108] R ５１ａ , R ５１ｂ , R ５１ｃ The number of carbon atoms in each aryl group represented by can be independently, for example, 6 to 20, preferably 6 to 16, and more preferably 6 to 12.

[0109] R ５１ａ , R ５１ｂ , R ５１ｃ Examples of aryl groups represented by R include phenyl, naphthyl, indenyl, and biphenyl groups. ５１ａ , R ５１ｂ Each of the aryl groups represented is preferably a phenyl group. ５１ｃ The aryl group represented is preferably a phenyl group.

[0110] In formula (4), ra is 0 or 1, sa is 1 or 2, and ra + sa is 2. When ra is 1 and sa is 1, the compound represented by formula (4) is represented by the following formula (4-1). When ra is 0 and sa is 2, the compound represented by formula (4) is represented by the following formula (4-2). The compound represented by formula (4-1) is bis(monoarylphosphine), and the compound represented by formula (4-2) is bis(diarylphosphine). Preferably, ra is 0 and sa is 2, that is, the compound represented by the following formula (4-2) is preferred.

[0111]

[0112] In formula (5), ta is 1 or 2, ua is 0 or 1, and ta + ua is 2. When ta is 2 and ua is 0, the compound represented by formula (5) is represented by formula (5-1) below. When ta is 1 and ua is 1, the compound represented by formula (5) is represented by formula (5-2) below. The compound represented by formula (5-1) is bis(monoarylphosphine), and the compound represented by formula (5-2) is bis(diarylphosphine). Ta is preferably 2 and ua is preferably 0, that is, the compound represented by formula (5-1) below is preferred.

[0113]

[0114] R ４１ａ , R ４１ｂ , R ４１ｃ Alkyl alkyl groups represented by R ５１ａ , R ５１ｂ , R ５１ｃ Each of the aryl groups represented by may independently have substituents.

[0115] R ４１ａ , R ４１ｂ One of the alkyl groups represented by may be substituted, or both may be substituted, but it is preferable that one is substituted. ４１ｃ The alkyl group represented by is preferably unsubstituted.

[0116] R ５１ａ , R ５１ｂOne of the aryl groups represented by R may be substituted, or both may be substituted, but it is preferable that one of them is substituted. ５１ｃ The aryl group represented by is preferably unsubstituted.

[0117] When the alkyl group has substituents, the substituents are not particularly limited and include, for example, halogen atoms and alkoxy groups having 1 to 6 carbon atoms, with alkoxy groups having 1 carbon atom being preferred.

[0118] When the aryl group has substituents, the substituents are not particularly limited and include, for example, halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, etc., with a C1 alkoxy group being preferred.

[0119] Examples of compounds represented by formula (4-2) include the compound represented by the following formula (4-2-1). In formula (4-2-1), R ８１ , R ８２ Each of these independently represents an alkyl group having 1 to 6 carbon atoms. Each of r83 and r84 independently represents an integer from 0 to 5, preferably 1 to 3, and more preferably 1.

[0120]

[0121] The compound represented by formula (4-2-1) specifically includes the compound represented by the following formula (4-2-1a). The compound represented by the following formula (4-2-1a) is named 1,2-ethanediylbis[(2-methoxyphenyl)phenylphosphine], and is hereinafter sometimes referred to as DIPAMP. The optically active form of DIPAMP is not particularly limited and may be any of the (S,S) isomer, (R,R) isomer, (S,R) isomer, (R,S) isomer, or racemic mixture.

[0122]

[0123] Bis(monoarylphosphine) or bis(diarylphosphine) may contain a compound represented by the following formula (6) or formula (7).

[0124] In formula (6) and formula (7), R ６１ａ , R ６１ｂ , R ６１ｃ , R６１ｄ Each of them is an alkyl group, R ７１ａ , R ７１ｂ , R ７１ｃ , R ７１ｄ Each of these is an aryl group independently. In formula (6), va is 0 or 1, wa is 1 or 2, and va + wa is 2. In formula (7), xa is 1 or 2, ya is 0 or 1, and xa + ya is 2. R ６１ａ , R ６１ｂ , R ６１ｃ , R ６１ｄ , R ７１ａ , R ７１ｂ , R ７１ｃ , R ７１ｄ Each of these may independently have substituents. ６１ａ These may be the same or different. Multiple R ６１ｂ These may be the same or different. Multiple R ７１ａ These may be the same or different. Multiple R ７２ｂ They may be the same or they may be different.

[0125]

[0126] R ６１ａ , R ６１ｂ , R ６１ｃ , R ６１ｄ The number of carbon atoms in each alkyl group represented by can be independently, for example, 1 to 10, preferably 2 to 8, and more preferably 2 to 6.

[0127] R ６１ａ , R ６１ｂ , R ６１ｃ , R ６１ｄ Each alkyl group represented by R may independently be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. ６１ａ , R ６１ｂ Each alkyl group represented is preferably a cyclic alkyl group. ６１ｃ , R ６１ｄ The alkyl group represented is preferably a linear alkyl group.

[0128] R ７１ａ, R ７１ｂ , R ７１ｃ , R ７１ｄ The number of carbon atoms in each aryl group represented by can be independently, for example, 6 to 20, preferably 6 to 16, and more preferably 6 to 12.

[0129] R ７１ａ , R ７１ｂ , R ７１ｃ , R ７１ｄ Examples of aryl groups represented by R include phenyl, naphthyl, indenyl, and biphenyl groups. ７１ａ , R ７１ｂ Each of the aryl groups represented is preferably a phenyl group. ７１ｃ , R ７１ｄ Each of the aryl groups represented is preferably a phenyl group.

[0130] In formula (6), va is 0 or 1, wa is 1 or 2, and va + wa = 2. When va is 1 and wa is 1, the compound represented by formula (6) is represented by the following formula (6-1). When va is 0 and wa is 2, the compound represented by formula (6) is represented by the following formula (6-2). The compound represented by formula (6-1) is bis(monoarylphosphine), and the compound represented by formula (6-2) is bis(diarylphosphine). Preferably, va is 0 and wa is 2, that is, the compound represented by the following formula (6-2) is preferred.

[0131]

[0132] In formula (7), xa is 1 or 2, ya is 0 or 1, and ta + ua is 2. When xa is 2 and ya is 0, the compound represented by formula (7) is represented by formula (7-1) below. When xa is 1 and ya is 1, the compound represented by formula (7) is represented by formula (7-2) below. The compound represented by formula (7-1) is bis(monoarylphosphine), and the compound represented by formula (7-2) is bis(diarylphosphine). xa is preferably 2 and ya is preferably 0, that is, the compound represented by formula (7-1) below is preferred.

[0133]

[0134] R ６１ａ , R ６１ｂ , R ６１ｃ , R ６１ｄ Alkyl alkyl groups represented by R ７１ａ , R ７１ｂ , R ７１ｃ , R ７１ｄ Each of the aryl groups represented by may independently have substituents.

[0135] R ６１ａ , R ６１ｂ One of the alkyl groups represented by R may be substituted, or both may be substituted. ６１ｃ , R ６１ｄ The alkyl group represented by is preferably unsubstituted.

[0136] R ７１ａ , R ７１ｂ One of the aryl groups represented by R may be substituted, or both may be substituted. ７１ｃ , R ７１ｄ The aryl group represented by is preferably unsubstituted.

[0137] When the alkyl group has substituents, the substituents are not particularly limited and include, for example, halogen atoms and alkoxy groups having 1 to 6 carbon atoms, with alkoxy groups having 1 carbon atom being preferred.

[0138] When the aryl group has substituents, the substituents are not particularly limited and include, for example, halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, etc., with a C1 alkoxy group being preferred.

[0139] The compound represented by formula (7-1) is preferably the compound represented by the following formula (7-1-1a). The name of the compound represented by the following formula (7-1-1a) is 1,1'-(oxydi-2,1-phenylene)bis[1,1-dicyclohexylphosphine], and it may be referred to as Cy-DPEphos below.

[0140]

[0141] The molar ratio of compound A to compound B may be in the range of 1:99 to 99:1, preferably in the range of 1:4 to 4:1, and more preferably in the range of 2:3 to 3:2.

[0142] The coupling reaction may also be carried out in the presence of a metal catalyst. Examples of metal catalysts include transition metal catalysts. Examples of transition metal catalysts include palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Palladium-based catalysts are preferred among these. The palladium in the palladium-based catalyst may be 0-valent or 2-valent.

[0143] Examples of palladium-based catalysts include palladium(II) chloride, palladium(II) bromide, palladium(II) iodide, palladium(II) oxide, palladium(II) sulfide, palladium(II) telluride, palladium(II) hydroxide, palladium(II) selenide, palladium cyanide, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, diacetate bis(triphenylphosphine)palladium(II), tetrakis(triphenylphosphine)palladium(II), dichlorobis(triphenylphosphine)palladium(II), dichlorobis(acetonitrile)palladium(II), dichlorobis(benzonitrile)palladium(II), dichloro[1,2-bis(diphenylphosphine)ethane]palladium(II), dichloro[1,3-bis(diphenylphosphine)propane]palladium(II), and dichloro[1,4-bis (Diphenylphosphino)butane]palladium(II), dichloro[1,1-bis(diphenylphosphinoferrocene)]palladium(II), dichloro[1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct, bis(dibenzylideneacetone)palladium(O), tris(dibenzylideneacetone)dipalladium(O), tris(dibenzylideneacetone)dipalladium(O) chloroform adduct, dichloro[1, Examples include 3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene](3-chloropyridyl)palladium(II), bis(tri-tert-butylphosphine)palladium(O), dichloro[2,5-norbornadiene]palladium(II), dichlorobis(ethylenediamine)palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), and dichlorobis(methyldiphenylphosphine)palladium(II). These catalysts may be used individually or in combination of two or more. Among them, dichlorobis(acetonitrile)palladium(II)[PdCl ２ (MeCN) ２ ] or Tris(dibenzylideneacetone) dipalladium(0) chloroform adduct [[Pd ２ (dba) ３]・CHCl ３ ] is preferred, and more preferably PdCl ２ (MeCN) ２ That is the case.

[0144] The molar ratio of compound A to the metal catalyst (compound A:metal catalyst) may be about 1:0.001 to 1:0.1, but from the viewpoint of yield and reaction efficiency, 1:0.005 to 1:0.08 is preferred, more preferably 1:0.01 to 1:0.06, and even more preferably 1:0.01 to 1:0.04.

[0145] The coupling reaction may also be carried out in the presence of a base. Examples of bases include alkali metal salt compounds such as lithium hydride, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, and barium carbonate; alkoxy-alkali metal compounds such as lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide, potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide, and potassium tert-amyl alkoxide; and metal hydride compounds such as lithium hydride, sodium hydride, and potassium hydride. These bases may be used individually or in combination of two or more. Among these, alkali metal salt compounds are preferred, with sodium carbonate, potassium carbonate, and cesium carbonate being more preferred, and cesium carbonate being even more preferred.

[0146] When a base is present in a coupling reaction, the molar ratio of compound A to base (compound A:base) may be, for example, about 1:1 to 1:8, but from the viewpoint of yield and reaction efficiency, 1:1.5 to 1:6 is preferred, more preferably 1:1.8 to 1:5, and even more preferably 1:2 to 1:4.

[0147] When reacting compound A and compound B, a solvent may be used, but the type of solvent is not particularly limited as long as it does not affect the reaction, and conventionally known solvents can be used.

[0148] Examples of solvents that can be used include ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents, nitrile solvents, sulfoxide solvents, and sulfone solvents. Examples of ether solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane. Examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin. Examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate. Examples of hydrocarbon solvents include pentane, hexane, heptane, octane, and decalin. Examples of halogen solvents include dichloromethane, chloroform, dichloroethane, and dichloropropane. Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidinone. Examples of nitrile solvents include acetonitrile. Examples of sulfoxide solvents include dimethyl sulfoxide. Examples of sulfone solvents include sulfolane. These solvents may be used individually or in combination of two or more. Among these, tetrahydrofuran, toluene, chlorobenzene, and N,N-dimethylformamide are preferred, and toluene is more preferred.

[0149] The mass ratio of compound A to solvent (compound A:solvent) may be, for example, about 1:4 to 1:50, but from the viewpoint of yield and reaction efficiency, 1:4 to 1:45 is preferred, and more preferably 1:4 to 1:40.

[0150] This disclosure also includes compositions containing the above polymer compounds. The above compositions may further contain n-type semiconductor compounds. Examples of n-type semiconductor compounds include fullerene compounds and non-fullerene compounds, with fullerene compounds being preferred.

[0151] The above composition may further contain a solvent. For example, an aromatic solvent can be used as the solvent. Examples of aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and tetralin. The aromatic solvent may be halogenated, for example. Examples of halogenated aromatic solvents include iodobenzene and diiodobenzene.

[0152] This disclosure also includes organic semiconductor materials containing the above polymer compound. The above organic semiconductor material may further contain an n-type semiconductor compound. Examples of n-type semiconductor compounds include fullerene compounds and non-fullerene compounds, with fullerene compounds being preferred. When the above organic semiconductor material contains the above polymer compound and a fullerene compound, the polymer compound acts as a donor material and the fullerene compound acts as an acceptor material.

[0153] Examples of fullerene compounds included in the above composition or organic semiconductor material include fullerenes represented by C60, C70, C76, C78, ​​C80, C82, C84, C86, C88, C90, C96, C116, C180, C240, C540, and the like. Among these, the inclusion of C60 is preferred. For example, C60 means that the number of carbon atoms is 60.

[0154] The fullerene compound may be unsubstituted or substituted, but substituted compounds are preferred.

[0155] When a fullerene compound is substituted, examples of substituents include aromatic rings, heterocycles, hydrocarbon groups, carboxyl groups, and carboxyalkyl groups. In particular, fullerene compounds can have aromatic rings and carboxyl groups as substituents. １－１０ It is preferable that the group has an alkyl group. Examples of aromatic rings include benzene rings. Examples of heterocycles include pyrrolidine rings. Examples of hydrocarbon groups include alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 3 to 10 carbon atoms. Examples of carboxyalkyl groups include carboxyC １－１０ Alkyl groups are examples. C １－１０ This means that the number of carbon atoms is between 1 and 10. １－１０ Alkyl alkyl groups refer to alkyl groups with 1 to 10 carbon atoms.

[0156] The fullerene compound is preferably a fullerene compound represented by substituted C60, C70, or C86, and more preferably a fullerene compound represented by substituted C60.

[0157] Examples of substituted fullerene compounds having an aromatic ring and a carboxymethyl group include

[60] PCBM (phenyl C ６１ Examples include methyl butyrate.

[0158] Other substituted fullerene compounds include, for example, those in which the C60 portion of

[60] PCBM is replaced with C70, C86, etc., those in which the benzene ring of the substituent is replaced with another aromatic ring or heterocycle, and those in which the carboxymethyl group is replaced with a carboxyethyl group, a carboxybutyl group, etc.

[0159] Examples of non-fullerene compounds included in the above composition or organic semiconductor material include perylene carboxylic acid diimide and its derivatives, fluorinated phthalocyanine, perfluorinated pentacene, cyanostilbene, cyanoparaphenylene vinylene, bisthiazole derivatives, thiophene oligomer derivatives, and ITIC.

[0160] This disclosure also includes organic electronic devices containing the above-mentioned organic semiconductor material. This disclosure also includes organic electronic devices containing the above-mentioned composition. Examples of organic electronic devices include organic electroluminescent devices, organic thin-film solar cells, and organic thin-film transistors.

[0161] This application claims the benefit of priority based on Japanese Patent Application No. 2025-015507, filed on 31 January 2025. The entire contents of the specification of the aforementioned Japanese Patent Application No. 2025-015507 are incorporated herein by reference.

[0162] The contents of this disclosure will be explained in more detail below with reference to examples, but the contents of this disclosure are not limited by the examples below, and it is of course possible to implement modifications to the extent that are consistent with the spirit described above and below, and all such modifications are included within the technical scope of this disclosure. In the following, unless otherwise specified, "%" means "mass %".

[0163] The following raw materials were used in the examples and comparative examples.

[0164] (Raw materials) 4,8-bis(5-bromothiophen-2-yl)-2,6-bis[5-(2-hexyldecyl)thiophen-2-yl]-benzo[1,2-d;4,5-d']bisthiazole (hereinafter sometimes referred to as DTH-DBTH-HDTH-DB) was synthesized by the method of Reference Example 7 described in WO2016 / 121589. 5-(3,7-dimethyloctyl)thieno[3,4-c]pyrrole-4,6-dione (hereinafter sometimes referred to as DMO-IMTH) was synthesized by the method of Example 1 described in WO2022 / 054459. 2,6-bis[5-(2-ethylhexyl)thiophen-2-yl]-4,8-bis(5-trimethylstannylthiophen-2-yl)-benzo[1,2-d;4,5-d']bisthiazole (hereinafter sometimes referred to as DTH-DBTH-HDTH-DSM) was synthesized by the method of Example 17 described in Japanese Patent No. 6500786.

[0165] (Gel Permeation Chromatography (GPC)) The molecular weight of the compound was measured using gel permeation chromatography (GPC). The measurement was performed by dissolving the compound in the mobile phase solvent to a concentration of 1 g / L, under the following conditions, and calculating the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the compound based on a calibration curve prepared using polystyrene as a standard sample. The GPC measurement conditions were as follows: Mobile phase: Orthodichlorobenzene (0.5% BHT) Flow rate: 0.3 mL / min Apparatus: HLC-8321 GPC / HT (Tosoh Corporation) Column: Styragel HT6E, HT4, HT3 (Waters, 4.6 mm × 300 mm, 3-pack, fractionation range 500 to 10,000,000) Detector: RI (differential refraction) detector Measurement temperature: 140°C

[0166] (Ultraviolet-Visible Absorption Spectrum; Single Film) The obtained donor material was dissolved in chlorobenzene to a concentration of 8.0 g / L, deposited on a glass substrate using a spin coater, and dried under reduced pressure to produce a single film. The ultraviolet-visible absorption spectrum of this film was measured using an ultraviolet-visible spectrometer (Shimadzu Corporation, "UV-3600iPlus").

[0167] (UV-Vis absorption spectrum; mixed film) Obtained donor material and acceptor material [

[60] PCBM (phenyl C ６１ A mixed film was prepared by dissolving the total concentration of methyl butyrate (-methyl butyrate) in chlorobenzene in a 1:1 mass ratio, so that the total concentration was 40 mg / mL to 44 mg / mL, depositing the film on a glass substrate using a spin coater, and drying it under reduced pressure. The ultraviolet-visible absorption spectrum of this film was measured using an ultraviolet-visible spectrometer (Shimadzu Corporation, "UV-3600iPlus").

[0168] (Example 1) Under a nitrogen atmosphere, in a 20 mL flask, add DTH-DBTH-HDTH-DB (0.300 g, 0.266 mmol), DMO-IMTH (0.078 g, 0.266 mmol), and bis(acetonitrile)dichloropalladium(II) [PdCl ２ (MeCN) ２, 1.4 mg, 2 mol%], bis(2-methoxyphenyl)vinylphosphine [(anisyl) ２ P(C) ２ H ３ Adding 4.1 mg, 6 mol% of [1,1'-(oxydi-2,1-phenylene)bis(1,1-dicyclohexylphosphine)[Cy-DPEphos, 7.4 mg, 5 mol%], neodecanoic acid (0.045 g, 1.0 equivalent), cesium carbonate (0.252 g, 2.9 equivalents), and toluene (2.7 mL), the mixture was reacted at 110°C for 23 hours. After the reaction was complete, the reaction solution was added to methanol (6 mL), and the precipitated solid was filtered off. The obtained solid was then washed with Soxhlet (methanol, acetone, hexane). Subsequently, Soxhlet extraction (chloroform) yielded 0.313 g of black solid P-THDT-DBTH-DMO-IMTH. GPC measurement results: weight-average molecular weight (Mw) = 31600, number-average molecular weight (Mn) = 14400, Mw / Mn = 2.2

[0169]

[0170] (Comparative Example 1) Under a nitrogen atmosphere, a 200 mL flask was filled with DTH-DBTH-HDTH-DSM (1.52 g, 1.17 mmol), DMO-IMTH-DB (0.528 g, 1.17 mmol), and Tris(dibenzylideneacetone)dipalladium(0)chloroform adduct [[Pd ２ (dba) ３ ]・CHCl ３ 54.6 mg, 4 mol%], Tris(2-methoxyphenyl)phosphine [P(2MeO-Ph)] ３[60.6 mg, 15 mol%] and chlorobenzene (60 mL) were added and the mixture was reacted at 135°C for 23 hours. After the reaction was complete, the reaction solution was added to methanol (130 mL), the precipitated solid was filtered off, and the obtained solid was washed with Soxhlet (methanol, acetone, hexane). Then, Soxhlet extraction (chloroform) was performed to obtain 1.41 g of black solid P-THDT-DBTH-DMO-IMTH (yield 95.6%). Note that DMO-IMTH-DB is a brominated form of DMO-IMTH. GPC measurement results: weight-average molecular weight (Mw) = 37600, number-average molecular weight (Mn) = 16400, Mw / Mn = 2.3

[0171]

[0172] A film containing P-THDT-DBTH-DMO-IMTH (donor material) obtained in Example 1 was prepared, and the ultraviolet-visible absorption spectrum of the film was measured. The measurement results are shown in Figure 1 below. A film containing P-THDT-DBTH-DMO-IMTH (donor material) obtained in Comparative Example 1 was prepared, and the ultraviolet-visible absorption spectrum of the film was measured. The measurement results are shown in Figure 2 below.

[0173] As is clear from Figure 1, the ultraviolet-visible absorption spectrum of the film containing P-THDT-DBTH-DMO-IMTH alone obtained in Example 1 had one maximum peak between 500 nm and 800 nm. As is clear from Figure 2, the ultraviolet-visible absorption spectrum of the film containing P-THDT-DBTH-DMO-IMTH alone obtained in Comparative Example 1 had two maximum peaks between 500 nm and 800 nm.

[0174] (Preparation of mixed solution 1 of p-type semiconductor compound and n-type semiconductor compound) As the p-type semiconductor compound, P-THDT-DBTH-DMO-IMTH obtained in Example 1 was used, and as the n-type semiconductor compound,

[60] PCBM (phenyl C ６１Using methyl butyrate, the mass ratio of the p-type semiconductor compound to the n-type semiconductor compound was set to 1:1, and dissolved in chlorobenzene together with diiodobenzene (0.03 mL / mL). The total concentration of the p-type and n-type semiconductor compounds was 44 mg / mL. The resulting solution was stirred and mixed on a hot stirrer at a temperature of 100°C for more than 2 hours. After stirring and mixing, the solution was filtered through a 0.45 μm filter to prepare a mixed solution 1 of the p-type and n-type semiconductor compounds.

[0175] (Preparation of mixed solution 2 of p-type semiconductor compound and n-type semiconductor compound) As the p-type semiconductor compound, P-THDT-DBTH-DMO-IMTH obtained in Comparative Example 1 was used, and as the n-type semiconductor compound,

[60] PCBM (phenyl C ６１ Using methyl butyrate, the mass ratio of the p-type semiconductor compound to the n-type semiconductor compound was set to 1:1, and dissolved in chlorobenzene together with diiodobenzene (0.03 mL / mL). The total concentration of the p-type and n-type semiconductor compounds was 40 mg / mL. The resulting solution was stirred and mixed on a hot stirrer at a temperature of 100°C for more than 2 hours. After stirring and mixing, the solution was filtered through a 0.45 μm filter to prepare a mixed solution 2 of the p-type and n-type semiconductor compounds.

[0176] A film was prepared using mixed solution 1, and its ultraviolet-visible absorption spectrum was measured. The measurement results are shown in Figure 3 below. A film was prepared using mixed solution 2, and its ultraviolet-visible absorption spectrum was measured. The measurement results are shown in Figure 4 below.

[0177] As is clear from Figure 3, the ultraviolet-visible absorption spectrum of the film using mixed solution 1 had two maximum peaks between 500 nm and 800 nm. As is clear from Figure 4, the ultraviolet-visible absorption spectrum of the film using mixed solution 2 also had two maximum peaks between 500 nm and 800 nm.

[0178] Next, using the obtained mixed solution 1 or mixed solution 2, an inverse configuration device was fabricated as an organic electronic device, and the photoelectric conversion efficiency η was measured.

[0179] (Fabrication of Organic Electronic Devices) A ​​glass substrate manufactured by Geomatec, which had a transparent conductive film of indium tin oxide (ITO) patterned on it to serve as the cathode electrode, was ultrasonically cleaned with acetone, then ultrasonically cleaned with ethanol, and then dried with nitrogen blow. After UV-ozone treatment was performed on the dried glass substrate, an electron transport layer was formed. The electron transport layer was formed by applying a 0.5 M zinc acetate / 0.5 M aminoethanol / 2-methoxyethanol solution to the glass substrate using a spin coater (3000 rpm, 40 seconds), and then annealing at 175°C for 30 minutes. The glass substrate with the electron transport layer formed was brought into a glove box, and either the above mixed solution 1 or the above mixed solution 2 was spin-coated under an inert gas atmosphere, followed by annealing or vacuum drying on a hot plate to form the active layer. Next, molybdenum oxide, which would serve as the hole transport layer, was deposited using a vapor deposition machine. Then, silver, which would serve as the anode electrode, was deposited to fabricate an inverted configuration device. The obtained inverse configuration device was evaluated using a solar simulator according to the following procedure for evaluating the organic electronic device.

[0180] (Evaluation method for organic electronic devices) A ​​0.05027 mm square metal mask is attached to an inverted configuration device, and a solar simulator (OTENTO-SUNIIII manufactured by Spectrometer Co., Ltd., AM1.5G filter, radiant intensity 100 mW / cm²) is used as the illumination light source. ２ Using a source meter (Kaysley, Model 2400), the current-voltage characteristics between the ITO electrode (cathode electrode) and the silver electrode (anode electrode) were measured. From the measurement results, the short-circuit current density Jsc (mA / cm²) was calculated. ２ The open-circuit voltage Voc (V), curve factor FF, and photoelectric conversion efficiency η (%) were calculated. The short-circuit current density Jsc is the current density when the voltage value is 0V. The open-circuit voltage Voc is the current density when the current value is 0mA / cm². ２ This is the voltage value at that time. The curve factor FF is a factor representing the internal resistance, and if the maximum output is Pmax, the curve factor FF is expressed by the following equation: FF = Pmax / (Jsc × Voc)

[0181] The photoelectric conversion efficiency η is calculated using the following formula: η = Jsc × Voc × FF

[0182] The inverted device fabricated using the above mixed solution 1 has a short-circuit current density Jsc of 13.135 mA / cm². ２ The open-circuit voltage Voc was 0.839 V, the curve factor FF was 0.702, and the photoelectric conversion efficiency η was 7.74%.

[0183] The inverted device fabricated using the above mixed solution 2 has a short-circuit current density Jsc of 12.80 mA / cm². ２ The open-circuit voltage Voc was 0.799 V, the curve factor FF was 0.707, and the photoelectric conversion efficiency η was 7.23%.

[0184] As is clear from Figures 1 to 4 and the evaluation results of the organic electronic device, the polymer compounds obtained in Example 1 and Comparative Example 1 were both P-THDT-DBTH-DMO-IMTH, but differences in crystallinity were detected, such that the peaks were almost undetectable by X-ray crystallography (XRD) according to the ultraviolet-visible absorption spectra. It was found that by using the polymer compound obtained in Example 1, the short-circuit current density Jsc and open-circuit voltage Voc of the organic electronic device could be increased compared to using the polymer compound obtained in Comparative Example 1, and the photoelectric conversion efficiency η could be increased by 0.51%.

Claims

1. A polymer compound having alternating donor units and acceptor units, satisfying the UV characteristics shown in (1) and (2) below. (1) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound alone is measured, it shows one maximum peak between 500 nm and 800 nm. (2) When the ultraviolet-visible absorption spectrum of a film containing the polymer compound and [60]PCBM in a mass ratio of 1:1 is measured, it shows two maximum peaks between 500 nm and 800 nm.

2. The polymer compound according to claim 1, wherein the donor unit has a structural unit represented by the following formula (1). [In formula (1), T １ , T ２ Each of these independently represents: a hydrogen atom; an alkoxy group; a thioalkoxy group; a thiophene ring which may be substituted with a hydrocarbon group or an organosilyl group; a thiazole ring which may be substituted with a hydrocarbon group or an organosilyl group; or a benzene ring which may be substituted with one or more selected from hydrocarbon groups, alkoxy groups, thioalkoxy groups, organosilyl groups, halogen atoms, and trifluoromethyl groups. １ , B ２ This represents an ethynylene group, which may be a single bond; a thiophene ring that may be substituted with a hydrocarbon group; or a thiazole ring that may be substituted with a hydrocarbon group. * represents a bond.

3. The T １ and T ２ in the polymer compound according to claim 2 are each independently a group represented by any one of the following formulas (t1) to (t5). [In formulas (t1) to (t5), R １３ and R １４ each independently represent a hydrocarbon group having 6 to 30 carbon atoms. R １５ and R １６ each independently represent a hydrocarbon group having 6 to 30 carbon atoms or a group represented by *-Si(R １８ ). R １７ each independently represent a hydrocarbon group having 6 to 30 carbon atoms, *-Si(R １８ ), *-O-R １９ , *-S-R ２０ , a halogen atom, or *-CF ３ . n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 2, n3 represents an integer of 0 to 5, respectively, and a plurality of R １５ may be the same or different, a plurality of R １６ may be the same or different, and a plurality of R １７ may be the same or different. 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 and R ２０ each independently represent a hydrocarbon group having 6 to 30 carbon atoms. * represents a bond.]​​​​ 4. The above B １ , B ２ The polymer compound according to claim 2, wherein each group is independently represented by any of the following formulas (b1) to (b3). [In formulas (b1) to (b3), R ２１ , R ２２ n4 represents a hydrogen atom or a hydrocarbon group with 6 to 30 carbon atoms. n4 represents an integer from 0 to 2. * represents a bonding bond.

5. The polymer compound according to claim 1, wherein the acceptor unit has a structural unit represented by the following formula (2). [In formula (2), R １ * represents a hydrogen atom; a hydrocarbon group; or an alkoxy group. * represents a bond.

6. A composition comprising the polymer compound described in any one of claims 1 to 5.

7. The composition according to claim 6, further comprising a fullerene compound.

8. An organic electronic device comprising the composition described in claim 6.

9. The organic electronic device according to claim 8, wherein the composition further comprises a fullerene compound.

10. An organic semiconductor material comprising the polymer compound described in any one of claims 1 to 5.

11. The organic semiconductor material according to claim 10, further comprising a fullerene compound.

12. The organic semiconductor material according to claim 11, wherein the fullerene compound contains C60.

13. The fullerene compound further comprises an aromatic ring and a carboxyl C １－１０ The organic semiconductor material according to claim 11, which is a fullerene compound having an alkyl group as a substituent.

14. An organic electronic device comprising the organic semiconductor material described in claim 10.

15. The organic electronic device according to claim 14, wherein the organic semiconductor material further comprises a fullerene compound.

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