Compound, composition, ink, photoelectric conversion element, and light sensor

Abstract

To provide: a novel compound; a composition and an ink that contain the compound; a photoelectric conversion element having a lower dark current; and a light sensor.SOLUTION: A compound is represented by the formula (1) in the figure. In the formula (1), D moieties are each independently a polycyclic aromatic group having two bonding sites; there are four or more double bonds in a conjugated structure that connects the two bonding sites by the shortest distance; L1 and L1' each independently denote an aromatic group having two bonding sites; there are three or fewer double bonds in a conjugated structure that connects the two bonding sites by the shortest distance; L2 is not the same chemical structure as D, and is an aromatic group having two bonding sites; n is 1 or 2; m is 0 or 1; n+m=2; and A1 and A2 are acceptor groups.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to compounds, compositions, inks, photoelectric conversion elements, and optical sensors.

Background Art

[0002] Photoelectric conversion elements are extremely useful devices, for example, from the viewpoints of energy saving and reduction of carbon dioxide emissions, and have attracted attention.

[0003] A photoelectric conversion element is an element including at least a pair of electrodes including an anode and a cathode, and an active layer provided between the pair of electrodes. In the photoelectric conversion element, at least one of the pair of electrodes is made of a transparent or translucent material, and light is incident on the active layer from the transparent or translucent electrode side. By the energy (hν) of the light incident on the active layer, charges (holes and electrons) are generated in the active layer, and the generated holes move toward the anode, and the electrons move toward the cathode. Then, the charges that have reached the anode and the cathode are taken out to the outside of the element.

[0004] Non-Patent Document 1 discloses that in an organic photodetector (OPD), which is one of photoelectric conversion elements, it is important to minimize dark current. By reducing the dark current, important performance indices such as the signal / noise ratio, linear dynamic range, and specific detectivity of the photoelectric conversion element can be improved.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] As a compound that can be used in a photoelectric conversion element, a non-fullerene acceptor (NFA) is known. However, the dark current in a conventional photoelectric conversion element using NFA was not sufficiently low. The present disclosure has been made in view of the above, and the present disclosure relates to providing a novel compound, a composition and an ink containing the compound, a photoelectric conversion element with reduced dark current, and an optical sensor.

Means for Solving the Problems

[0007] Specific means for solving the above problems include the following aspects. <1> A compound represented by the following formula (1).

[0008]

Chemical Formula

[0009] In formula (1), D is, independently of each other, a polycyclic aromatic group having two bonds, and the number of double bonds included in the conjugated structure that shortest connects the two bonds is 4 or more. L1 and L1' are, independently of each other, aromatic groups having two bonds, and the number of double bonds included in the conjugated structure that shortest connects the two bonds is 3 or less. L2 is not the same chemical structure as D and is an aromatic group having two bonds. n is 1 or 2, m is 0 or 1, and n + m = 2. A1 and A2 are acceptor groups. <2> The compound according to <1>, which is represented by the following formula (2).

[0010]

Chemical formula

[0011] In formula (2), D is a polycyclic aromatic group having two bonds, and the number of double bonds contained in the conjugated structure connecting the two bonds in the shortest way is 4 or more. L1 and L1' are each independently an aromatic group having two bonds, and the number of double bonds contained in the conjugated structure connecting the two bonds in the shortest way is 3 or less. L2 is an aromatic group having two bonds and is not of the same chemical structure as D. A1 and A2 are acceptor groups. <3> The compound according to <1> or <2>, wherein the polycyclic aromatic group contains a 5-membered ring structure, and the two bonds of the polycyclic aromatic group extend from the 5-membered ring structure respectively. <4> The compound according to any one of <1> to <3>, wherein the number of double bonds contained in the conjugated structure connecting the two bonds in L2 in the shortest way is 3 or less. <5> The compound according to any one of <1> to <4>, wherein L1, L1' and L2 are each independently such that the number of double bonds contained in the conjugated structure connecting the two bonds in the shortest way is 2 or less. <6> In D, the polycyclic aromatic group has a side chain, and the carbon to which the side chain is bonded is sp3 carbon or sp2 carbon. The compound according to any one of <1> to <5>, wherein the side chain has an aromatic ring or a branched chain. <7> The compound according to any one of <1> to <6>, wherein all of L1, L1' and L2 have different chemical structures from each other, or any two of L1, L1' and L2 have the same chemical structure. <8> D is a donor group and is a compound according to any one of <1> to <7> having a side chain with 6 or more carbon atoms. <9> D, L1, L1’ and L2 are all compounds according to any one of <1> to <8> having a sulfur-containing heterocyclic ring. <10> D is, independently of each other, any group represented by the following formula (D-1) to the following formula (D-7), and is a compound according to any one of <1> to <9>.

[0012]

Chemical formula

[0013] In formula (D-1), formula (D-2), formula (D-6) and formula (D-7), X is any group represented by the following formula (X-1) to formula (X-6).

[0014]

Chemical formula

[0015] In formula (D-3) to formula (D-7) and formula (X-1) to formula (X-6), R D1 is, independently of each other, a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substitutedoxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group, and Ar 1 and Ar 2 each independently represents an aromatic carbocyclic ring which may have a substituent and in which a plurality of ring structures may be further fused, or an aromatic heterocyclic ring which may have a substituent and in which a plurality of ring structures may be further fused. Either Ar 1 or Ar 2 may not be present. <11> L1 and L1’ are each independently any one of the groups represented by the following formula (L1-1) to formula (L1-9); the compound according to any one of <1> to <10>.

[0016]

Chemical formula

[0017] In formula (L1-1) to formula (L1-9), R L1 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group. <12> L2 is, independently of each other, any group represented by the following formula (L2-1) to formula (L2-9), and is a compound according to any one of <1> to <11>.

[0018]

Chemical formula

[0019] In formula (L2-1) to formula (L2-9), R L2 is, independently of each other, a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group. <13> A1 and A2 are each independently any one of the groups represented by the following formula (a-1) to formula (a-8), and are the compound according to any one of <1> to <12>.

[0020] [Chemical formula]

[0021] In formulas (a-1) to (a-8), a plurality of Rs A1 are each independently a hydrogen atom, a halogen atom, or a cyano group. <14> A composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material contains the compound according to any one of <1> to <13>. <15> The composition according to <14>, wherein the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

[0022]

Chemical formula

[0023] In formula (3), Ar 3 and Ar 4 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any group represented by the following formulas (Z-1) to (Z-7).

[0024]

Chemical formula

[0025] In formulas (Z-1) to (Z-7), Rs are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, A cycloalkylthio group which may have a substituent, An arylthio group which may have a substituent, A monovalent heterocyclic group which may have a substituent, A substituted amino group which may have a substituent, An acyl group which may have a substituent, An imine residue which may have a substituent, An amide group which may have a substituent, An acid imide group which may have a substituent, A substituted carbonyl group which may have a substituent, A substituted oxycarbonyl group which may have a substituent, A substituted sulfonyl group which may have a substituent, A substituted oxysulfonyl group which may have a substituent, An alkenyl group which may have a substituent, A cycloalkenyl group which may have a substituent, An alkynyl group which may have a substituent, A cycloalkynyl group which may have a substituent, A cyano group, or A nitro group, and In each of Formula (Z-1) to Formula (Z-7), when there are two Rs, the two Rs may be the same as or different from each other. In Formula (4), Ar 5 represents a divalent aromatic heterocyclic group. <16> An ink containing a p-type semiconductor material, an n-type semiconductor material, and a solvent, wherein the n-type semiconductor material contains the compound according to any one of <1> to <13>. <17> A photoelectric conversion element including an anode, a cathode, and an active layer provided between the anode and the cathode and containing a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material contains the compound according to any one of <1> to <13>. <18> The photoelectric conversion element according to <17>, which is a photodetector. <19> A photosensor including the photoelectric conversion element according to <18>. <20>A composition comprising a compound represented by the following formula (1) and a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

[0026]

Chemical formula

[0027] In formula (1), D is, independently of each other, a polycyclic aromatic group having two bonds, and the number of double bonds contained in the conjugated structure that shortest connects the two bonds is 4 or more, L1 and L1' are, independently of each other, aromatic groups having two bonds, and the number of double bonds contained in the conjugated structure that shortest connects the two bonds is 3 or less, L2 is not the same chemical structure as D and is an aromatic group having two bonds, n is 1 or 2, m is 0 or 1, and n + m = 2, A1 and A2 are, independently of each other, acceptor groups of any one of the following formulas (a-5) to (a-8).

[0028]

Chemical formula

[0029] In formula (3), Ar 3 and Ar 4 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any group represented by the following formulas (Z-1) to (Z-7).

[0030]

Chemical formula

[0031] In formulas (Z-1) to (Z-7), R is, independently of each other, An aryl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, or a cycloalkyl group which may have a substituent, and in each of Formula (Z-1) to Formula (Z-7), when there are two Rs, the two Rs may be the same as or different from each other. In Formula (4), Ar 5 represents a divalent aromatic heterocyclic group.

[0032] [Chemical formula]

[0033] In Formula (a-5) to Formula (a-8), a plurality of Rs A1 are each independently a hydrogen atom, a halogen atom, or a cyano group. [Advantages of the Invention]

[0034] According to the present disclosure, a novel compound, a composition and an ink containing the compound, a photoelectric conversion element with reduced dark current, and a photosensor are provided. [Brief Description of the Drawings]

[0035]

Figure 1

[0036] Hereinafter, an embodiment of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following disclosure, its components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present disclosure.

[0037] Hereinafter, the compounds of the present disclosure will be described, and further, the photoelectric conversion elements using the compounds of the present disclosure will be described with reference to the drawings. Note that the drawings only schematically show the shapes, sizes, and arrangements of the components to the extent that the invention can be understood. The present disclosure is not limited by the following description, and each component can be appropriately changed without departing from the gist of the present disclosure. Also, the configuration of the present disclosure is not necessarily manufactured or used in the arrangement shown in the drawings.

[0038] In the present disclosure, in the numerical range indicated by using "~", the numerical values described before and after "~" are included as the lower limit value and the upper limit value, respectively. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described stepwise. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, the content rate of each component in the composition means the total content rate of the plurality of substances corresponding to each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In the present disclosure, when a plurality of elements are listed using "or" or "alternatively", unless otherwise specified, the selection of combining the plurality of elements is not excluded as long as there is no technical contradiction. In the present disclosure, even when an element is represented in the singular form, unless otherwise specified, the existence of a plurality is not excluded as long as there is no technical contradiction. In the present disclosure, a plurality of separately described exemplary embodiments may be combined with each other to form a new embodiment as long as they do not contradict each other.

[0039] In the present disclosure, commonly used terms will be explained. In the description of the present disclosure, the following explanations apply unless otherwise specified individually.

[0040] The term "non-fullerene compound" refers to a compound that is neither a fullerene nor a fullerene derivative.

[0041] The term "π-conjugated system" means a system in which π electrons are delocalized over multiple bonds.

[0042] The term "polymer compound" means a polymer having a molecular weight distribution and a number average molecular weight in terms of polystyrene of 1×10 3 or more and 1×10 8 or less. The constituent units contained in the polymer compound total 100 mol%.

[0043] The term "constituent unit" means a residue derived from a raw material compound (monomer) that is present in one or more in a compound and a polymer compound.

[0044] The "hydrogen atom" may be a light hydrogen atom or a deuterium atom.

[0045] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0046] The aspect of "optionally having a substituent" includes both aspects where all hydrogen atoms constituting a compound or a group are unsubstituted and where some or all of one or more hydrogen atoms are substituted by a substituent.

[0047] Examples of the "substituent" include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkyloxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group, and a nitro group. In the present specification, when referring to the number of carbon atoms, usually, the number of carbon atoms of the substituent is not included in the number of carbon atoms.

[0048] In this specification, unless otherwise specified, the "alkyl group" may be linear, branched, or cyclic. The number of carbon atoms in the linear alkyl group, excluding the carbon atoms of the substituent, is usually preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20. The number of carbon atoms in the branched or cyclic alkyl group, excluding the carbon atoms of the substituent, is usually preferably 3 to 50, more preferably 3 to 30, and even more preferably 4 to 20.

[0049] Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isoamyl group, 2-ethylbutyl group, n-hexyl group, cyclohexyl group, n-heptyl group, cyclohexylmethyl group, cyclohexylethyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, adamantyl group, n-decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-n-hexyl-decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group.

[0050] The alkyl group may have a substituent. The alkyl group having a substituent is, for example, a group in which a hydrogen atom in the above-exemplified alkyl group is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.

[0051] Specific examples of the alkyl having a substituent include trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-dihexylphenyl)propyl group, 6-ethyloxyhexyl group.

[0052] The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group, excluding the number of carbon atoms in the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0053] Examples of the cycloalkyl group include alkyl groups having no substituent such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0054] Specific examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.

[0055] The "aromatic carbocyclic group" means a group remaining after removing any number of hydrogen atoms directly bonded to the carbon atoms constituting the ring from an aromatic hydrocarbon which may have a substituent. The aromatic carbocyclic group may further have a substituent. The "aromatic carbocycle" includes a structure in which two or more carbocycles (aromatic rings) are bridged by a group (substituent) containing a heteroatom, for example.

[0056] The "aryl group" is a monovalent aromatic carbocyclic group, and means a group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting the ring from an aromatic hydrocarbon which may have a substituent.

[0057] The aryl group may have a substituent. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a 4-pyrenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, a 2-phenylphenyl group, a 3-phenylphenyl group, a 4-phenylphenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0058] The "alkyloxy group" (alkoxy group) may be linear, branched, or cyclic. The number of carbon atoms in the linear alkyloxy group, excluding the carbon atoms of the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms in the branched or cyclic alkyloxy group, excluding the carbon atoms of the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0059] The alkyloxy group may have a substituent. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an n-decyloxy group, a 3,7-dimethyloctyloxy group, a 3-heptyldodecyloxy group, a lauryloxy group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0060] The cycloalkyl group of the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group, excluding the carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0061] Examples of the cycloalkyloxy group include cycloalkyloxy groups having no substituent, such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, and groups in which a hydrogen atom in these groups is substituted with a fluorine atom or an alkyl group.

[0062] The number of carbon atoms in the "aryloxy group", excluding the carbon atoms of the substituent, is usually preferably 6 to 60, more preferably 6 to 48.

[0063] The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 9-anthracenyloxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkyloxy group, or a fluorine atom.

[0064] The "alkylthio group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkylthio group, excluding the number of carbon atoms of the substituent, is usually preferably 1 to 40, more preferably 1 to 10. The number of carbon atoms of the branched and cyclic alkylthio groups, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 40, more preferably 4 to 10.

[0065] The alkylthio group may have a substituent. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a cyclohexylthio group, a heptylthio group, an octylthio group, a 2-ethylhexylthio group, a nonylthio group, a decylthio group, a 3,7-dimethyloctylthio group, a laurylthio group, and a trifluoromethylthio group.

[0066] The cycloalkyl group of the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms of the cycloalkylthio group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0067] An example of the cycloalkylthio group that may have a substituent is a cyclohexylthio group.

[0068] The number of carbon atoms in the "arylthio group" is usually preferably 6 to 60, more preferably 6 to 48, not including the carbon atoms of the substituent.

[0069] The arylthio group may have a substituent. Examples of the arylthio group include a phenylthio group, a C1-C12 alkyloxyphenylthio group (C1-C12 indicates that the number of carbon atoms in the group described immediately after is 1 to 12. The same applies hereinafter), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.

[0070] The "heterocyclic group" means a remaining atomic group obtained by removing any number of hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting the ring from a heterocyclic compound which may have a substituent.

[0071] The heterocyclic group may further have a substituent. The number of carbon atoms in the heterocyclic group is usually preferably 2 to 30, more preferably 2 to 6, not including the carbon atoms of the substituent.

[0072] Examples of the substituent that the heterocyclic compound may have include, for example, a halogen atom, an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group. The heterocyclic group includes an "aromatic heterocyclic group".

[0073] The "aromatic heterocyclic group" means a remaining atomic group obtained by removing any number of hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting the ring from an aromatic heterocyclic compound which may have a substituent. The aromatic heterocyclic group may further have a substituent.

[0074] Aromatic heterocyclic compounds include compounds in which the heterocyclic ring itself exhibits aromaticity, and in addition, compounds in which an aromatic ring is fused to the heterocyclic ring even if the heterocyclic ring itself does not exhibit aromaticity.

[0075] Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocyclic ring itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0076] Among aromatic heterocyclic compounds, specific examples of compounds in which the aromatic heterocyclic ring itself does not exhibit aromaticity and an aromatic ring is fused to the heterocyclic ring include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0077] The number of carbon atoms of the monovalent heterocyclic group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 60, more preferably 4 to 20.

[0078] The monovalent heterocyclic group may have a substituent. Specific examples of the monovalent heterocyclic group include, for example, thienyl group, pyrrolyl group, furyl group, pyridyl group, piperidyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group, and groups in which hydrogen atoms in these groups are substituted with an alkyl group, an alkyloxy group, etc.

[0079] The "substituted amino group" means an amino group having a substituent. Examples of the substituent of the amino group include an alkyl group, an aryl group, and a monovalent heterocyclic group, and an alkyl group, an aryl group, or a monovalent heterocyclic group is preferred. The number of carbon atoms of the substituted amino group is usually preferably 2 to 30.

[0080] Examples of the substituted amino group include dialkylamino groups such as dimethylamino group and diethylamino group; diarylamino groups such as diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl)amino group, and bis(3,5-di-tert-butylphenyl)amino group.

[0081] The "acyl group" may have a substituent. The number of carbon atoms of the acyl group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 20, more preferably 2 to 18. Specific examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group.

[0082] The "imine residue" means the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom or nitrogen atom constituting the carbon atom-nitrogen atom double bond from an imine compound. The "imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of the imine compound include aldimine, ketimine, and a compound in which the hydrogen atom bonded to the nitrogen atom constituting the carbon atom-nitrogen atom double bond in aldimine is substituted with an alkyl group or the like.

[0083] The imine residue usually preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formulas. In the following structural formulas, Me represents a methyl group.

[0084]

Chemical formula

[0085] The "amide group" means the remaining atomic group after removing one hydrogen atom bonded to the nitrogen atom from an amide. The number of carbon atoms in the amide group is usually preferably 1 to 20, more preferably 1 to 18. Specific examples of the amide group include formamide group, acetamide group, propionamide group, butyramide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropionamide group, dibutyramide group, dibenzamide group, ditrifluoroacetamide group, and dipentafluorobenzamide group.

[0086] The "acid imide group" means the remaining atomic group after removing one hydrogen atom bonded to the nitrogen atom from an acid imide. The number of carbon atoms in the acid imide group is usually preferably 4 to 20. Specific examples of the acid imide group include groups represented by the following structural formulas. In the following structural formulas, Me represents a methyl group.

[0087] [Chemical formula]

[0088] The "substituted carbonyl group" means a group represented by -(C=O)-R X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0089] The "substituted oxycarbonyl group" means a group represented by -(C=O)-O-R X or -O-(C=O)-R X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0090] The "substituted sulfonyl group" means a group represented by -SO2-R X Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0091] The "substituted oxysulfonyl group" refers to -(SO2)-O-R X or -O-(SO2)-R X and means a group represented thereby. Here, R X represents an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

[0092] The number of carbon atoms of the substituted oxycarbonyl group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 60, more preferably 2 to 48.

[0093] Specific examples of the substituted oxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group.

[0094] The "alkenyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkenyl group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 30, more preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkenyl group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 4 to 20.

[0095] The alkenyl group may have a substituent. Specific examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0096] The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group, excluding the number of carbon atoms of the substituent, is usually preferably 3 to 30, more preferably 12 to 19.

[0097] Examples of the cycloalkenyl group include cycloalkenyl groups having no substituent such as a cyclohexenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0098] Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.

[0099] The "alkynyl group" may be linear, branched, or cyclic. The number of carbon atoms of the linear alkynyl group, excluding the number of carbon atoms of the substituent, is usually preferably 2 to 20, more preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkynyl group, excluding the number of carbon atoms of the substituent, is usually preferably 4 to 30, more preferably 4 to 20.

[0100] The alkynyl group may have a substituent. Specific examples of the alkynyl group include an ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyloxy group, an aryl group, or a fluorine atom.

[0101] The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, excluding the number of carbon atoms in the substituent, is usually preferably 4 to 30, more preferably 12 to 19.

[0102] Examples of the cycloalkynyl group include cycloalkynyl groups having no substituent such as a cyclohexynyl group, and groups in which hydrogen atoms in these groups are substituted with an alkyl group, an alkyloxy group, an aryl group, or a fluorine atom.

[0103] Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.

[0104] The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group, excluding the number of carbon atoms in the substituent, is usually preferably 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0105] The symbol "*" that can be attached to a chemical formula represents a bond. The dotted line in the chemical formula also indicates a bond. When two "*" and dotted lines are included in the chemical formula, the bond to which of the two units that are the bonding destinations is not particularly limited.

[0106] "Ink" means a liquid substance used in a coating method and is not limited to a colored liquid. Further, the "coating method" includes a method of forming a film (layer) using a liquid substance. Examples thereof include a slot die coating method, a slit coating method, a knife coating method, a spin coating method, a casting method, a microgravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a gravure printing method, a flexographic printing method, an offset printing method, an inkjet coating method, a dispenser printing method, a nozzle coating method, and a capillary coating method.

[0107] The ink may be a solution or a dispersion such as an emulsion or a suspension.

[0108] The "absorption peak wavelength" is a parameter specified based on the absorption peak of the absorption spectrum measured in a predetermined wavelength range, and refers to the wavelength of the absorption peak having the largest absorbance among the absorption peaks of the absorption spectrum.

[0109] The "external quantum efficiency" is also referred to as EQE (External Quantum Efficiency), and is a value indicating, as a ratio (%), the number of electrons that could be extracted outside the photoelectric conversion element out of the electrons generated with respect to the number of photons irradiated to the photoelectric conversion element.

[0110] ≪Compound≫ The compound of the present disclosure is represented by the following formula (1).

[0111]

Chemical formula

[0112] In formula (1), D is, independently of each other, a polycyclic aromatic group having two bonds, and there are four or more double bonds included in the conjugated structure that shortest-connects the two bonds. L1 and L1’ are each independently an aromatic group having two bonding hands, and the number of double bonds contained in the conjugated structure that shortest connects the two bonding hands is three or less. L2 is an aromatic group having two bonding hands and having a chemical structure different from that of D. n is 1 or 2, m is 0 or 1, and n + m = 2. A1 and A2 are acceptor groups.

[0113] The compound of the present disclosure is a novel compound, and when used as a photoelectric conversion element, the dark current is reduced. The action of the compound of the present disclosure is not clear, but is presumed as follows.

[0114] In the formula (1) which is the compound of the present disclosure, the groups represented by L1 and L1’, and (L2) m are each a linker, the group represented by (D) n is a core, and the groups represented by the group represented by A1 and the group represented by A2 are each an acceptor. In the formula (1) which is the compound of the present disclosure, A1, L1, L1’, D, L2, and A2 are each one structural unit, and the structural unit is referred to as a unit. That is, the compound of the present disclosure is a compound composed of a total of (4 + n + m) units of A1, L1, L1’, n Ds, m L2s, and A2 as represented by the formula (1). The linker existing between the acceptor A1 and (D) n is composed of two units (L1 and L1’), and the linker existing between the acceptor A2 and (D) n is composed of m units ((L2) m ). In the photoelectric conversion element using the compound of the present disclosure, the molecules of the compound of the present disclosure are in an associated state through a part of the unit.

[0115] As factors of dark current in a photoelectric conversion element, there are currents derived from impurity potential and currents due to the broadening of the density of states (DOS) in the injection current or the current due to interband transition. In particular, when the DOS broadens, electrons can flow more easily and the value of the dark current increases. Therefore, in order to reduce the dark current, it is required to narrow the broadening of the DOS.

[0116] The compound of the present disclosure has an appropriately controlled association state, a narrow broadening of the DOS, and can reduce the dark current in a photoelectric conversion element. It should be noted that the present disclosure is not limited to the above-mentioned estimation mechanism at all.

[0117] <D; core> [Polycyclic aromatic group] In formula (1), each D is independently a polycyclic aromatic group having two bonds (that is, a divalent polycyclic aromatic group). It should be noted that D has a different chemical structure from L1, L1', and L2 described later.

[0118] The polycyclic aromatic group in D may be either a polycyclic aromatic heterocyclic group or a polycyclic aromatic hydrocarbon group. From the viewpoint of being likely to absorb light of long wavelengths, a polycyclic aromatic heterocyclic group is preferred. The heteroatom in the polycyclic aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the polycyclic aromatic group in D preferably has a sulfur-containing heterocycle and is more preferably a sulfur-containing heterocyclic group.

[0119] In the polycyclic aromatic group having two bonding hands in D, the number of double bonds included in the conjugated structure that connects the two bonding hands in the shortest way is 4 or more. From the viewpoint of reducing the dark current in the photoelectric conversion element, the number of double bonds included in the conjugated structure that connects the two bonding hands in the shortest way is preferably 4 to 12, more preferably 4 to 8, still more preferably 4 to 6, even more preferably 4 or 5, and even more preferably 4.

[0120] From the viewpoint that the compound easily absorbs light with a long wavelength, in the formula (1), D is preferably a donor group (also referred to as a donor-like group).

[0121] Since the planarity of the compound is increased, the polycyclic aromatic group in D preferably includes a 5-membered ring structure, and the two bonding hands of the polycyclic aromatic group preferably extend from the 5-membered ring structure respectively. The polycyclic aromatic group in D preferably includes two or more 5-membered ring structures, and more preferably consists only of 5-membered ring structures.

[0122] [Side chain] In the formula (1), in D, the polycyclic aromatic group preferably has a side chain. In the present disclosure, the side chain represents a group that replaces a hydrogen atom bonded to an atom constituting the main skeleton (monocyclic or condensed ring, etc.). In D, the side chain is a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, An optionally substituted amino group, An optionally substituted acyl group, An optionally substituted imine residue, An optionally substituted amide group, An optionally substituted acid imide group, An optionally substituted carbonyl group, An optionally substituted oxycarbonyl group, An optionally substituted sulfonyl group, An optionally substitutedoxysulfonyl group, An optionally substituted alkenyl group, An optionally substituted cycloalkenyl group, An optionally substituted alkynyl group, An optionally substituted cycloalkynyl group, A cyano group, or A nitro group is preferred.

[0123] In D, the side chain preferably has an aromatic ring or a branched chain, and more preferably has a branched chain.

[0124] In D, the polycyclic aromatic group may have a plurality of side chains, and when having a plurality of side chains, the plurality of side chains may be the same or different from each other.

[0125] In D, when there are a plurality of the side chains, each is independently preferably an optionally substituted alkyl group, cycloalkyl group, aryl group, alkyloxy group, cycloalkyloxy group or aryloxy group, more preferably an optionally substituted alkyl group or aryl group, and even more preferably an alkyl group.

[0126] In D, the side chain preferably has 6 or more carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 6 to 20 carbon atoms, and still more preferably 6 to 10 carbon atoms.

[0127] The atom to which the side chain in D is bonded is preferably sp3 carbon, sp3 silicon, sp2 carbon, or sp2 silicon, more preferably sp3 carbon or sp2 carbon, and even more preferably sp3 carbon from the viewpoint of reducing dark current. When the side chain is bonded to sp3 carbon, the side chain protrudes in the vertical direction with respect to the π plane of the ring structure of the polycyclic aromatic group containing sp3 carbon in the main skeleton, and the pattern of the association state of the molecules of the compound of the present disclosure is limited.

[0128] [Chemical structure of D] From the viewpoint that the compound easily absorbs light of a long wavelength, in the formula (1), D is preferably any group represented by the following formula (D-1) to formula (D-7), and more preferably a group represented by the following formula (D-1), formula (D-2) or formula (D-6). In the following formula (D-1) to formula (D-7), the symbol "*" indicates a bond with L1' or (L2) when n in the formula (1) is 1. m The symbol "*" indicates a bond with L1' or a bond with D or a bond with D or (L2) when n in the formula (1) is 2. m The bond with which each of the two symbols "*" in the chemical formula is bonded is not particularly limited.

[0129] [Chemical formula]

[0130] In formula (D-1), formula (D-2), formula (D-6) and formula (D-7), X is any group represented by the following formula (X-1) to formula (X-6).

[0131] [Chemical formula]

[0132] In formula (X-1) to formula (X-6), R D1 are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group, and Ar 1 and Ar 2 each independently represents an aromatic carbon ring which may have a substituent and in which a plurality of ring structures may be further fused, or an aromatic heterocyclic ring which may have a substituent and in which a plurality of ring structures may be further fused. Ar 1 and Ar2 Either one of them may not exist.

[0133] Since the polycyclic aromatic group in D preferably has a side chain, in Formula (X-1) to Formula (X-6), at least one of the plurality of R D1 is preferably not a hydrogen atom.

[0134] In each of Formula (X-1) to Formula (X-6), when there are two R D1 the two R D1 may be the same as or different from each other. From the viewpoint that the compound is likely to absorb light of a long wavelength, X is preferably any group represented by Formula (X-1) to Formula (X-4), and more preferably the group represented by Formula (X-1). In Formula (X-1) to Formula (X-6), R D1 is each independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group or an aryloxy group which may have a substituent, more preferably an alkyl group or an aryl group which may have a substituent, and even more preferably an alkyl group.

[0135] In Formula (D-2), Formula (D-5) and Formula (D-7), Ar 1 and Ar 2 are each independently an aromatic carbon ring which may have a substituent and in which a plurality of ring structures may be further condensed, or an aromatic heterocyclic ring which may have a substituent and in which a plurality of ring structures may be further condensed. Either one of Ar 1 and Ar 2 may not exist.

[0136] Ar 1 and Ar 2 The aromatic heterocyclic rings that can form Ar include, in addition to monocyclic and condensed rings in which the heterocyclic ring itself exhibits aromaticity, rings in which an aromatic ring is condensed to the heterocyclic ring even if the heterocyclic ring itself that constitutes the ring does not exhibit aromaticity.

[0137] Ar1 and Ar 2 The aromatic heterocyclic rings that can form 1 and Ar may each be a monocyclic ring or a condensed ring. When the aromatic heterocyclic ring is a condensed ring, all of the rings constituting the condensed ring may be condensed rings having aromaticity, or only some of them may be condensed rings having aromaticity. When these rings have a plurality of substituents, these substituents may be the same or different.

[0138] Ar 1 and Ar 2 Specific examples of the aromatic carbon rings that can form 1 and Ar include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, and phenanthrene ring. Preferably, they are benzene ring and naphthalene ring, more preferably benzene ring and naphthalene ring, and still more preferably benzene ring. These rings may have substituents.

[0139] Ar 1 and Ar 2 Specific examples of the aromatic heterocyclic rings that can form 1 and Ar include oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphole ring, and also phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

[0140] Since the planarity of the compound is increased, Ar 1 and Ar 2 each preferably contain a 5-membered ring structure, and the two bonds in D preferably extend from the 5-membered ring structure, respectively.

[0141] In Formula (D-3) to Formula (D-7), the definition and preferred embodiment of R D1 are the same as those of R D1 in the above Formula (X-1) to Formula (X-6).

[0142] (Example of D) Examples of formula (D-1) include groups represented by the following formulas (d-1-1) to (d-1-6). Examples of formula (D-2) include groups represented by the following formulas (d-2-1) to (d-2-23). Examples of formula (D-3) include groups represented by the following formulas (d-3-1) to (d-3-6). Examples of formula (D-4) include groups represented by the following formulas (d-4-1) to (d-4-4). Examples of formula (D-5) include groups represented by the following formulas (d-5-1) to (d-5-10). Examples of formula (D-6) include groups represented by the following formulas (d-6-1) to (d-6-2). Examples of formula (D-7) include groups represented by the following formulas (d-7-1) to (d-7-9).

[0143] In formulas (d-1-1) to (d-1-6), (d-2-1) to (d-2-23), (d-3-1) to (d-3-6), (d-4-1) to (d-4-4), (d-5-1) to (d-5-10), (d-6-1) to (d-6-2), and (d-7-1) to (d-7-9), the definition of R D1 is, independently of each other, the same as the definition of the above-mentioned R D1 . In the following formulas (d-2-1) to (d-2-23), (d-5-1) to (d-5-10), and (d-7-1) to (d-7-9), U is, independently of each other, CR D1 2, S, SiR D1 2, Se, NR D1 , or O. U is preferably S. In the following formulas (d-1-1) to (d-1-6), (d-2-1) to (d-2-23), (d-3-1) to (d-3-6), (d-4-1) to (d-4-4), (d-5-1) to (d-5-10), (d-6-1) to (d-6-2), and (d-7-1) to (d-7-9), the symbol "*" indicates a bond with L1' or (L2) when n in formula (1) is 1 m . The symbol "*" indicates a bond with L1' or a bond with D or a bond with D or (L2) when n in formula (1) is 2m It shows a bonding hand with [specific entity]. In the chemical formula, the two symbols "*" do not have specific limitations on which entity they are bonded to respectively.

[0144] From the perspective that the compound is likely to absorb light with a long wavelength, D is a group represented by formula (d-1-1), formula (d-1-3) to formula (d-1-6), formula (d-2-3) to formula (d-2-8), formula (d-2-13) to formula (d-2-18), formula (d-3-5) to formula (d-3-6), formula (d-4-1) to formula (d-4-4), formula (d-5-1), formula (d-5-3), formula (d-6-1), formula (d-6-2) or formula (d-7-2) to formula (d-7-5), preferably a group represented by formula (d-1-1), formula (d-1-3) to formula (d-1-6), formula (d-2-3), formula (d-2-5), formula (d-2-8), formula (d-2-13), formula (d-2-15), formula (d-2-18), formula (d-4-1) to formula (d-4-3), formula (d-6-1) or formula (d-6-2), more preferably a group represented by formula (d-1-1), formula (d-1-4) to formula (d-1-6), formula (d-2-3), formula (d-2-13) or formula (d-6-1), even more preferably.

[0145]

Chemical formula

[0146]

Chemical formula

[0147]

Chemical formula

[0148]

Chemical formula

[0149]

Chemical formula

[0150] [Chemical formula]

[0151] [Chemical formula]

[0152] [Chemical formula]

[0153] [Chemical formula]

[0154] (Specific examples of D) Specific examples of D include groups represented by the following formulas. In each formula, the symbol "*" represents a bond to L1' or (L2) when n in formula (1) is 1. m A bond to L1' or a bond to D or a bond to D or (L2) when n in formula (1) is 2. m A bond to. Which two of the "*" symbols in the chemical formula are bonds to is not particularly limited.

[0155] [Chemical formula]

[0156] [Chemical formula]

[0157] [Chemical formula]

[0158] [Chemical formula]

[0159] [Chemical formula]

[0160] [(D) n In formula (1), (D) n n is 1 or 2. From the perspective of compound synthesis, n is preferably 1. When n is 2, the two Ds may be the same or different.

[0161] [(D) n Examples of (D) n Examples of (D) include groups represented by the following formulas (dn-1-1) to (dn-1-9) and (dn-2-1) to (dn-2-4).

[0162] In the following formulas (dn-1-1) to (dn-1-9) and (dn-2-1) to (dn-2-4), the definition of R D1 is, independently of each other, the same as the definition of the above-mentioned R D1 . In the following formulas (dn-1-1) to (dn-1-9) and (dn-2-1) to (dn-2-4), the symbol "*" indicates a bond with L1' in formula (1) or a bond with (L2) m .

[0163] From the perspective of compound synthesis, (D) n is preferably a group represented by formula (dn-1-1), formula (dn-1-3), or formula (dn-1-5).

[0164] [Chemical formula]

[0165] [Chemical formula] ​

[0166] <L1 and L1'; A1 and (D) n a linker connecting them [Aromatic group] In formula (1), L1 and L1' are each independently an aromatic group having two bonds (i.e., a divalent aromatic group). Note that neither L1 nor L1' has the same chemical structure as D, and they have different chemical structures.

[0167] The aromatic group in L1 or L1' preferably has a monocyclic or condensed-ring main skeleton. The aromatic group in L1 or L1' may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and from the viewpoint of being likely to absorb light of long wavelengths, an aromatic heterocyclic group is preferred. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the aromatic group in L1 or L1' preferably has a sulfur-containing heterocycle, and more preferably is a sulfur-containing heterocyclic group. It is even more preferable that L1 and L1' are sulfur-containing heterocyclic groups.

[0168] In L1 and L1', in the aromatic group having two bonds, the double bonds contained in the conjugated structure that connects the two bonds in the shortest way are each independently three or less. From the viewpoint of reducing the dark current in the photoelectric conversion element, the double bonds contained in the conjugated structure that connects the two bonds in the shortest way are each independently preferably 1 to 3, more preferably 2 or less, even more preferably 1 or 2, and most preferably 2.

[0169] In the above formula (1), it is preferable that all of L1, L1', and L2 described below have different chemical structures from each other, or that any two of L1, L1', and L2 described below have the same chemical structure.

[0170] L1, L1', and L2 described below are preferably divalent aromatic heterocyclic groups that contain a thiophene ring, may have substituents, and may have multiple ring structures fused together.

[0171] Specifically, L1, L1', and L2 described below refer to the atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon that may have substituents. Here, aromatic hydrocarbons include compounds having a condensed ring in which multiple ring structures are fused together.

[0172] The number of carbon atoms of the divalent aromatic carbocyclic group represented by L1, L1', and L2 described below is usually preferably 6 to 60, more preferably 6 to 20, not including the number of carbon atoms of the substituents. The number of carbon atoms of the aromatic carbocyclic group including substituents is usually preferably 6 to 100.

[0173] Examples of the divalent aromatic carbocyclic group represented by L1, L1', and L2 described below include divalent aromatic carbocyclic groups represented by the following formula. The divalent aromatic carbocyclic group represented by the following formula may further have substituents.

[0174]

Chemical formula

[0175] The number of carbon atoms of the divalent aromatic heterocyclic group represented by L1, L1', and L2 described below is usually preferably 2 to 60, more preferably 4 to 60, and even more preferably 4 to 20.

[0176] Examples of the substituent that the divalent aromatic heterocyclic group represented by L1, L1', and L2 described below may have include a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cyano group, and a nitro group.

[0177] Specific examples of the divalent aromatic heterocyclic group represented by L1, L1', and L2 described below include divalent aromatic heterocyclic groups represented by the following formulas. These groups may further have a substituent.

[0178]

Chemical formula

[0179]

Chemical formula

[0180]

Chemical formula

[0181] As the divalent aromatic heterocyclic group represented by L1, L1', and L2 described below, divalent aromatic heterocyclic groups represented by the following formulas are preferable. These groups may further have a substituent.

[0182]

Chemical formula

[0183] [Side chain] The aromatic group in L1 or L1' may have a side chain. In L1 and L1', the side chains are each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group, preferably.

[0184] The aromatic group in L1 or L1' may have a plurality of side chains, and when it has a plurality of side chains, the plurality of side chains may be the same or different from each other.

[0185] When there are a plurality of side chains of the aromatic group in L1 or L1', each of them is independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, an aryloxy group, an amide group, or a substituted oxycarbonyl group which may have a substituent, more preferably an alkyloxy group which may have a substituent, and even more preferably an alkyloxy group.

[0186] [Chemical structure of L1] From the viewpoint that the dark current of the photoelectric conversion element using the compound of the present disclosure is likely to be reduced, in the formula (1), L1 is preferably any group represented by the following formula (L1-1) to formula (L1-9), more preferably any group represented by the following formula (L1-1) to formula (L1-7), even more preferably any group represented by the following formula (L1-1) to formula (L1-4), and still more preferably any group represented by the following formula (L1-1), formula (L1-2), or formula (L1-4). In each formula, the dotted line indicates a bond with A1 or a bond with L1' in the formula (1). The dotted line in the chemical formula is not particularly limited as to which of A1 and L1' it is bonded to. That is, from the viewpoint that the dark current of the photoelectric conversion element using the compound of the present disclosure is likely to be reduced and from the viewpoint that the compound is likely to absorb light of a long wavelength, L1 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0187] [Chemical formula]

[0188] In formula (L1-1) to formula (L1-9), R L1 are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cycloalkynyl group which may have a substituent, a cyano group, or a nitro group.

[0189] In formulas (L1-1) to (L1-9), R L1is independently preferably an alkyl group, a cycloalkyl group, an aryl group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an alkylthio group, a substituted amino group, or a substituted oxycarbonyl group, more preferably an alkyl group, an aryl group, an alkyloxy group, a substituted amino group, or a substituted oxycarbonyl group, and even more preferably an alkyl group, an alkyloxy group or a substituted oxycarbonyl group, each of which may have a substituent.

[0190] (Specific examples of L1) Specific examples of L1 include groups represented by the following formulas. In each formula, the dotted line indicates a bond to A1 or a bond to L1' in formula (1).

[0191] [Chemical formula]

[0192] [Chemical formula]

[0193] [Chemical formula]

[0194] [Chemical formula]

[0195] [Chemical structure of L1'] The description of the chemical structure of L1' and specific examples of L1' is the same as the description of [Chemical structure of L1] and (Specific examples of L1) above, including definitions, examples, and preferred embodiments. In each formula, * and the dotted line indicate a bond to L1 or (D) n in formula (1). In formula (1), the chemical structures of L1 and L1' may be the same or different.

[0196] [Chemical structure of L1-L1'] As the structure of L1-L1', the following chemical structure is preferable. In each formula, * or a dotted line indicates a bond with A1 in formula (1) or a bond with (D). n indicates a bond with (D).

[0197] [Chemical formula]

[0198] <(L2) m ; linker connecting A2 and (D) n > [Aromatic group] In formula (1), L2 is an aromatic group having two bonds (that is, a divalent aromatic group). Note that L2 has a chemical structure different from that of D.

[0199] The aromatic group of L2 preferably has a monocyclic or condensed ring main skeleton. The aromatic group in L2 may be either an aromatic heterocyclic group or an aromatic carbocyclic group, and from the viewpoint of being likely to absorb light with a long wavelength, an aromatic heterocyclic group is preferable. The heteroatom in the aromatic heterocyclic group is preferably at least one selected from the group consisting of a sulfur atom, a silicon atom, a selenium atom, a nitrogen atom, and an oxygen atom, more preferably at least one selected from the group consisting of a sulfur atom, a nitrogen atom, a silicon atom, and an oxygen atom, and even more preferably a sulfur atom. That is, the aromatic group in L2 preferably has a sulfur-containing heterocyclic ring, and more preferably is a sulfur-containing heterocyclic group. L2 is even more preferably a sulfur-containing heterocyclic group.

[0200] In the aromatic group having two bonding hands in L2, the number of double bonds included in the conjugated structure that shortest connects the two bonding hands is preferably three or less. From the viewpoint of reducing the dark current in the photoelectric conversion element, the number of double bonds included in the conjugated structure that shortest connects the two bonding hands is more preferably 1 to 3, still more preferably 2 or less, even more preferably 1 or 2, and still even more preferably 2.

[0201] As described above, in the formula (1), it is preferable that all of L1, L1', and L2 have different chemical structures from each other, or any two of L1, L1', and L2 have the same chemical structure.

[0202] [Side chain] The aromatic group in L2 may have a side chain. In L2, the side chains are each independently a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, An optionally substituted oxycarbonyl group, An optionally substituted sulfonyl group, An optionally substituted oxysulfonyl group, An optionally substituted alkenyl group, An optionally substituted cycloalkenyl group, An optionally substituted alkynyl group, An optionally substituted cycloalkynyl group, A cyano group, or A nitro group is preferred.

[0203] The aromatic group in L2 may have a plurality of side chains. When it has a plurality of side chains, the plurality of side chains may be the same as or different from each other.

[0204] When there are a plurality of side chains of the aromatic group in L2, each of them is independently preferably an optionally substituted alkyl group, cycloalkyl group, aryl group, alkyloxy group, cycloalkyloxy group, aryloxy group, substituted amino group, or substituted oxycarbonyl group, more preferably an optionally substituted alkyl group, aryl group, alkyloxy group, substituted amino group, or substituted oxycarbonyl group, and even more preferably an alkyl group, alkyloxy group or substituted oxycarbonyl group.

[0205] [Chemical structure of L2] From the viewpoint that the dark current of the photoelectric conversion element using the compound of the present disclosure is likely to be reduced, in the formula (1), L2 is preferably any group represented by the following formula (L2-1) to formula (L2-9), more preferably any group represented by the following formula (L2-1) to formula (L2-8), and even more preferably any group represented by the following formula (L2-1), formula (L2-2), formula (L2-4) or formula (L2-7). In each formula, the dotted line indicates the bond with (D) n in the formula (1) or the bond with A2. That is, from the viewpoint that the dark current of the photoelectric conversion element using the compound of the present disclosure is likely to be reduced, and from the viewpoint that the compound is likely to absorb long-wavelength light, L2 preferably has a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure.

[0206]

Chemical formula

[0207] In formulas (L2-1) to (L2-9), R L2 is, independently of each other, a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, a cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, a cycloalkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted carbonyl group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, a substituted sulfonyl group which may have a substituent, a substituted oxysulfonyl group which may have a substituent, an alkenyl group which may have a substituent, An optionally substituted cycloalkenyl group, An optionally substituted alkynyl group, An optionally substituted cycloalkynyl group, A cyano group, or A nitro group.

[0208] In formulas (L2-1) to (L2-9), R L2 is each independently preferably an optionally substituted alkyl group, cycloalkyl group, aryl group, alkyloxy group, cycloalkyloxy group, aryloxy group, substituted amino group, or substituted oxycarbonyl group, more preferably an optionally substituted alkyl group, aryl group, alkyloxy group, substituted amino group, or substituted oxycarbonyl group, and even more preferably an alkyl group, alkyloxy group or substituted oxycarbonyl group.

[0209] (Specific examples of L2) Specific examples of L2 are the same as the above (Specific examples of L1). In each formula, the dotted line indicates the bond to (D) n in formula (1) or the bond to A2.

[0210] [(L2) m In formula (1), m in (L2) m is 0 or 1. From the viewpoint of synthesis, m is preferably 1. When m is 0, it means that (D) n is directly bonded to A2, that is, it means that (L2) m does not exist. The description of (L2) m when m is 1 is the same as the above description of L2, including definitions, examples, and preferred embodiments.

[0211] [n and m] As described above, in formula (1), n + m = 2. That is, n and m may be any combination of n = 1 and m = 1, or n = 2 and m = 0.

[0212] ​ [Examples of the combination of D and L2] When n and m are such that n = 1 and m = 1, examples of the combination of D and L2 include groups represented by the following formulas (dn-3-1) to (dn-3-12), (dn-4-1) to (dn-4-12), (dn-5-1) to (dn-5-12), and (dn-6-1) to (dn-6-12).

[0213] In the following formulas (dn-3-1) to (dn-3-12), (dn-4-1) to (dn-4-12), (dn-5-1) to (dn-5-12), and (dn-6-1) to (dn-6-12), R D1 is independently defined in the same way as the above-defined R D1 . In the following formulas (dn-3-1) to (dn-3-12), (dn-4-1) to (dn-4-12), (dn-5-1) to (dn-5-12), and (dn-6-1) to (dn-6-12), the symbol "*" indicates a bond with L1' or a bond with A2 in formula (1).

[0214] From the perspective of compound synthesis, the combination of D and L2 is preferably a group represented by formulas (dn-3-1) to (dn-3-12), formulas (dn-4-1) to (dn-4-12), formulas (dn-5-1) to (dn-5-12), or formulas (dn-6-1) to (dn-6-12), more preferably a group represented by formulas (dn-3-1), (dn-3-4) to (dn-3-8), (dn-4-1), (dn-4-4) to (dn-4-8), (dn-5-1), (dn-5-4) to (dn-5-8), or formulas (dn-6-1) to (dn-6-12), and even more preferably a group represented by formulas (dn-3-1), (dn-3-4), (dn-4-1), (dn-4-4), (dn-5-1), or (dn-5-4).

[0215] [Chemical formula]

[0216] [Chemical formula]

[0217] [Chemical]

[0218] [Chemical]

[0219] <A1 and A2; acceptor> In the formula (1) above, A1 and A2 are acceptor groups. In the formula (1) above, A1 and A2 are preferably each independently a group represented by the following formula (A-1). In each formula, the dotted line indicates a bond with L1 or (L2) in the formula (1). m represents a bond with.

[0220] [Chemical]

[0221] In the formula (A-1), Ar represents an optionally substituted carbocyclic ring or an optionally substituted heterocyclic ring, and the carbocyclic ring and the heterocyclic ring are each independently a monocyclic ring or a condensed ring. When the carbocyclic ring or the heterocyclic ring has a plurality of substituents, the plurality of substituents may be the same or different.

[0222] The carbocyclic ring may be an aromatic carbocyclic ring. Specific examples of the aromatic carbocyclic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and even more preferably a benzene ring. These rings may have substituents.

[0223] The complex ring may be an aromatic complex ring. Specific examples of the aromatic complex ring include an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, and a dibenzophosphole ring, and a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have substituents.

[0224] [Chemical structures of A1 and A2] In formula (1), A1 and A2 are each independently preferably any group represented by the following formula (a-1) to formula (a-8). In each formula, the symbol "*" represents a bond with L1 in formula (1) or a bond with (L2) m indicating a bond. The chemical structures of A1 and A2 may be the same as or different from each other. From the viewpoint of ease of compound synthesis, the chemical structures of A1 and A2 are preferably the same.

[0225] [Chemical formula]

[0226] In formula (a-1) to formula (a-8), a plurality of R A1 are each independently a hydrogen atom, a halogen atom, or a cyano group. From the viewpoint that the compound easily absorbs light of a long wavelength, R A1 are each independently preferably a hydrogen atom, a chlorine atom, a fluorine atom, or a cyano group, and more preferably a cyano group. From the viewpoint that the compound easily absorbs light of a long wavelength, A1 and A2 are each independently preferably any group represented by formula (a-1) or formula (a-3) to formula (a-5), more preferably any group represented by formula (a-1), formula (a-3), or formula (a-5), and still more preferably any group represented by formula (a-1) or formula (a-5).

[0227] (Specific examples of A1 and A2) Specific examples of A1 and A2 include groups represented by the following formulas. In each formula, the symbol "*" represents a bond with L1 in formula (1) or a bond with (L2) m and indicates a bond with (L2).

[0228] [Chemical formula]

[0229] [Chemical formula]

[0230] [Compound] The compounds of the present disclosure are preferably represented by the following formula (2).

[0231] [Chemical formula]

[0232] In formula (2), D is a polycyclic aromatic group having two bonds, and the number of double bonds included in the conjugated structure connecting the two bonds in the shortest way is 4 or more, L1 and L1' are each independently an aromatic group having two bonds, and the number of double bonds included in the conjugated structure connecting the two bonds in the shortest way is 3 or less, L2 is an aromatic group having two bonds and is not the same chemical structure as D, A1 and A2 are acceptor groups.

[0233] In formula (2), the descriptions of D, L1, L1', L2, A1, and A2 are the same as the descriptions of D, L1, L1', L2, A1, and A2 in formula (1), including definitions, examples, and preferred embodiments, etc.

[0234] In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the compounds of the present disclosure, in Formula (1) and Formula (2), D is any group represented by Formula (D-1) to Formula (D-7), L1, L1' and L2 each independently have a thiophene structure, a thienothiophene structure, a thiazole structure, or a benzothiadiazole structure, A1 and A2 are each independently a group represented by Formula (A-1), L1, L1' and L2 all have different chemical structures and are not the same chemical structure as D, In Formula (2), it is preferable that n = m = 1.

[0235] In the compounds of the present disclosure, in Formula (1) and Formula (2), D is any group represented by Formula (d-1-1) to Formula (d-1-6), Formula (d-2-3) or Formula (d-2-8), L1 and L1' are each independently any group represented by Formula (L1-1) to Formula (L1-9), L2 is any group represented by Formula (L2-1) to Formula (L2-9), A1 and A2 are each independently any group represented by Formula (a-1) to Formula (a-8), L1, L1' and L2 all have different chemical structures and are not the same chemical structure as D, L1, L1', and L2 all have different chemical structures from each other, or any two of L1, L1' and L2 have the same chemical structure, In Formula (2), it is more preferable that n = m = 1.

[0236] <Specific examples of the compounds of the present disclosure> Preferable specific examples of the compounds of the present disclosure include compounds represented by the following formula. In the compound, tol represents a toluene group.

[0237]

Chemical formula

[0238] [Chemistry]

[0239] [Chemistry]

[0240] [Chemistry]

[0241] [Chemistry]

[0242] [Chemistry]

[0243] [Chemistry]

[0244] ≪Composition≫ The composition of the present disclosure includes a p-type semiconductor material and an n-type semiconductor material. As the n-type semiconductor material, it is preferable to include the compound of the present disclosure.

[0245] The composition of the present disclosure may include components other than the p-type semiconductor material and the n-type semiconductor material. Further, the composition of the present disclosure may include only the compound of the present disclosure as the n-type semiconductor material, or may include other compounds other than the compound of the present disclosure. Other compounds that may be included as the n-type semiconductor material may be low molecular weight compounds or high molecular weight compounds.

[0246] <n-type semiconductor material> Examples of the low molecular weight compounds that may be included as the n-type semiconductor material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, and phenanthrene derivatives such as bathocuproine.

[0247] Examples of the high molecular weight compounds that may be included as the n-type semiconductor material include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.

[0248] Also, other compounds may be fullerene derivatives.

[0249] Here, the fullerene derivative refers to a compound in which at least a part of fullerene (C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, and C 84 fullerene) is modified. In other words, it refers to a compound having one or more groups added to the fullerene skeleton. Hereinafter, the fullerene derivative of C 60 fullerene is sometimes referred to as the "C 60 fullerene derivative", and the fullerene derivative of C 70 fullerene is sometimes referred to as the "C 70 fullerene derivative".

[0250] The fullerene derivatives that may be included as the n-type semiconductor material are not particularly limited as long as the object of the present disclosure is not impaired.

[0251] C that may be included as an n-type semiconductor material 60 Specific examples of fullerene derivatives include the following compounds.

[0252] [Chemical formula]

[0253] The above C 60 In the formula of the fullerene derivative, R is a hydrogen atom a halogen atom an alkyl group that may have a substituent a cycloalkyl group that may have a substituent an aryl group that may have a substituent an alkyloxy group that may have a substituent a cycloalkyloxy group that may have a substituent an aryloxy group that may have a substituent an alkylthio group that may have a substituent a cycloalkylthio group that may have a substituent an arylthio group that may have a substituent a monovalent heterocyclic group that may have a substituent a substituted amino group that may have a substituent an acyl group that may have a substituent an imine residue that may have a substituent an amide group that may have a substituent an acid imide group that may have a substituent a substituted carbonyl group that may have a substituent a substituted oxycarbonyl group that may have a substituent a substituted sulfonyl group that may have a substituent a substituted oxysulfonyl group that may have a substituent an alkenyl group that may have a substituent a cycloalkenyl group that may have a substituent An alkynyl group which may have a substituent, A cycloalkynyl group which may have a substituent, A cyano group, or A nitro group. In addition, when there are a plurality of Rs, the plurality of Rs may be the same as or different from each other.

[0254] C 70 Examples of the fullerene derivative include the following compounds.

[0255]

Chemical formula

[0256] <p-type semiconductor material> The p-type semiconductor material is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.

[0257] Here, the weight average molecular weight in terms of polystyrene means the weight average molecular weight calculated using gel permeation chromatography (GPC) with a standard sample of polystyrene.

[0258] From the viewpoint of particularly improving the solubility in a solvent, the weight average molecular weight in terms of polystyrene of the p-type semiconductor material is preferably 3000 or more and 500000 or less.

[0259] The p-type semiconductor material is preferably a π-conjugated polymer compound (also referred to as a D-A type conjugated polymer compound) containing a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as an A structural unit). Whether a certain unit is a donor structural unit or an acceptor structural unit can be relatively determined from the energy levels of HOMO or LUMO.

[0260] Here, the donor structural unit is a structural unit with excessive π electrons, and the acceptor structural unit is a structural unit lacking π electrons.

[0261] In the present disclosure, the structural units that can constitute a p-type semiconductor material include structural units in which a donor structural unit and an acceptor structural unit are directly bonded, and further include structural units in which a donor structural unit and an acceptor structural unit are bonded via an arbitrarily suitable spacer (group or structural unit).

[0262] Examples of the p-type semiconductor material that is a polymer compound include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.

[0263] The p-type semiconductor material is preferably a polymer compound containing at least one selected from the group consisting of the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4). The structural unit represented by the following formula (3) is preferably usually a donor structural unit. The structural unit represented by the following formula (4) is preferably usually an acceptor structural unit.

[0264]

Chemical formula

[0265] - Formula (3) - In formula (3), Ar 3 and Ar 4 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any group represented by the following formula (Z-1) to formula (Z-7).

[0266]

Chemical formula

[0267] In formula (Z-1) to formula (Z-7), the definition of R is each independently C60 It is the same as the definition of R in the fullerene derivative formula. In each of Formula (Z-1) to Formula (Z-7), when there are two Rs, the two Rs may be the same as each other or different from each other.

[0268] Ar 3 and Ar 4 Aromatic heterocycles that can form Ar and Ar include, in addition to monocyclic and condensed rings in which the heterocycle itself exhibits aromaticity, rings in which an aromatic ring is condensed to the heterocycle even if the heterocycle itself that forms the ring does not exhibit aromaticity.

[0269] Ar 3 and Ar 4 Aromatic heterocycles that can form Ar and Ar may each be a monocyclic ring or a condensed ring. When the aromatic heterocycle is a condensed ring, the condensed ring may be a condensed ring in which all of the rings that make up the condensed ring have aromaticity, or a condensed ring in which only some of them have aromaticity. When these rings have a plurality of substituents, these substituents may be the same or different.

[0270] Ar 3 and Ar 4 Specific examples of aromatic carbon rings that can form Ar and Ar include benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, and phenanthrene ring, preferably benzene ring and naphthalene ring, more preferably benzene ring and naphthalene ring, and even more preferably benzene ring. These rings may have substituents.

[0271] Specific examples of the aromatic heterocyclic ring include the ring structures of the compounds already described as aromatic heterocyclic compounds, such as oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring, and dibenzophosphole ring, as well as phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring, and benzopyran ring. These rings may have substituents.

[0272] The structural unit represented by formula (3) is preferably a structural unit represented by the following formula (3-1), (3-2) or (3-3).

[0273]

Chemical formula

[0274] In formula (3-1), (3-2) and (3-3), the definitions of Ar 3 , Ar 4 and R are the same as the definitions of Ar 3 , Ar 4 in formula (3) and the definition of R in the formula of the C 60 fullerene derivative.

[0275] Specific examples of the preferred structural unit represented by formula (3) include the structural units represented by the following formulas.

[0276]

Chemical formula

[0277] In the above formulas, the definition of R is the same as the definition of R in the formula of the C 60 fullerene derivative. When there are two Rs, the two Rs may be the same or different.

[0278] More specific examples of preferred structural units represented by formula (3) include structural units represented by the following formulas.

[0279] [ka]

[0280] [ka]

[0281] -Formula (4)- In formula (4), Ar 5 represents a divalent aromatic heterocyclic group.

[0282] Ar 5 The divalent aromatic heterocyclic group represented by the following formula (I) preferably has 2 to 60 carbon atoms, more preferably 4 to 60 carbon atoms, and further preferably 4 to 20 carbon atoms.

[0283] Ar 5 The divalent aromatic heterocyclic group represented by the formula (1) may have a substituent. 5 Examples of the substituent that the divalent aromatic heterocyclic group represented by the formula (I) may have include a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an acid imide group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cyano group, and a nitro group.

[0284] As the constitutional unit represented by formula (4), constitutional units represented by the following formulae (4-1) to (4-10) are preferred.

[0285]

Chem.

[0286] In formulas (4-1) to (4-10), R is C 60 as defined for R in the formula of the fullerene derivative. X 3 and X 4 each independently represents an oxygen atom or a sulfur atom. Z 1 and Z 2 each independently represents a group represented by =C(R)- or a nitrogen atom. When there are two Rs, the two Rs may be the same or different.

[0287] X in formulas (4-1) to (4-10) 3 and X 4 are both preferably sulfur atoms from the viewpoint of availability of the starting compound.

[0288] Note that the structural units represented by formulas (4-1) to (4-10) can usually function as acceptor structural units as described above. However, it is not limited thereto, and in particular, the structural units represented by formulas (4-4), (4-5) and (4-7) can also function as donor structural units.

[0289] The p-type semiconductor material preferably contains a structural unit containing a thiophene skeleton and is a π-conjugated polymer compound containing a π-conjugated system.

[0290] Ar 5 Specific examples of the divalent aromatic heterocyclic group represented by include the groups represented by the following formulas (101) to (191). These groups may further have substituents.

[0291]

Chem.

[0292] [Chemistry]

[0293] [Chemistry]

[0294] [Chemistry]

[0295] The polymer compound that is a p-type semiconductor material preferably is a π-conjugated polymer compound containing a structural unit represented by formula (3) as a donor structural unit and a structural unit represented by formula (4) as an acceptor structural unit.

[0296] In the polymer compound that is a p-type semiconductor material, the polymer compound that is a p-type semiconductor material may contain, as a structural unit, a structure in which the structural unit represented by formula (3) and the structural unit represented by formula (4) already described are linked.

[0297] The polymer compound that is a p-type semiconductor material may contain two or more structural units represented by formula (3), and may contain two or more structural units represented by formula (4).

[0298] For example, from the viewpoint of improving solubility in a solvent, the polymer compound that is a p-type semiconductor material may contain a structural unit represented by the following formula (5).

[0299] [Chemistry]

[0300] In formula (5), Ar 6 represents an arylene group.

[0301] Ar 6The arylene group represented by means the atomic group remaining after removing two hydrogen atoms from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon includes compounds having a condensed ring, compounds in which two or more selected from the group consisting of an independent benzene ring and a condensed ring are directly bonded or bonded via a divalent group such as a vinylene group.

[0302] Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituent that the heterocyclic compound may have.

[0303] Ar 6 The number of carbon atoms of the arylene group represented by is usually preferably 6 to 60, more preferably 6 to 20, not including the number of carbon atoms of the substituent. The number of carbon atoms of the arylene group including the substituent is usually preferably 6 to 100.

[0304] Ar 6 Examples of the arylene group represented by include a phenylene group (for example, the following Formula 1 to Formula 3), a naphthalene-diyl group (for example, the following Formula 4 to Formula 13), an anthracene-diyl group (for example, the following Formula 14 to Formula 19), a biphenyl-diyl group (for example, the following Formula 20 to Formula 25), a terphenyl-diyl group (for example, the following Formula 26 to Formula 28), a condensed ring compound group (for example, the following Formula 29 to Formula 35), a fluorene-diyl group (for example, the following Formula 36 to Formula 38), and a benzofluorene-diyl group (for example, the following Formula 39 to Formula 46).

[0305]

Chemical formula

[0306]

Chemical formula

[0307]

Chemical formula

[0308]

Chem.

[0309]

Chem.

[0310]

Chem.

[0311]

Chem.

[0312]

Chem.

[0313] In the formula, the definition of R is the same as that of R in the formula of the fullerene derivative. A plurality of Rs may be the same or different. 60 The definition of R in the formula of the fullerene derivative is the same. A plurality of Rs may be the same or different.

[0314] The structural unit represented by formula (5) is preferably a structural unit represented by the following formula (5-1) and formula (5-2).

[0315]

Chem.

[0316] In formula (5-1) and formula (5-2), the definition of R is the same as that of R in the formula of the fullerene derivative. The two Rs may be the same or different. 60 The definition of R in the formula of the fullerene derivative is the same. The two Rs may be the same or different.

[0317] The structural unit constituting the polymer compound which is a p-type semiconductor material may be a structural unit in which two or more structural units selected from the above structural units are combined and linked.

[0318] When the polymer compound as the p-type semiconductor material contains a structural unit represented by the formula (3) and / or a structural unit represented by the formula (4), the total amount of the structural unit represented by the formula (3) and the structural unit represented by the formula (4) is usually preferably 20 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and still more preferably 50 mol% to 100 mol% based on 100 mol% of the amount of all the structural units contained in the polymer compound, from the viewpoint of improving the charge transport property as the p-type semiconductor material.

[0319] Specific examples of the polymer compound as the p-type semiconductor material include polymer compounds represented by the following formulas (P-1) to (P-21).

[0320]

Chem.

[0321]

Chem.

[0322]

Chem.

[0323]

Chem.

[0324]

Chem.

[0325]

Chem.

[0326]

Chem.

[0327]

Chem.

[0328]

Chem.

[0329]

Chem.

[0330] In the above formula, the definition of R is the same as the definition of R in the formula of the fullerene derivative. A plurality of Rs may be the same as or different from each other. 60 When the above-exemplified polymer compound is used as the p-type semiconductor material, it is possible to suppress a decrease in EQE or further improve the EQE with respect to heat treatment in the manufacturing process of the photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, and it is possible to improve the heat resistance of the photoelectric conversion element.

[0331] <Combination of p-Type Semiconductor Material and n-Type Semiconductor Material>

[0332] ​The composition of the present disclosure adopts a polymer compound containing at least one selected from the group consisting of the structural unit represented by the above formula (3) and the structural unit represented by the formula (4) as a p-type semiconductor material, and a compound represented by the above formula (1) as an n-type semiconductor material, in which D is each independently a polycyclic aromatic group having two bonds, and the double bonds contained in the conjugated structure connecting the two bonds at the shortest distance are four or more, L1 and L1' are each independently an aromatic group having two bonds, and the double bonds contained in the conjugated structure connecting the two bonds at the shortest distance are three or less, L2 is not the same chemical structure as D, and is an aromatic group having two bonds, n is 1 or 2, m is 0 or 1, n + m = 2, and A1 and A2 are preferably an acceptor group containing a quinoxaline skeleton. By combining this p-type semiconductor material and n-type semiconductor material, the composition can reduce the dark current in a photoelectric conversion element, and further high D * It is possible to provide a photoelectric conversion element that exhibits the following: * is the specific detectability, and it is an index that indicates that the larger the value, the higher the light detectability and the more excellent the resolution.

[0333] The quinoxaline skeleton in A1 and A2 may have a carbon atom substituted with another atom. The acceptor groups (A1 and A2) containing a quinoxaline skeleton are preferably each independently any one of the groups represented by the following formulae (a-5) to (a-8).

[0334] [ka]

[0335] In the formulas (a-5) to (a-8), there are multiple R A1 are each independently a hydrogen atom, a halogen atom, or a cyano group.

[0336] Also, high D *From the viewpoint of obtaining a photoelectric conversion element shown, as the p-type semiconductor material, it is preferable that at least one selected from the group consisting of the structural unit represented by the formula (3) and the structural unit represented by the formula (4) has an aryl group as a substituent in its structure. When the p-type semiconductor material contains the structural unit represented by the formula (3), as the R in the formulas (Z-1) to (Z-7) represented by Z in the formula (3), those containing an aryl group among the above-described substituents are preferable, and it is preferably any one of an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, or a cycloalkyl group which may have a substituent. When a plurality of Rs exist, the plurality of Rs may be the same as or different from each other.

[0337] ≪Ink≫ The ink of the present disclosure contains a p-type semiconductor material, an n-type semiconductor material, and a solvent, and it is preferable that the n-type semiconductor material contains the compound of the present disclosure. As described above, the composition of the present disclosure contains a p-type semiconductor material and an n-type semiconductor material, and since the n-type semiconductor material contains the compound of the present disclosure, the ink of the present disclosure is preferably an ink for forming an active layer of a photoelectric conversion element, and more preferably an ink for forming a bulk heterojunction type active layer.

[0338] According to the ink of the present disclosure, by containing a p-type semiconductor material and the compound of the present disclosure, the dark current in the photoelectric conversion element can be reduced.

[0339] Further, according to the ink of the present disclosure, as the p-type semiconductor material, a polymer compound containing at least one selected from the group consisting of the structural unit represented by the above formula (3) and the structural unit represented by the above formula (4) is adopted. As the n-type semiconductor material, the compound represented by the above formula (1) is used. In the formula (1), D is independently a polycyclic aromatic group having two bonds, and the number of double bonds contained in the conjugated structure connecting the two bonds in the shortest manner is 4 or more. L1 and L1' are independently aromatic groups having two bonds, and the number of double bonds contained in the conjugated structure connecting the two bonds in the shortest manner is 3 or less. L2 is an aromatic group having two bonds and having a chemical structure different from that of D. n is 1 or 2, m is 0 or 1, n + m = 2, and it is preferable to adopt an acceptor group containing a quinoxaline skeleton for A1 and A2. By combining this p-type semiconductor material and n-type semiconductor material, the ink can reduce the dark current in the photoelectric conversion element and further provide a photoelectric conversion element with a higher D * can be provided.

[0340] The quinoxaline skeleton in A1 and A2 may be one in which the carbon atoms constituting it are substituted with other atoms. As the acceptor group (A1 and A2) containing a quinoxaline skeleton, it is preferably any of the above groups of formula (a-5) to formula (a-8) independently.

[0341] Also, from the viewpoint of obtaining a photoelectric conversion element with a higher D * the preferred embodiment of the p-type semiconductor material is the same as the preferred embodiment of the p-type semiconductor material described in the above <combination of p-type semiconductor material and n-type semiconductor material>.

[0342] As the solvent, for example, a mixed solvent obtained by combining the first solvent and the second solvent described later can be used. Specifically, when the ink contains two or more solvents, it preferably contains a main solvent (the first solvent) as the main component and other additive solvents (the second solvent) added for improving solubility or the like. The solvent may be only the first solvent.

[0343] Hereinafter, the first solvent and the second solvent that can be preferably used in the ink for forming the active layer and their combinations will be described.

[0344] <First Solvent> As the first solvent, a solvent in which the p-type semiconductor material can be dissolved is preferable. The first solvent is preferably an aromatic hydrocarbon.

[0345] Examples of the aromatic hydrocarbon include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, trimethylbenzene (e.g., mesitylene, 1,2,4-trimethylbenzene (pseudocumene)), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1-chloronaphthalene, bromobenzene, tetralin, and indane.

[0346] The first solvent may be composed of one kind of aromatic hydrocarbon or two or more kinds of aromatic hydrocarbons. The first solvent is preferably composed of one kind of aromatic hydrocarbon.

[0347] The first solvent is preferably at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, and indane, and more preferably toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, mesitylene, 1,2,4-trichlorobenzene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, 1-chloronaphthalene, bromobenzene, tetralin, or indane.

[0348] <Second solvent> The second solvent is preferably selected from the viewpoint of facilitating the implementation of the manufacturing process and further improving the characteristics of the photoelectric conversion element. Examples of the second solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone; ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl benzoate, butyl benzoate, and benzyl benzoate; ether solvents such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and 1-methoxynaphthalene; 1,2,4-trimethylbenzene, 1,2,4-trichlorobenzene, tetralin, 2-isopropylphenol, 2-isopropyl-5-methylanisole, and bromobenzene.

[0349] The second solvent is preferably acetophenone, propiophenone, butyl benzoate, or methyl benzoate, for example, from the viewpoint of further reducing the dark current.

[0350] <Combination of the first solvent and the second solvent> Examples of suitable combinations of the first solvent and the second solvent include combinations of tetralin and ethyl benzoate, tetralin and propyl benzoate, tetralin and butyl benzoate, o-dichlorobenzene and 1,2-dimethoxybenzene, and combinations of o-dichlorobenzene, methyl benzoate, more preferably combinations of tetralin and butyl benzoate, and o-dichlorobenzene and 1,2-dimethoxybenzene.

[0351] <Mass ratio of the first solvent and the second solvent> The mass ratio of the first solvent, which is the main solvent, to the second solvent, which is the additive solvent (first solvent: second solvent), is preferably in the range of 50:50 to 99:1 from the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material.

[0352] <Any other solvent> The solvent may contain any other solvent other than the first solvent and the second solvent. When the total mass of all the solvents contained in the ink is 100% by mass, the content of any other solvent is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. As any other solvent, a solvent having a boiling point higher than that of the second solvent is preferred.

[0353] In addition to the first solvent, the second solvent, the p-type semiconductor material, and the n-type semiconductor material, the ink may contain any components such as a surfactant, an ultraviolet absorber, an antioxidant, a sensitizer for enhancing the function of generating charges by the absorbed light, and a light stabilizer for increasing the stability against ultraviolet rays, as long as the objects and effects of the present disclosure are not impaired.

[0354] The concentrations of the p-type semiconductor material and the n-type semiconductor material in the ink can be set to any suitable concentrations within a range that does not impair the object of the present disclosure, taking into account the solubility in the solvent and the like.

[0355] The mass ratio of the "p-type semiconductor material" to the "n-type semiconductor material" in the ink is usually preferably in the range of 1 / 0.1 to 1 / 10, more preferably in the range of 1 / 0.5 to 1 / 2, and still more preferably 1 / 1.5.

[0356] The total content of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.25% by mass or more. Also, the total content of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink is usually preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7.50% by mass or less.

[0357] The content of the "p-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.10% by mass or more. Also, the content of the "p-type semiconductor material" in the ink is usually preferably 10% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less.

[0358] The content of the "n-type semiconductor material" in the ink is usually preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.15% by mass or more. Also, the content of the "n-type semiconductor material" in the ink is usually preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 4.50% by mass or less.

[0359] The ink can be prepared by known methods. For example, a method of preparing a mixed solvent by mixing a first solvent or a first solvent and a second solvent, and adding a p-type semiconductor material and an n-type semiconductor material to the obtained mixed solvent, a method of adding a p-type semiconductor material to a first solvent and adding an n-type semiconductor material to a second solvent, and then mixing the first solvent and the second solvent to which each material has been added, etc., can be used for preparation.

[0360] The first solvent and the second solvent, and the p-type semiconductor material and the n-type semiconductor material may be heated and mixed to a temperature below the boiling point of the solvent.

[0361] After mixing the first solvent and the second solvent with the p-type semiconductor material and the n-type semiconductor material, the obtained mixture may be filtered using a filter, and the obtained filtrate may be used. As the filter, for example, a filter formed of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.

[0362] <<Photovoltaic conversion element>> The photoelectric conversion element of the present disclosure includes an anode, a cathode, and an active layer provided between the anode and the cathode and containing a p-type semiconductor material and an n-type semiconductor material. As the n-type semiconductor material, it is preferable to include the compound of the present disclosure. Preferred embodiments of the p-type semiconductor material and the n-type semiconductor material are as described above.

[0363] According to the photoelectric conversion element of the present disclosure, by having the above configuration, it is possible to suppress a decrease in the external quantum efficiency with respect to heat treatment in the manufacturing process of the photoelectric conversion element or the process of incorporating the photoelectric conversion element into a device to which the photoelectric conversion element is applied, and effectively improve the heat resistance.

[0364] Here, a configuration example that the photoelectric conversion element of the present disclosure can take will be described. FIG. 1 is a diagram schematically showing the configuration of the photoelectric conversion element of the present disclosure.

[0365] As shown in FIG. 1, the photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes an anode 12 provided so as to be in contact with the support substrate 11, a hole transport layer 13 provided so as to be in contact with the anode 12, an active layer 14 provided so as to be in contact with the hole transport layer 13, an electron transport layer 15 provided so as to be in contact with the active layer 14, and a cathode 16 provided so as to be in contact with the electron transport layer 15. In this configuration example, a sealing member 17 is further provided so as to be in contact with the cathode 16.

[0366] As another configuration example of the photoelectric conversion element, it includes a cathode provided so as to be in contact with a support substrate, an electron transport layer provided so as to be in contact with the cathode, an active layer provided so as to be in contact with the electron transport layer, a hole transport layer provided so as to be in contact with the active layer, and an anode provided so as to be in contact with the hole transport layer. In this configuration example, a sealing member is further provided so as to be in contact with the anode.

[0367] Hereinafter, the components that can be included in the photoelectric conversion element of the present disclosure will be specifically described.

[0368] <Substrate> A photoelectric conversion element is usually formed on a substrate (support substrate). In addition, it may be further encapsulated by a substrate (encapsulation substrate). Usually, one of a pair of electrodes consisting of an anode and a cathode is formed on the substrate. The material of the substrate is not particularly limited as long as it does not chemically change when forming a layer containing an organic compound in particular.

[0369] Examples of the material of the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, the electrode on the side opposite to the electrode provided on the opaque substrate side (in other words, the electrode far from the opaque substrate) is preferably a transparent or translucent electrode.

[0370] <Electrode> A photoelectric conversion element includes an anode and a cathode which are a pair of electrodes. Among the anode and the cathode, at least one of the electrodes is preferably a transparent or translucent electrode for allowing light to enter.

[0371] Examples of the material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, and composites thereof such as indium tin oxide (ITO), indium zinc oxide (IZO), and NESA, and conductive materials such as gold, platinum, silver, and copper are mentioned. As the material of the transparent or translucent electrode, ITO, IZO, and tin oxide are preferable. In addition, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives, etc. may be used as the material. The transparent or translucent electrode may be an anode or a cathode.

[0372] If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode with low light transmittance. Examples of materials for the electrode with low light transmittance include metals and conductive polymers. Specific examples of materials for the electrode with low light transmittance include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, etc., alloys of two or more of these, or alloys of one or more of these metals and one or more metals selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin, graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.

[0373] <Active layer> The active layer included in the photoelectric conversion element of the present disclosure is assumed to have a bulk heterojunction structure, includes a p-type semiconductor material and an n-type semiconductor material, and the active layer includes the compound of the present disclosure as the n-type semiconductor material.

[0374] The thickness of the active layer is not particularly limited. The thickness of the active layer can be any suitable thickness in consideration of the balance between suppression of dark current and extraction of the generated photocurrent. From the viewpoint of further reducing dark current in particular, the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and still more preferably 200 nm or more. Also, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.

[0375] <Intermediate layer> As shown in FIG. 1, the photoelectric conversion element of the present disclosure preferably includes an intermediate layer (buffer layer) such as a charge transport layer (electron transport layer, hole transport layer, electron injection layer, hole injection layer), etc., as a component for improving characteristics such as photoelectric conversion efficiency.

[0376] Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and a mixture of PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly(4-styrenesulfonate)) (PEDOT:PSS).

[0377] As shown in FIG. 1, the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the electrode.

[0378] The hole transport layer provided in contact with the anode is sometimes particularly referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the anode has a function of promoting the injection of holes into the anode. The hole transport layer (hole injection layer) may be in contact with the active layer.

[0379] The hole transport layer contains a hole transporting material. Examples of hole transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, CuSCN, CuI, NiO, tungsten oxide (WO3), and molybdenum oxide (MoO3). Examples of hole transporting material products include P-10 and P-21 from Avantama.

[0380] The intermediate layer can be formed by any conventionally known suitable formation method. The intermediate layer can be formed by a vacuum evaporation method or a coating method similar to the method for forming the active layer.

[0381] The photoelectric conversion element of the present disclosure preferably has a structure in which the intermediate layer is an electron transport layer, and the substrate (support substrate), anode, hole transport layer, active layer, electron transport layer, and cathode are laminated in this order so as to be in contact with each other.

[0382] As shown in FIG. 1, it is preferable that the photoelectric conversion element of the present disclosure includes an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode. The electron transport layer may be in contact with the active layer.

[0383] The electron transport layer provided in contact with the cathode is sometimes particularly referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the cathode has a function of promoting the injection of electrons generated in the active layer into the cathode.

[0384] The electron transport layer contains an electron transporting material. Examples of the electron transporting material include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0385] Examples of polyalkyleneimine and its derivatives include alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine, particularly polymers obtained by polymerizing one or more alkyleneimines having 2 to 4 carbon atoms by a conventional method, and polymers chemically modified by reacting them with various compounds. As polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferable.

[0386] Examples of the polymer compound containing a fluorene structure include poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9,9'-dioctylfluorene)] (PFN) and PFN-P2.

[0387] Examples of the metal oxide include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and zinc oxide is particularly preferable. Examples of the metal oxide products include Avantama's N-10, N-11, N-12, N-13, N-20X, N-21X, Infinity PV's ZnO, ZnO(2.8%), ZnO(5.6%), and Doped ZnO.

[0388] Examples of other electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0389] <Sealing member> The photoelectric conversion element of the present disclosure further includes a sealing member, and it is preferable to form a sealed body sealed by such a sealing member. As the sealing member, any suitable conventionally known member can be used. Examples of the sealing member include a combination of a glass substrate (sealing substrate) as a substrate and a sealing material (adhesive) such as a UV curable resin.

[0390] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layers constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0391] The sealing layer is preferably formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials as the material of the sealing layer include organic materials such as polytetrafluoroethylene, polychlorotrifluoroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0392] The sealing member is usually composed of a material that can withstand the heat treatment performed when the photoelectric conversion element is incorporated into a device, for example, in the following application examples.

[0393] Dark current The dark current of the encapsulant of the photoelectric conversion element containing the compound of the present disclosure is 80 μA / cm 2 The following is preferable, 50 μA / cm 2 The following is more preferable, 20 μA / cm 2 The following is even more preferable, 10 μA / cm 2 The following is still more preferable, 8 μA / cm 2 The following is even more preferable. When the photoelectric conversion element is adopted as a photodetector element, from the viewpoint of detection sensitivity, the smaller the value of the dark current, the more preferable.

[0394] The dark current is measured, for example, by the following method. 0.56 mass% of the target compound to be measured, 0.8 mass% of the polymer compound P-1 described below, 0.24 mass% of the PCBM described below, and the remaining amount of the solvent (a mixed solvent of chloroform and 1-chloronaphthalene (mixing ratio: chloroform / 1-chloronaphthalene = 97 wt% / 3 wt%)) that makes the total ink 100 mass% are mixed and stirred at 60 °C for 8 hours. The obtained mixed solution is filtered using a filter to obtain an ink.

[0395] A glass substrate on which a thin film (anode) of ITO with a thickness of 45 nm is formed by sputtering is prepared, and ozone UV treatment is performed on this glass substrate as a surface treatment.

[0396] Next, the cleaned glass substrate is spin-coated with a solution obtained by diluting an 80% ethoxylated aqueous solution of polyethyleneimine (manufactured by Sigma-Aldrich, 37 mass% aqueous solution) 500 times with water to form a coating film, and then placed on a hot plate and dried in the atmosphere at 120 °C for 10 minutes to make the coating film an electron transport layer.

[0397] Next, the obtained ink was applied onto the electron transport layer by spin coating to form a coating film, and then heat-treated for 5 minutes using a hot plate heated to 70 °C under the atmosphere to dry it (pre-bake process). Subsequently, it was heat-treated at 100 °C for 10 minutes on a hot plate under a nitrogen atmosphere (post-bake process) to form an active layer. The thickness of the formed active layer is set to be about 350 nm.

[0398] Next, a molybdenum oxide (MoO3) layer was formed on the formed active layer to a thickness of about 30 nm to serve as a hole transport layer.

[0399] Subsequently, a silver (Ag) layer was formed on the formed hole transport layer to a thickness of about 60 nm to serve as a cathode. Through the above steps, a photoelectric conversion element is manufactured on a glass substrate.

[0400] Next, a UV curable sealant, which is a sealing material, was applied to the outer periphery of a glass substrate that is a sealing substrate, and after bonding the glass substrate that is a sealing substrate to the center of the glass substrate that is a support substrate, by irradiating UV light, the photodetection element was sealed in the gap between the support substrate and the sealing substrate to obtain a sealed body of the photoelectric conversion element. The planar shape when viewed from the thickness direction of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate is a square of 2 mm × 2 mm. The obtained sealed body is used as a sample.

[0401] For the sample manufactured as described above, in the dark state where no light is irradiated, a voltage of -10 V to 2 V is applied to the sealed body of the photodetection element, and the current value when a reverse bias voltage of -3 V measured using a known method is applied is obtained as the value of the dark current (Jd).

[0402] <Applications of the photoelectric conversion element> Examples of the applications of the photoelectric conversion element of the present disclosure include a photodetection element and a solar cell. More specifically, the photoelectric conversion element of the present disclosure can generate a photocurrent by irradiating light from the transparent or translucent electrode side while applying a voltage (reverse bias voltage) between the electrodes, and can operate as a photodetector (photosensor). Further, by integrating a plurality of photodetectors, it can also be used as an image sensor. Thus, the photoelectric conversion element of the present disclosure can be particularly preferably used as a photodetector.

[0403] In addition, when the photoelectric conversion element of the present disclosure is irradiated with light, it can generate a photoelectromotive force between the electrodes and can operate as a solar cell. By integrating a plurality of photoelectric conversion elements, a solar cell module can also be formed.

[0404] The photoelectric conversion element of the present disclosure can be preferably applied as a photodetector to detection units provided in various electronic devices such as workstations, personal computers, portable information terminals, entrance / exit management systems, digital cameras, and medical devices.

[0405] The photoelectric conversion element of the present disclosure can be preferably applied to detection units of image detection units for solid-state imaging devices (for example, image sensors such as X-ray sensors) included in the above-exemplified electronic devices, such as X-ray imaging devices and CMOS image sensors, detection units of biometric information authentication devices that detect predetermined features of a part of a living body, such as fingerprint detection units, face detection units, vein detection units, and iris detection units (for example, near-infrared sensors), and detection units of optical biosensors such as pulse oximeters.

[0406] Since the compound of the present disclosure is included in the photoelectric conversion element of the present disclosure, it is driven at a longer wavelength than in the past.

[0407] <Method for manufacturing a photoelectric conversion element> The method for manufacturing the photoelectric conversion element of the present disclosure is not particularly limited. The photoelectric conversion element of the present disclosure can be manufactured by combining formation methods suitable for the materials selected for forming the components.

[0408] Hereinafter, a method for manufacturing a photoelectric conversion element having a configuration in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are sequentially in contact with each other will be described.

[0409] (Step of preparing a substrate) In this step, for example, a support substrate provided with an anode is prepared. Alternatively, a substrate provided with a conductive thin film formed of the electrode material described above can be obtained from the market, and if necessary, the conductive thin film can be patterned to form an anode, thereby preparing a support substrate provided with an anode.

[0410] In the method for manufacturing a photoelectric conversion element of the present disclosure, the method for forming the anode when forming the anode on the support substrate is not particularly limited. The anode can be formed on a configuration (e.g., support substrate, active layer, hole transport layer) on which the anode is to be formed by any conventionally known and suitable method such as vacuum evaporation, sputtering, ion plating, plating, or coating using the materials described above.

[0411] (Step of forming a hole transport layer) The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode.

[0412] The method for forming the hole transport layer is not particularly limited. From the viewpoint of making the formation step of the hole transport layer simpler, it is preferable to form the hole transport layer by any conventionally known and suitable coating method. The hole transport layer can be formed, for example, by a coating method using a coating solution containing the materials of the hole transport layer and a solvent described above or by vacuum evaporation.

[0413] (Step of forming an active layer) In the method for manufacturing a photoelectric conversion element of the present disclosure, the active layer is formed on the hole transport layer. The active layer, which is a main component, can be formed by any conventionally known and suitable formation step. The active layer is preferably manufactured by a coating method using ink (coating solution). The preferred embodiments of the ink are as described above.

[0414] Hereinafter, steps (i) and (ii) included in the step of forming the active layer, which is the main component of the present disclosure, will be described.

[0415] Step (i) As a method of applying the ink to the application target, any suitable coating method can be used. Examples of the coating method include a slit coating method, a knife coating method, a spin coating method, a microgravure coating method, a gravure coating method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method. The slit coating method, the spin coating method, the capillary coating method, or the bar coating method is preferable, the slit coating method, the spin coating method, or the capillary coating method is more preferable, and the slit coating method or the spin coating method is even more preferable.

[0416] The ink for forming the active layer is applied to an application target selected according to the photoelectric conversion element and its manufacturing method. The ink for forming the active layer can be applied to a functional layer of the photoelectric conversion element in the manufacturing process of the photoelectric conversion element, which is a functional layer where the active layer may exist. Therefore, the application target of the ink for forming the active layer varies depending on the layer structure and the order of layer formation of the manufactured photoelectric conversion element. For example, when the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are laminated, and the layers described on the left side are formed first, the application target of the ink for forming the active layer is the hole transport layer. Also, for example, when the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are laminated, and the layers described on the left side are formed first, the application target of the ink for forming the active layer is the electron transport layer.

[0417] Step (ii) As a method of removing the solvent from the ink coating film, that is, a method of removing the solvent from the coating film and solidifying it, any suitable method can be used. Examples of the method of removing the solvent include a method of directly heating using a hot plate in an inert gas atmosphere such as nitrogen gas, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, a drying method such as a vacuum drying method.

[0418] The thickness of the active layer can be adjusted to any desired thickness by appropriately adjusting the solid content concentration in the coating solution and the conditions of step (i) and / or step (ii).

[0419] The step of forming the active layer may include other steps, provided that the object and effect of the present disclosure are not impaired, in addition to step (i) and step (ii).

[0420] The method for manufacturing a photoelectric conversion device according to the present disclosure may be a method for manufacturing a photoelectric conversion device including a plurality of active layers, or a method in which steps (i) and (ii) are repeated a plurality of times.

[0421] The method for manufacturing a photoelectric conversion device according to the present disclosure includes a step of forming an electron transport layer (electron injection layer) provided on the active layer.

[0422] The method for forming the electron transport layer is not particularly limited. From the viewpoint of making the formation process of the electron transport layer simpler, it is preferable to form the electron transport layer by any suitable conventionally known vacuum evaporation method.

[0423] (Step of forming the cathode) The method for forming the cathode is not particularly limited. The cathode can be formed on the electron transport layer by any suitable conventionally known method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, or a plating method using, for example, the electrode materials exemplified above. Through the above steps, the photoelectric conversion device according to the present disclosure is manufactured.

[0424] (Step of forming the encapsulant) In forming the encapsulant, any suitable conventionally known encapsulant (adhesive) and substrate (encapsulation substrate) are used. Specifically, after applying an encapsulant such as a UV curable resin on a support substrate so as to surround the periphery of the manufactured photoelectric conversion device, and then bonding it without gaps with the encapsulant, the photoelectric conversion device is encapsulated in the gap between the support substrate and the encapsulation substrate using a method suitable for the selected encapsulant such as irradiation with UV light, whereby an encapsulant of the photoelectric conversion device can be obtained.

[0425] <Photodetector element> The photoelectric conversion element of the present disclosure, particularly a photodetector element (optical sensor), can be incorporated into an image sensor or a biometric authentication device (fingerprint authentication device, vein authentication device) and function as described above.

Example

[0426] Examples are shown below to explain the present disclosure in more detail. The present disclosure is not limited to the examples described below.

[0427] A photoelectric conversion element was fabricated using a p-type semiconductor material and an n-type semiconductor material.

[0428] <p-type semiconductor material> As the polymer compound P-1, a material synthesized with reference to the method described in International Publication No. 2011 / 052709 was used. As the polymer compound P-2, a material synthesized with reference to the method described in International Publication No. 2013 / 051676 was used. As the polymer compound P-19, a product named PCE-10 manufactured by 1-material was obtained from the market and used. As the polymer compound P-20, a product named PM-6 manufactured by 1-material was obtained from the market and used. As the polymer compound P-21, a material synthesized by the method described below was used.

[0429] (Polymer compound P-1)

[0430]

Chemical formula

[0431] (Polymer compound P-2)

[0432]

Chemical formula

[0433] (Polymer compound P-19)

[0434]

Chem.

[0435] (Polymer Compound P-20)

[0436]

Chem.

[0437] (Polymer Compound P-21)

[0438]

Chem.

[0439] <n-Type Semiconductor Material> As the n-type semiconductor material, the following compound was used. The synthesis method will be described later.

[0440] (Compound N-1)

[0441]

Chem.

[0442] (Compound N-2)

[0443]

Chem.

[0444] (Compound N-3)

[0445]

Chem.

[0446] (Compound N-4)

[0447]

Chem.

[0448] (Compound N-5)

[0449]

Chem.

[0450] (Compound N-6)

[0451]

Chem.

[0452] (Compound N-7)

[0453]

Chem.

[0454] (Compound N-8)

[0455]

Chem.

[0456] (Compound N-9)

[0457]

Chem.

[0458] (Compound N-10)

[0459]

Chem.

[0460] (Compound N-11)

[0461]

Chem.

[0462] (Compound RN-1)

[0463] [Chem.]

[0464] (Compound RN-2)

[0465] [Chem.]

[0466] (Synthesis of Compound N-1) Compound 2 was synthesized using Compound 1.

[0467] [Chem.]

[0468] In a 300 mL four-necked flask, 3-Methoxythiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 5.00 g, 43.8 mmol), 2-Hexyl-1-decanol (31.9 g, 131 mmol), p-TsOH·H2O (0.833 g, 4.38 mmol), and toluene (100 g) were charged. After purging with nitrogen, the temperature was raised to 110 °C. After stirring for 23 hours, it was cooled to room temperature. After diluting with toluene and performing liquid-liquid extraction and washing twice with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: hexane = 100 wt%) to obtain 13.4 g of Compound 2 as a colorless transparent liquid. The NMR spectrum of the obtained Compound 2 was analyzed. The results are as follows. 1H-NMR (300 MHz, CHLOROFORM-D) δ 7.16 (1H), 6.75 (1H), 6.21 (1H), 3.81 (2H), 1.77-1.71 (1H), 1.46-1.28 (m, 24H), 0.90-0.86 (m, 6H)

[0469] Compound 3 was synthesized using Compound 2.

[0470]

Chemical Structure

[0471] A 200 mL four-necked flask was charged with Compound 2 (4.0 g, 12.3 mmol) and THF (45 mL), purged with nitrogen, and then cooled to -73 °C. LDA (1 M in THF / Hexane, 13.6 mL, 13.6 mmol) was charged, and the internal temperature was maintained at -65 °C for 1 hour. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.2 mL, 18.5 mmol) and THF (22.5 mL) were charged into a dropping funnel and slowly added dropwise to the reaction mass at an internal temperature of -65 °C. After completion of the dropwise addition, the internal temperature was maintained at -65 °C for 1 hour, then the temperature was raised to room temperature and stirred for 2 hours. Quenching was carried out by pouring 20% aqueous ammonium chloride solution (26 mL). After removing the aqueous layer from the resulting mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain 5.91 g of Compound 3 as a crude product. The obtained Compound 3 was analyzed by NMR spectrum. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.26 (1H), 6.56 (1H), 3.82 (2H), 1.74-1.72 (1H), 1.57-1.19 (m, 36H), 00.88 (6H)

[0472] Compound 4 was synthesized using Compound 3.

[0473]

Chemical Structure

[0474] The crude product of Compound 3 (5.90 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (4.60 g, 14.4 mmol) (manufactured by JiangSu GR-Chem), and THF (149 mL) were charged into a 500 mL four-necked flask, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.600 g, 0.655 mmol), P(tBu3)HBF4 (0.399 g, 1.38 mmol), and an aqueous solution of 3 mol / L K3PO4 (60.6 g) were charged in this order, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature. After dilution with toluene and liquid-liquid washing with water twice, it was dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 3.72 g of Compound 4 as a yellowish-brown liquid. For the obtained Compound 4, the NMR spectrum was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.08 (1H), 6.29 (1H), 4.06 (2H), 3.83 (2H), 1.85-1.27 (m, 34H), 0.98-0.86 (m, 12H)

[0475] Compound 5 was synthesized using Compound 4.

[0476]

Chemical Structure

[0477] A 100 mL four-necked flask was charged with Compound 4 (1.60 g, 2.84 mmol) and chloroform (56.0 g), purged with nitrogen, and then cooled to 0 °C. NBS (0.501 g, 2.81 mmol) was charged and stirred at 0 °C. After stirring for 2 hours, water (40.0 g) was charged, and after warming to room temperature, the aqueous layer was removed by liquid separation from the resulting mass, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 1.84 g of Compound 5 as a yellowish-brown liquid. The NMR spectrum of the obtained Compound 5 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (1H), 7.45 (1H), 7.02 (1H), 4.07 (2H), 3.93 (2H), 1.86-1.27 (m, 34H), 0.99-0.86 (m, 12H)

[0478] Compound 7 was synthesized using Compound 6.

[0479]

Chemical formula

[0480] A 50 mL four-necked flask was charged with 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol) and THF (11.2 mL). After purging with nitrogen, the mixture was cooled to -73 °C. nBuLi (1.56 mol / L in Hexane, 1.75 mL, 2.73 mmol) was charged, and the internal temperature was maintained at -65 °C for 1 hour. A dropping funnel was charged with 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.85 mL, 3.72 mmol) and THF (5.6 mL), and the mixture was slowly added dropwise to the reaction mass at an internal temperature of -65 °C. After completion of the dropwise addition, the internal temperature was maintained at -65 °C for 1 hour, then the temperature was raised to room temperature and stirred for 1 hour. Quenching was carried out by pouring 20% aqueous ammonium chloride solution (5.3 mL). After removing the aqueous layer from the resulting mass by liquid separation, it was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain 1.49 g of the crude product of Compound 7.

[0481] Compound 8 was synthesized using Compound 7 and Compound 5.

[0482]

Chemical Structure

[0483] A 100 mL four-necked flask was charged with the crude product of Compound 7 (1.49 g), Compound 5 (2.05 g, 3.20 mmol), and THF (29.6 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.113 g, 0.123 mmol), P(tBu3)HBF4 (0.0749 g, 0.258 mmol), and a 3 mol / L aqueous solution of K3PO4 (11.4 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness by a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 1.27 g of Compound 8 as a red liquid. The NMR spectrum of the obtained Compound 8 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.46 (1H), 7.20 (1H), 7.13 - 7.10 (m, 2H), 6.93 - 6.91 (m, 1H), 4.10 (2H), 4.05 (2H), 1.93 - 0.57 (m, 80H)

[0484] Compound 9 was synthesized using Compound 8.

[0485]

Chemical Structure

[0486] Into a 50 mL four-necked flask, compound 8 (1.25 g, 1.30 mmol), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.497 g, 1.56 mmol) (manufactured by JiangSu GR-Chem), Pd(OAc)2 (0.0364 g, 0.162 mmol), [(tBu)2MePH]BF4 (0.0644 g, 0.259 mmol), pivalic acid (0.133 g, 1.30 mmol), K2CO3 (0.538 g, 3.89 mmol), and DMF (12.5 g) were charged, and nitrogen bubbling was carried out for 30 minutes. After nitrogen substitution, the internal temperature was raised to 120 °C and stirred for 5 hours. After cooling to room temperature, it was diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.620 g of compound 9 as a dark red-purple liquid. The NMR spectrum of the obtained compound 9 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.74 (1H), 7.47 (2H), 7.32 (1H), 7.20 (1H), 7.12 (1H), 4.13 -4.06 (m, 6H), 1.89-0.60 (m, 95H)

[0487] Compound N-1 was synthesized using compound 9.

[0488]

Chemical Structure

[0489] Into a 50 mL four-necked flask, compound 9 (0.600 g, 0.499 mmol), compound 10 (0.366 g, 1.50 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H2O (0.285 g, 1.50 mmol), EtOH (5.5 g), toluene (11.0 g), and MgSO4 (0.300 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.632 g (yield 78%) of compound N-1 as a black solid. The NMR spectrum of the obtained compound N-1 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.98-8.95 (m, 2H), 8.76-8.72 (m, 2H), 8.14-8.11 (m, 2H), 7.74 (1H), 7.50-7.32 (m, 4H), 4.19 (6H), 2.06-0.64 (m, 95H)

[0490] (Synthesis of Compound N-2) Compound 11 was synthesized using compound 2.

[0491]

Chemical Structure

[0492] A 1 L four-necked flask was charged with Compound 2 (15.35 g, 47.3 mmol) and THF (460.5 g), purged with nitrogen, and then cooled to 0 °C. NBS (8.33 g, 46.8 mmol) was charged and stirred at 0 °C. After stirring for 2 hours, an aqueous solution of 3% sodium sulfite (249 g) was charged. After warming to room temperature, the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: hexane) to obtain 18.53 g of Compound 11 as a colorless liquid.

[0493] Compound 12 was synthesized using Compound 11.

[0494]

Chemical formula

[0495] A 3 L four-necked flask was charged with Compound 11 (92.28 g, 228.7 mmol) and THF (1038 mL), purged with nitrogen, and then cooled to -73 °C. LDA (1 M in THF / Hexane, 228.7 mL, 228.7 mmol) was slowly added dropwise. After the addition was complete, the internal temperature was maintained at -73 °C for 2 hours. DMF (35.3 mL, 457.4 mmol) was slowly added dropwise to the reaction mass at an internal temperature of -73 °C. After the addition was complete, the temperature was raised to room temperature and stirred for 2 hours. Quenching was carried out by pouring a 20% aqueous ammonium chloride solution (489 mL). After that, the aqueous layer was removed from the resulting mass by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: hexane / ethyl acetate = 70 / 1 (volume ratio)) to obtain 45.00 g of Compound 12 as a yellow liquid. The obtained Compound 12 was analyzed by NMR spectrum. The results are as follows. 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.70 (1H), 7.37 (1H), 3.95 (2H), 1.80 - 1.72 (m, 1H), 1.57 - 1.27 (m, 24H), 0.90 - 0.86 (m, 6H)

[0496] Compound 13 was synthesized using Compound 8.

[0497]

Chemical Structure

[0498] Into a 50 mL four-necked flask, Compound 8 (0.96 g, 1.0 mmol), 5-Bromo-4-((2-octhlyldecyl)oxy)thiophene-2-carbaldehyde (0.864 g, 1.2 mmol), Pd(OAc)2 (0.168 g), [(tBu)2MePH]BF4 (0.099 g), pivalic acid (0.102 g), K2CO3 (0.415 g), and DMF (9.5 g) were charged, and nitrogen bubbling was carried out for 30 minutes. After nitrogen substitution, the internal temperature was raised to 110 °C and stirred for 7 hours. After cooling to room temperature, it was diluted with heptane, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 0.28 g of Compound 13. 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.76 (1H), 9.73 (1H), 7.46 (2H), 7.33 (1H), 7.20 (1H), 7.12 (1H), 4.12 - 4.06 (m, 6H), 1.89 - 0.60 (m, 111H)

[0499] Compound N-2 was synthesized using Compound 13.

[0500]

Chemical Structure

[0501] Into a 50 mL four-necked flask, compound 13 (0.28 g), compound 10 (0.15 g) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H2O (0.12 g), EtOH (2.5 g), toluene (5.6 g), and MgSO4 (0.14 g) were charged, and it was placed in an oil bath heated to 50 °C and kept warm. After stirring for 1 hour, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.22 g (yield 59%) of compound N-2 as a black solid. The NMR spectrum of the obtained compound N-2 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.99-8.96 (m, 2H), 8.77-8.72 (m, 2H), 8.15-8.11 (m, 2H), 7.74 (1H), 7.50-7.33 (m, 4H), 4.21-4.18 (m, 6H), 1.98-0.63 (m, 111H)

[0502] (Synthesis of Compound N-3) Compound 14 was synthesized using compound 3.

[0503]

Chemical Structure

[0504] A 200 mL four-necked flask was charged with the crude form of Compound 3 (5.52 g), Compound 12 (5.29 g), and THF (50 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.561 g), P(tBu3)HBF4 (0.373 g), and a 3 mol / L aqueous K3PO4 solution (22.7 g) were charged in sequence, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with heptane, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 100 to 50 / 5 (volume ratio)) to obtain 7.55 g of the crude form of Compound 14 as a yellowish-brown liquid. 1 H NMR (300 MHz, CDCl3) δ9.75 (s, 1H), 7.46 (s,1H), 7.08 (d, 1H), 6.28 (d, 1H),4.04 (d,2H)m,3.83 (d,2H),1.85 - 1.27 (m,44H),0.90 - 0.86 (m,12H)

[0505] Compound 15 was synthesized using Compound 14.

[0506]

Chemical Structure

[0507] A 100 mL four-necked flask was charged with Compound 14 (6.70 g) and chloroform (133 g). After nitrogen substitution by nitrogen flow, it was cooled to 0 °C using an ice bath. Then, NBS (1.75 g) was charged. After stirring for 1 hour, water was added and the temperature was raised to room temperature. After extracting the organic layer, it was washed once with water and once with saturated brine, dried over magnesium sulfate, and the solvent was distilled off using a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 100 / 100 to 95 / 5 (volume ratio)) to obtain 6.98 g of the crude form of Compound 15 as a yellowish-brown liquid. 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.77 (s, 1H), 7.45 (s 1H), 7.02 (s, 1H), 4.05 (d, 2H), 3.93 (d, 2H), 1.89 - 1.27 (m, 44H), 0.93 - 0.86 (m, 12H)

[0508] Compound 16 was synthesized using Compound 15.

[0509]

Chemical Structure

[0510] A 100 mL four-necked flask was charged with the crude form of Compound 7 (2.99 mmol), Compound 15 (3.89 mmol), and THF (36.1 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.137 g, 0.150 mmol), P(tBu3)HBF4 (0.0913 g, 0.315 mmol), and an aqueous solution of 3 mol / L K3PO4 (13.9 g) were charged in this order, and then the temperature was raised to 60°C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator. Half of the obtained crude product was purified by recycled GPC to obtain 0.930 g of Compound 16 as a red liquid. The NMR spectrum of the obtained Compound 16 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (1H), 7.44 (1H), 7.13 (1H), 7.12 (2H), 6.93 (1H), 4.04 - 4.10 (4H), 1.88 (6H), 0.57 - 1.60 (m, 90H)

[0511] Compound 17 was synthesized using Compound 16.

[0512]

Chemical Structure

[0513] To a 50 ml four-necked flask, compound 16 (0.761 g, 0.707 mmol) and chloroform (7.61 g) were added. While cooling in an ice bath, N-bromosuccinimide (0.126 g, 0.707 mmol) was added in three portions. The mixture was stirred for 30 minutes, 3% aqueous sodium sulfite solution (3.8 g) was added, and the temperature was raised to room temperature. After dilution with chloroform and liquid separation twice with water, it was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was subjected to short column chromatography (heptane / ethyl acetate = 10 / 1) to obtain 0.891 g of compound 17. The obtained compound 17 was analyzed by NMR spectrum. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.75(1H), 7.44(1H),7.19(1H),7.08(1H),6.94(1H), 4.03 - 4.10(4H), 1.84(6H), 0.58 - 1.84(m, 90H)

[0514] Compound 19 was synthesized using compound 18.

[0515]

Chemical formula

[0516] A 100 ml four-necked flask was purged with nitrogen, and compound 18 (1.00 g, 4.11 mmol, manufactured by Frontier Scientific), bis(pinacolato)diboron (1.57 g, 6.17 mmol), Pd(dppf)Cl2 (0.151 g, 0.206 mmol), potassium acetate (1.21 g, 12.3 mmol), and cyclopentyl methyl ether (20.0 g) were added, and the temperature was raised to 100 °C. After stirring for 2 hours, the reaction mass was cooled to room temperature and filtered through celite while washing with toluene. The filtrate was washed with water and dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and the crude product of compound 19 was obtained by concentrating to dryness on an evaporator. The obtained compound 19 was analyzed by NMR spectrum. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 10.83 (1H), 8.33 (1H), 8.20 (1H), 1.26 (12H)

[0517] Compound 20 was synthesized using Compound 17 and Compound 19.

[0518]

Chem.

[0519] A 50 mL four-necked flask was charged with Compound 17 (0.792 g, 0.686 mmol), Compound 19 (0.298 g, 1.03 mmol), and THF (18.0 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.314 g, 0.0342 mmol), P(tBu3)HBF4 (0.0209 g, 0.0720 mmol), and an aqueous solution of 3 mol / L K3PO4 (3.17 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain 0.952 g of the crude product of Compound 20. The crude product of the obtained Compound 20 was analyzed by NMR spectrum. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 10.68 (1H), 9.78 (1H), 8.26 (1H), 8.19 (1H), 7.92 (1H), 7.46 (1H), 7.22 (1H), 7.15 (1H), 4.10 (4H), 1.80 - 2.01 (6H), 0.50 - 1.70 (90H)

[0520] Compound N-3 was synthesized using Compound 20 and Compound 10.

[0521]

Chem.

[0522] In a 100 mL four-necked flask, charge the crude product of Compound 20 (0.850 g), Compound 10 (0.558 g, 2.06 mmol) synthesized according to the method described in WO 2020 / 109823, p-TsOH·H2O (0.391 g, 2.06 mmol), EtOH (7.70 g), toluene (17.0 g), and MgSO4 (0.425 g). Place it in an oil bath heated to 65 °C and keep it warm. After stirring for 1.5 hours, take it out of the oil bath and let it cool to room temperature. After removing MgSO4 by filtration, wash it while dissolving the precipitate with chloroform. After concentrating the filtrate with an evaporator, repulp wash it with methanol to obtain a crude product. The obtained crude product was purified by recycled GPC to obtain 0.102 g of Compound N-3 as a black solid. For the obtained Compound N-3, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ8.94(2H), 8.70(1H), 8.58(2H),8.10(2H), 7.50(2H), 4.15(4H), 1.95(6H), 0.64-1.40(90H)

[0523] (Synthesis of Compound N-4) Compound 21 was synthesized using Compound 8.

[0524]

Chemical Structure

[0525] A 100 mL four-necked flask was charged with compound 8 (2.27 g, 2.35 mmol), neopentyl glycol (0.43 g, 4.15 mmol), 10-camphorsulfonic acid (0.05 g, 0.21 mmol), and toluene (50 mL). After purging with nitrogen, the internal temperature was raised to 80 °C and stirred for 3 hours. After cooling to room temperature, it was quenched with a 5% aqueous K3PO4 solution. It was washed twice by liquid separation with water, the organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and then the whole amount was concentrated with a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 2.20 g of compound 21 as a red liquid (yield 89%). The obtained compound 21 was analyzed by NMR spectrum. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ7.07(1H),6.95(2H), 6.89(2H), 5.54(1H), 4.01(4H), 3.75(2H), 3.62(2H), 1.85(6H), 0.55-1.60(80H)

[0526] Compound 22 was synthesized using compound 21.

[0527]

Chemical formula

[0528] A 100 mL four-necked flask was charged with compound 21 (1.769 g, 1.685 mmol), bis(pinacolato)diboron (0.535 g, 2.106 mmol), 4,4'-di-tert-butyl-2,2'-dipyridyl (0.022 g, 0.0008 mmol), [Ir(OMe)(cod)]2 (0.0027 g, 0.0004 mmol), and cyclohexane (34 mL). After purging with nitrogen, the internal temperature was raised to 80 °C and stirred for 2 hours. Another 100 mL four-necked flask was charged with 8.48 g of water, and the cooled reaction mass was added dropwise. The aqueous layer was removed by liquid separation, and the organic layer was dried over magnesium sulfate and then filtered while passing through silica gel. The resulting filtrate was concentrated to dryness on a rotary evaporator to obtain 1.98 g of compound 22 (yield 84%). The NMR spectrum of the obtained compound 22 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.42(1H), 6.98(2H), 6.91(1H), 5.54(1H), 4.01(4H), 3.76(2H), 3.64(2H), 1.84(6H), 0.55 - 1.60(80H)

[0529] Compound 24 was synthesized using compound 22.

[0530]

Chemical formula

[0531] A 50 mL four-necked flask was charged with compound 22 (0.70 g, 0.595 mmol), compound 23 (0.28 g, 0.714 mmol, manufactured by Chem Shuttle), and THF (17.9 mL), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.027 g, 0.030 mmol), P(tBu3)HBF4 (0.018 g, 0.063 mmol), and 3 mol / L aqueous K3PO4 solution (1.9 mL) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. The reaction mass was diluted with toluene, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by recycled GPC to obtain 0.82 g of compound 24 (yield 50%). The NMR spectrum of the obtained compound 24 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.81(1H), 8.12(1H), 7.38(1H), 7.02(1H), 6.99(1H), 6.93(1H), 5.55(1H), 4.29(2H), 4.04(4H), 3.78(2H), 3.64(2H), 1.84 - 1.94(7H), 0.55 - 1.60(94H)

[0532] Compound 25 was synthesized using compound 24.

[0533]

Chemical Structure

[0534] A 50 mL four-necked flask was purged with nitrogen, charged with Compound 24 (0.39 g, 0.289 mmol), THF (18.5 mL), water (4.5 mL), and trifluoroacetic acid (0.45 mL), and stirred at room temperature for 3 hours. The reaction mass was diluted with heptane, quenched with a 5% aqueous solution of disodium hydrogen phosphate, and then washed twice with water by liquid separation. The organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 → 10 / 1 (volume ratio)) to obtain 0.32 g of Compound 25 (yield 87%). The NMR spectrum of the obtained Compound 25 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ9.84(1H),9.78(1H), 8.12(1H), 7.49(1H), 7.40(1H), 7.22(1H), 7.13(1H), 4.30(2H), 4.16(4H), 1.60-1.94(7H), 0.55-1.60(88H)

[0535] Compound N-4 was synthesized using Compound 25.

[0536]

Chemical Structure

[0537] In a 50 mL four-necked flask, compound 25 (0.32 g, 0.247 mmol), compound 10 (0.181 g, 0.742 mmol), p-TsOH·H2O (0.141 g, 0.742 mmol), EtOH (3.6 ml), toluene (7.3 ml), and MgSO4 (0.141 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration with an evaporator, the crude product was obtained by repulping with methanol. The obtained crude product was purified by recycled GPC to obtain 0.342 g (yield 79%) of compound N-4 as a black solid. The NMR spectrum of the obtained compound N-4 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.99(1H), 8.91(1H), 8.90(1H), 8.79(1H), 8.20(1H), 8.17(1H), 8.09(1H), 7.78(1H), 7.50(2H), 7.31(1H), 4.34(2H), 4.21(4H), 1.84 - 1.94(7H), 0.55 - 1.60(88H)

[0538] (Synthesis of Compound N-5) Compound 26 was synthesized using compound 8.

[0539]

Chemical Structure

[0540] Into a 50 mL four-necked flask, compound 8 (2.89 g), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (1.34 g), Pd(OAc)2 (0.126 g), [(tBu)2MePH]BF4 (0.223 g), pivalic acid (0.306 g), K2CO3 (1.24 g), and DMF (20 mL) were charged, and nitrogen bubbling was carried out for 30 minutes. After nitrogen substitution, the internal temperature was raised to 120 °C and stirred for 1 hour. After cooling to room temperature, it was diluted with heptane, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 9 / 1 (volume ratio)) to obtain 3.32 g of compound 26.

[0541] Compound N-5 was synthesized using compound 26.

[0542]

Chemical formula

[0543] Into a 100 mL four-necked flask, compound 26 (1.30 g, 1.10 mmol), compound 10 (0.767 g, 3.14 mmol) synthesized according to the method described in International Publication No. 2020 / 109823, p-TsOH·H2O (0.597 g, 1.50 mmol), EtOH (12 g), toluene (26 g), and MgSO4 (0.65 g) were charged, and it was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it in chloroform. After concentration on an evaporator, the crude product was obtained by repulping with methanol. The obtained crude product was purified by silica gel column (developing solvent: chloroform = 100 wt%) to obtain 1.26 g (yield 70%) of compound N-5 as a black solid. The NMR spectrum of the obtained compound N-5 was analyzed. The results are as follows. 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.03 (1H), 9.00 (1H), 8.85 (1H), 8.78 (1H), 8.19 (1H), 8.15 (1H), 7.71 (1H), 7.61 - 7.51 (m, 3H), 7.31 (1H), 4.19 (t, 4H), 2.85 (2H), 0.64 - 1.99 (m, 95H)

[0544] (Synthesis of Compound RN-1) Compound 27 was synthesized using Compound 6.

[0545]

Chemical Structure

[0546] Into a 50 mL four-necked flask, 4-Bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b’]dithiophene (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 g, 2.48 mmol), bis(pinacolato)diboron (1.58 g, 6.21 mmol), [Ir(OMe)(cod)]2 (19.8 mg, 0.0298 mmol), and tBu-bpy (16.0 mg, 0.0596 mmol) were charged. After purging with nitrogen, 15.0 g of cyclohexane was charged, and the flask was placed in an oil bath heated to 60 °C and kept warm. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. The cooled mass was quenched by pouring it into water. After removing the aqueous layer from the obtained mass by liquid separation, it was dried over magnesium sulfate, filtered while passing through silica gel, and then concentrated to dryness using a rotary evaporator to obtain 2.30 g of the crude form of Compound 27.

[0547] Compound 28 was synthesized using Compound 27 and Compound 5.

[0548]

Chemical Structure

[0549] A 50 mL four-necked flask was charged with the crude form of Compound 27 (1.13 g), Compound 5 (1.80 g, 2.81 mmol), and THF (18.2 g), and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.0560 g, 0.0612 mmol), P(tBu3)HBF4 (0.0372 g, 0.128 mmol), and a 3 mol / L aqueous solution of K3PO4 (5.66 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 8 / 1 (volume ratio)) to obtain 1.19 g of Compound 28 as a dark red viscous liquid. The NMR spectrum of the obtained Compound 28 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.46 (2H), 7.20 (2H), 7.13 (2H), 4.10 (4H), 4.06 (2H), 1.94 - 0.61 (m, 126H)

[0550] Compound RN-1 was synthesized using Compound 28.

[0551]

Chemical Structure

[0552] Into a 100 mL four-necked flask, compound 28 (1.15 g, 0.754 mmol), compound 10 (0.553 g, 2.26 mmol), p-TsOH·H2O (0.431 g, 2.26 mmol), EtOH (10.5 g), toluene (23.0 g), and MgSO4 (0.575 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%) to obtain 0.890 g (yield 60%) of compound RN-1 as a black solid. For the obtained compound RN-1, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.94-8.93 (m, 2H), 8.69 (2H), 8.10 (2H), 7.50-7.35 (m, 6H), 4.19-4.15 (m, 8H), 1.94-0.64 (m, 126H)

[0553] (Synthesis of Compound RN-2) Compound 29 was synthesized using compound 27.

[0554]

Chemical Structure

[0555] Into a 50 mL three-necked flask, compound 27 (0.775 g), 5-Bromo-4-((2-ethylhexyl)oxy)thiophene-2-carbaldehyde (0.870 g, 2.72 mmol), and THF (7.0 g) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.054 g, 0.06 mmol), P(tBu3)HBF4 (0.034 g, 0.12 mmol), and a 3 mol / L aqueous solution of K3PO4 (2.19 g) were charged in sequence, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with toluene, washed twice with water, dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 100 / 0 to 75 / 25 (mass ratio)) to obtain 0.521 g of compound 29 as a red-violet viscous liquid. The NMR spectrum of the obtained compound 29 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.75 (2H), 7.47 (2H), 7.32 (2H), 4.11 (4H), 1.79-1.96 (m, 6H), 1.37-171 (m, 16H), 0.88-1.02(m, 28H), 0.60-0.73(m, 14H)

[0556] Compound RN-2 was synthesized using compound 29.

[0557]

Chemical Structure

[0558] Into a 50 mL four-necked flask, compound 29 (0.521 g, 0.59 mmol), compound 10 (0.434 g, 1.78 mmol), p-TsOH·H2O (0.338 g, 1.78 mmol), EtOH (4.7 g), toluene (10.4 g), and MgSO4 (0.26 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. After concentration with an evaporator, the crude product was obtained by repulping and washing with methanol. The obtained crude product was purified by a silica gel column (developing solvent: chloroform = 100 wt%), and then repulping and washing with acetone gave 0.432 g (yield 55%) of compound RN-2 as a blue-green-black solid. For the obtained compound RN-2, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.00 (2H), 8.79 (2H), 8.17 (2H), 7.73 (2H), 4.21 (4H), 1.89 - 2.08 (m, 6H), 1.40 - 1.73 (m, 16H), 0.95 - 1.06 (m, 28H), 0.64 - 0.74 (m, 14H)

[0559] (Synthesis of compound N-6) Compound 36 was synthesized according to the following scheme. For the obtained compound 36, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, DMSO-d6) δ 8.36(1H), 8.18(1H), 6.05(1H)

[0560]

Chemical formula

[0561] Compound N-6 was synthesized using compound 26 and compound 36.

[0562]

Chemical formula

[0563] A 100 mL four-necked flask was charged with Compound 26 (0.300 g, 0.25 mmol), Compound 36 (0.399 g, 1.26 mmol), p-TsOH·H2O (0.336 g, 1.77 mmol), EtOH (19.5 g), and toluene (8.1 g), and then placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was taken out of the oil bath and allowed to cool to room temperature. The precipitated solid was collected by filtration, washed with methanol, ethanol, and heptane to obtain a crude product. The obtained crude product was purified by recycled GPC (developing solvent: chloroform = 100 wt%) to obtain 0.297 g of Compound N-6 as a black solid. The NMR spectrum of the obtained Compound N-6 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ8.90(s, 1H), 8.73(s, 1H), 8.48(m, 1H), 8.42(s, 1H), 8.32 - 8.24(m, 2H), 7.77(s, 1H), 7.68 - 7.64(m, 1H), 7.36 - 7.24(m, 3H), 4.25 - 4.10(m, 4H), 2.88(d, 2H), 2.03 - 0.68(m, 95H)

[0564] (Synthesis of Compound N-7) Compound 37 was synthesized using Compound 3.

[0565]

Chemical formula

[0566] Into a 500 mL four-necked flask, the crude product of Compound 3 (7.80 g), 5-Bromo-4-(2-ethylhexyl)thiophene-2-carbaldehyde (5.51 g, 18.1 mmol), and THF (197 mL) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.792, 0.866 mmol), P(tBu3)HBF4 (0.527 g, 1.81 mmol), and an aqueous solution of 3 mol / L K3PO4 (80.1 g) were charged in this order, and then the temperature was raised to 65 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with heptane, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by a silica gel column (developing solvent: heptane / ethyl acetate = 20 / 1 (volume ratio)) to obtain 7.78 g of Compound 37 as a brown liquid. The NMR spectrum of the obtained Compound 37 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 7.51 (1H), 6.93 (1H), 6.32 (1H), 3.84 (2H), 2.73 (2H), 0.83-1.77 (m, 46H)

[0567] Compound 38 was synthesized using Compound 37.

[0568]

Chemical Structure

[0569] Into a 500 mL four-necked flask, compound 37 (6.60 g, 12.0 mmol) and chloroform (231.0 g) were charged. After purging with nitrogen, the mixture was cooled to 0 °C. NBS (2.12 g, 11.9 mmol) was charged and stirred at 0 °C. After stirring for 2 hours, water (165.0 g) was charged. After warming to room temperature, the aqueous layer was removed from the resulting mass by liquid separation. The organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 25 / 1 (volume ratio)) to obtain 5.13 g of compound 38 as a brown liquid. The NMR spectrum of the obtained compound 38 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 7.53 (1H), 6.89(1H), 3.94 (2H), 2.69 (2H), 0.84-1.77 (m, 46H)

[0570] Compound 39 was synthesized using compound 7 and compound 38.

[0571]

Chemical Structure

[0572] Into a 200 mL four-necked flask, the crude product of Compound 7 (3.00 g), Compound 38 (3.19 g, 5.10 mmol), and THF (68.3 g) were charged, and nitrogen bubbling was carried out for 30 minutes. Pd2(dba)3 (0.259 g, 0.284 mmol), P(tBu3)HBF4 (0.172 g, 0.596 mmol), and an aqueous solution of 3 mol / L K3PO4 (26.2 g) were charged in this order, and then the temperature was raised to 60 °C. After stirring for 2 hours, it was cooled to room temperature. It was diluted with heptane, washed twice by liquid separation with water, dried over magnesium sulfate, filtered, and then concentrated to dryness with a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / toluene = 1 / 1 (volume ratio)) to obtain 3.37 g of Compound 39 as a red liquid. The NMR spectrum of the obtained Compound 39 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.82 (1H), 7.54 (1H), 7.10 - 7.19 (2H), 7.04 (1H), 6.91 - 6.94 (1H), 4.05 (2H), 2.78 (2H), 0.57 - 1.94 (m, 80H)

[0573] Compound 40 was synthesized using Compound 39 and Compound 12.

[0574]

Chemical Structure

[0575] Into a 100 mL four-necked flask, compound 39 (3.35 g, 3.53 mmol), compound 12 (2.13 g, 4.4 mmol), Pd(OAc)2 (0.149 g, 0.665 mmol), [(tBu)2MePH]BF4 (0.263 g, 1.06 mmol), pivalic acid (0.361 g, 3.53 mmol), K2CO3 (1.46 g, 10.6 mmol), and DMF (33.5 g) were charged, and nitrogen bubbling was carried out for 30 minutes. After nitrogen substitution, the internal temperature was raised to 120 °C and stirred for 1 hour. After cooling to room temperature, it was diluted with heptane, washed twice with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness on a rotary evaporator. The obtained crude product was purified by silica gel column (developing solvent: heptane / ethyl acetate = 10 / 1 (volume ratio)) to obtain 3.53 g of compound 40 as a red-violet liquid. The NMR spectrum of the obtained compound 40 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.83 (1H), 9.74 (1H), 7.54 (1H), 7.46 (1H), 7.33 (1H), 7.14 (1H), 7.04 (1H), 4.06 -4.09 (m, 4H), 2.79( 2H),0.60-1.90 (m, 111H)

[0576] Compound N-7 was synthesized using compound 40 and compound 10.

[0577]

Chemical Structure

[0578] In a 50 mL four-necked flask, compound 40 (1.001 g, 0.770 mmol), compound 10 (0.564 g, 2.311 mmol), p-TsOH·H2O (0.440 g, 2.311 mmol), EtOH (9.0 g), toluene (20.0 g), and magnesium sulfate (0.500 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, it was removed from the oil bath and allowed to cool to room temperature. Magnesium sulfate was removed by filtration, and the filtrate was concentrated. Methanol (20 g) was added to the concentrate, and after stirring at room temperature for 10 minutes, it was filtered and dried to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform). The column-purified product was dissolved in chloroform (5 g), heptane (5 g) was added at room temperature for crystallization, and after filtration and drying, 0.207 g of compound N-7 was obtained. The NMR spectrum of the obtained compound N-7 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 9.05(s, 1H), 8.95(s, 1H), 8.88(s, 1H), 8.72(br, 1H), 8.22(s, 1H) 8.11(s, 1H), 7.75(m, 1H), 7.71(s, 1H), 7.38 - 7.31(br, 3H), 4.21 - 4.17(m, 4H), 2.87(d, 2H), 1.99 - 0.63(m, 111H)

[0579] (Synthesis of Compound N-8) Compound N-8 was synthesized using compound 40 and compound 36.

[0580]

Chemical Structure

[0581] Into a 100 mL four-necked flask, compound 40 (0.272 g, 0.210 mmol), compound 36 (0.330 g, 1.04 mmol), p-TsOH·H2O (0.279 g, 1.46 mmol), EtOH (17.7 g), and toluene (7.4 g) were charged, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The crude product was obtained by filtration and washing with methanol. The obtained crude product was purified by recycled GPC (developing solvent: chloroform). 0.25 g of the purified product obtained by recycled GPC was dissolved in chloroform (4.0 g), methanol (17.5 g) was added at room temperature for crystallization, and compound N-8 (0.240 g) was obtained by filtration and drying. The NMR spectrum of the obtained compound N-8 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 8.93(1H),8.79 (1H), 8.38-8.48 (4H), 7.75-7.78(2H), 7.27-7.43 (3H), 4.20 (4H),2.88(4H),0.65-2.01 (111H)

[0582] (Synthesis of Compound N-9) Compound 41 was synthesized using compound 1.

[0583]

Chemical Structure

[0584] A 200 ml four-necked flask was purged with nitrogen, and pTsOH monohydrate (0.42 g, 2.19 mmol), 2-ethyl-1-hexanethiol (9.42 ml, 54.7 mmol), Compound 1 (2.16 ml, 21.9 mmol), and toluene (43.2 ml) were added. The mixture was stirred at 100 °C for 2.5 hours. After allowing it to cool to room temperature, it was washed twice by liquid separation with water. The organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane) to obtain 4.05 g of Compound 41. The NMR spectrum of the obtained Compound 41 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.31(1H), 7.08(1H), 7.00(1H), 2.84(2H), 1.20 - 1.55(9H), 0.83 - 0.95(6H)

[0585] Compound 42 was synthesized using Compound 41.

[0586]

Chemical formula

[0587] A 200 ml four-necked flask was purged with nitrogen, and Compound 41 (1.99 g, 8.76 mmol) and chloroform (21.1 ml) were added. The mixture was cooled in an ice bath, and N-bromosuccinimide (1.50 g, 8.42 mmol) was charged in three portions. After stirring for 4 hours, it was quenched with a 3% aqueous Na2SO3 solution, warmed to room temperature, and the aqueous layer was removed. After further washing once by liquid separation with water, the organic layer was dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product. The obtained crude product was dissolved in heptane and filtered through silica gel spread 10 mm thick on a Kiriyama funnel, and then concentrated again to obtain 2.45 g of Compound 42. The NMR spectrum of the obtained Compound 42 was analyzed. The results are as follows. 1H-NMR (300 MHz, CHLOROFORM-D) δ 7.25 (1H), 6.93 (2H), 2.83 (2H), 1.20 - 1.55 (9H), 0.83 - 0.95 (6H)

[0588] Compound 43 was synthesized using Compound 27 and Compound 11.

[0589]

Chemical Structure

[0590] A 100 mL four-necked flask was purged with nitrogen, and Compound 27 (1.375 g, 2.10 mmol), Compound 11 (1.86 g, 4.62 mmol), and THF (30.9 mL) were added. After nitrogen bubbling for 30 minutes, Pd2(dba)3 (0.096 g, 0.11 mmol), [(tBu)3PH]BF4 (0.061 g, 0.21 mmol), and 3M aqueous K3PO4 solution (7.00 mL) were added, and the temperature was raised to 60 °C. After maintaining the temperature for 1 hour, the reaction solution was cooled to room temperature, diluted with 25 mL of heptane, and washed twice by liquid separation with 12.5 mL of water. After drying over magnesium sulfate and removing the magnesium sulfate by filtration, the solution was concentrated using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column (developing solvent: hexane / ethyl acetate = 9 / 1 (v / v)) to obtain 2.15 g of Compound 43 as a red liquid. The NMR spectrum of the obtained Compound 43 was analyzed. The results are as follows. 1 H-NMR (300 MHz, CHLOROFORM-D) δ 7.08 (2H), 6.99 (2H), 6.84 (2H), 4.01 (4H), 1.84 (4H), 0.50 - 1.60 (H)

[0591] Compound 44 was synthesized using Compound 43.

[0592]

Chemical Structure

[0593] A 300 ml four-necked flask was purged with nitrogen, and compound 43 (5.93 g, 5.66 mmol) and THF (66.8 ml) were added. The internal temperature was cooled to -78 °C in a dry ice / acetone bath. A 1.6 M nBuLi hexane solution (4.17 ml, 6.51 mmol) was added dropwise and stirred for 1 hour. A solution of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.58 g, 8.50 mmol) in THF (33.4 ml) was prepared and added dropwise over 20 minutes. After the addition, the mixture was stirred at -78 °C for 1 hour, warmed to room temperature, and left overnight. The reaction vessel was cooled in an ice bath and quenched with a 20% aqueous ammonium chloride solution (12.1 ml). The reaction solution was diluted with heptane, the aqueous layer was removed, and the liquid-liquid washing with water was repeated twice. The organic layer was dried over magnesium sulfate, filtered, and concentrated by an evaporator to obtain 5.89 g of the crude product of compound 44.

[0594] Compound 45 was synthesized using compound 42 and compound 44.

[0595]

Chemical formula

[0596] To a 100 mL four-necked flask, add compound 42 (0.524 g, 1.70 mmol), the crude product of compound 44 (3.83 g), and tetrahydrofuran (51.3 mL). Replace the atmosphere with nitrogen, then charge Pd2(dba)3 (0.0781 g, 0.085 mmol, manufactured by Strem Chemicals), [(tBu)3PH]BF4 (0.0495 g, 0.171 mmol, manufactured by Tokyo Chemical Industry), and 3M aqueous K3PO4 solution (5.7 mL). Heat the mixture to 60 °C. After stirring for 1 hour while maintaining the temperature, cool the reaction solution to room temperature, dilute it with heptane, and perform liquid-liquid extraction and washing twice with water. Dry over magnesium sulfate, remove the magnesium sulfate by filtration, and then concentrate using a rotary evaporator to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane → heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.19 g of compound 45 as an orange oil. The NMR spectrum of the obtained compound 45 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 7.10 - 7.17(3H), 7.08(1H), 7.03(2H), 6.84(1H), 4.00 - 4.06(4H), 2.85(2H), 1.85(6H), 0.50 - 1.65(105H)

[0597] Compound 46 was synthesized using compound 45.

[0598]

Chemical Structure

[0599] To a 50 mL four-necked flask, compound 45 (1.04 g, 0.823 mmol) and CHCl3 (10.0 ml) were added, and the flask was purged with nitrogen. (Chloromethylene)dimethyliminium Chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 0.969 g, 7.57 mmol) was added, and the temperature was raised to 60 °C and the mixture was stirred while maintaining the temperature. After stirring for 5 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The reaction mixture was quenched by sequentially adding water (4.9 ml) and 5 wt% NaHCO3 aq. (9.9 ml) while stirring to the cooled mass, and the aqueous layer was removed from the resulting mass by liquid separation. The organic layer was washed with water by liquid separation, dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product of compound 46. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane / ethyl acetate = 10 / 1 (v / v)) to obtain 1.09 g of compound 46 as a reddish-purple oil. The NMR spectrum of the obtained compound 46 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.81(1H), 9.73(1H), 7.67(1H), 7.45(1H), 7.34(2H), 7.20(1H), 4.08(4H), 2.89(2H), 1.90(6H), 0.50 - 1.65(105H)

[0600] Compound N-9 was synthesized using compound 46 and compound 36.

[0601]

Chemical Structure

[0602] In a 100 mL four-necked flask, compound 46 (0.400 g, 0.301 mmol), compound 36 (0.237 g, 0.752 mmol), p-TsOH·H2O (0.200 g, 1.05 mmol), EtOH (26.0 g), and toluene (10.8 g) were added, and the flask was placed in an oil bath heated to 65 °C and kept warm. After stirring for 2 hours, the flask was removed from the oil bath and allowed to cool to room temperature. The precipitated solid was collected by filtration, washed with methanol, ethanol, and heptane to obtain the crude product. The obtained crude product was purified by recycled GPC (developing solvent: chloroform = 100 wt%) to obtain 0.359 g of compound N-9 as a black solid. The NMR spectrum of the obtained compound N-9 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 8.84(1H), 8.78(1H), 8.44(2H), 8.38(2H), 7.85 (1H) 7.78(1H), 7.53(1H), 7.41(1H), 7.34(1H), 4.19(4H), 3.07(2H), 2.01(5H), 0.60-1.85(104H)

[0603] (Synthesis of compound N-10) Compound N-10 was synthesized using compound 46 and compound 10.

[0604]

Chemical formula

[0605] Into a 100 mL four-necked flask, compound 46 (0.300 g, 0.23 mmol), compound 10 (0.165 g, 0.68 mmol), p-TsOH·H2O (0.129 g, 0.68 mmol), EtOH (3.4 ml), toluene (6.9 ml), and MgSO4 (0.150 g) were charged. After purging with nitrogen, the mixture was heated to 65 °C and kept warm with stirring. After stirring for 3 hours, it was removed from the oil bath and allowed to cool to room temperature. After removing MgSO4 by filtration, the precipitate was washed while dissolving it with chloroform. The solution obtained by the evaporator was concentrated, and then washed with methanol by Kiriyama filtration to obtain a crude product. The obtained crude product was purified by recycled GPC to obtain 0.29 g of compound N-10 as a black solid (yield 72%). The NMR spectrum of the obtained compound N-10 was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ9.84(1H), 9.04(1H), 8.96(1H), 8.82(1H), 8.71(1H), 8.21(1H), 8.11(1H), 7.84 (1H), 7.75(1H), 7.60(1H), 7.39(1H), 7.33(1H), 4.21(2H), 4.19(2H), 3.03(2H), 1.99-0.5(118H)

[0606] (Synthesis of Compound N-11) As shown in the following formula, compound 48 was synthesized using compound 47.

[0607]

Chemical Structure

[0608] To a 50 ml four-necked eggplant flask, add Compound 47 (manufactured by Tokyo Chemical Industry Co., Ltd., 1.76 g, 7.0 mmol) and tetrahydrofuran (9.9 ml). After purging with nitrogen, charge 1,3-Dibromo-5,5-dimethylhydantoin (manufactured by Tokyo Chemical Industry Co., Ltd., 1.20 g, 3.5 mmol), and place it in an oil bath heated to 30 °C for heat preservation. After stirring for 1 hour, remove it from the oil bath and allow it to cool to room temperature. Add 40.8 ml of heptane to the reaction mass, filter off the precipitated solid, dry the filtrate over magnesium sulfate, filter, and concentrate the whole volume using a rotary evaporator to obtain the crude form of Compound 48. The obtained crude product was purified by silica gel column (developing solvent: heptane) to obtain 1.47 g of Compound 48 as a transparent liquid (yield 63%).

[0609] As shown in the following formula, Compound 49 was synthesized using Compound 48 and Compound 44.

[0610]

Chemical formula

[0611] To a 100 mL four-necked flask, add Compound 48 (0.239 g, 0.72 mmol), Compound 44 (1.86 g, 0.79 mmol), and tetrahydrofuran (10.7 ml). After purging with nitrogen, charge Pd2(dba)3 (manufactured by Strem Chemicals, 0.033 g, 0.04 mmol), [(tBu)3PH]BF4 (manufactured by Tokyo Chemical Industry Co., Ltd., 0.021 g, 0.07 mmol), and 3M K3PO4 aqueous solution (2.4 ml), and heat to 60 °C. After keeping warm and stirring for 1 hour, cool the reaction solution to room temperature, dilute with heptane (16.5 ml), and wash by liquid separation twice with water (9.5 ml). Dry over magnesium sulfate, filter to remove magnesium sulfate, and concentrate using a rotary evaporator to obtain the crude product. The obtained crude product was purified by silica gel column (developing solvent: heptane / toluene = 95 / 5 (v / v)) to obtain 0.37 g of Compound 49 as a red liquid (yield 40%).

[0612] As shown in the following formula, Compound 50 was synthesized using Compound 49.

[0613]

Chem.

[0614] Into a 50 mL four-necked flask, Compound 49 (0.36 g, 0.28 mmol) and CHCl3 (10.5 ml) were added, and the flask was purged with nitrogen. (Chloromethylene)dimethyliminium Chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 0.18 g, 1.40 mmol) was charged, and the temperature was raised to 60 °C and the mixture was kept warm and stirred. After stirring for 1 hour, the flask was removed from the oil bath and allowed to cool to room temperature. Quenching was carried out by sequentially pouring water (14.5 ml) and 5 wt% NaHCO3 aq. (10.5 ml) into the cooled mass while stirring. The aqueous layer was removed from the resulting mass by liquid separation, the organic layer was washed with water (14.5 ml), dried over magnesium sulfate, filtered, and then concentrated to dryness using a rotary evaporator to obtain a crude product of Compound 50. The obtained crude product was purified by silica gel column chromatography (developing solvent: heptane / toluene = 7 / 3 (v / v)) to obtain 0.24 g of Compound 50 as a red liquid (yield 63%).

[0615] Compound N-11 was synthesized using Compound 50 and Compound 36.

[0616]

Chem.

[0617] In a 100 mL four-necked flask, compound 50 (0.24 g, 0.18 mmol), compound 36 (0.215 g, 0.44 mmol), p-TsOH·H2O (0.118 g, 0.62 mmol), EtOH (19.7 ml), and toluene (7.5 ml) were charged. After nitrogen bubbling for 30 minutes, the temperature was raised to 65 °C and the mixture was kept warm with stirring. After 1 hour, compound 36 (0.106 g, 0.22 mmol) and p-TsOH·H2O (0.60 g, 0.31 mmol) were added, and the mixture was further kept warm with stirring for 2 hours and then cooled to room temperature. The precipitated solid was filtered, washed successively with methanol (24.2 ml), ethanol (24.3 ml), and heptane (23.8 ml), and air-dried to obtain the crude product of the target compound. Purification was carried out by recycling GPC using CHCl3 as the mobile phase. The concentrated fraction was washed into a Kiriyama filter with methanol for washing, and the residue was dried to obtain compound N-11 (yield 81%). For the obtained compound N-11, the NMR spectrum was analyzed. The results are as follows. 1 1H-NMR (300 MHz, CHLOROFORM-D) δ 9.16(1H), 8.80(1H), 8.51(1H), 8.46(1H), 8.42(1H), 8.39(1H), 7.78(1H), 7.46(1H), 7.33(1H), 4.20(4H), 2.97(4H), 2.00(4H), 1.9 - 0.5(114H)

[0618] (Synthesis of polymer compound P-21) Compound 53 was synthesized using compound 51 and compound 52.

[0619]

Chemical formula

[0620] Magnesium (1.61 g, 0.066 mol), THF (47 g), and iodine (32 mg) were added to a nitrogen-substituted 1-L four-necked flask and stirred. After the purple color of iodine disappeared, a solution of compound 52 (19.8 g, 0.063 mmol) in THF (36 g) was added dropwise to generate a Grignard reagent. A solution containing compound 51 (5.21 g, 0.025 mol) synthesized by the method described in WO 2011 / 136311 and THF (107 g) was added dropwise to the four-necked flask so that the internal temperature did not exceed 40 °C to obtain a reaction solution. Then, the mixture was stirred for 1 hour, an aqueous ammonium chloride solution was poured into the reaction solution to stop the reaction, and liquid separation was performed. The organic layer was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and then the filtrate was concentrated using a rotary evaporator. By purification using silica gel column chromatography (the developing solvent used was hexane and ethyl acetate), 14.21 g (20.7 mmol, yield 83%) of compound 53 was obtained.

[0621] For compound 53 1 The results of 1H-NMR measurement are as follows. δ (ppm): 7.82 - 7.76 (m, 1H), 7.64 (s, 2H), 7.43 (m, 2H), 7.31 (m, 10H), 7.25 (m, 2H), 7.21 (m, 1H), 7.13 (m, 2H), 6.91 (d, 1H), 6.64 (d, 1H), 6.43 (d, 1H), 3.72 - 3.64 (m, 1H), 2.63 (t, 4H), 1.61 (m, 4H), 1.22 - 1.34 (m, 12H), 0.86 (t, 6H)

[0622] Compound 54 was synthesized using compound 53.

[0623]

Chemical formula

[0624] A four-necked flask with a capacity of 500 mL was charged with Compound 53 (14.21 g, 0.0208 mmol) and heptane (130 g). After purging the inside of the reaction vessel with nitrogen, trifluoroacetic acid (0.409 g, 0.0036 mmol) was charged, the temperature was raised to 60 °C, and the mixture was stirred for 30 minutes and then cooled to room temperature to obtain a reaction solution. The reaction solution was washed twice with water, the organic layer was dehydrated with magnesium sulfate, passed through a Kiritani funnel filled with silica gel, and the filtrate was concentrated using a rotary evaporator to obtain 13.37 g of Compound 54 (yield 96.6%).

[0625] For Compound 54 1 The results of 1H-NMR measurement are as follows. δ (ppm): 7.73 (s, 2H), 7.64 (s, 2H), 7.45 - 7.43 (m, 7H), 7.33 - 7.31 (m, 2H), 7.26 (s, 2H), 7.22 (s, 1H), 7.16 - 7.13 (m, 1H), 6.93 (d, 1H), 6.65 (d, 1H), 6.44 (d, 1H), 2.64 (t, 4H), 1.67 - 1.58 (m, 4H), 1.34 - 1.26 (m, 12H), 0.86 (t, 6H)

[0626] Compound 55 was synthesized using Compound 54.

[0627]

Chemical Structure

[0628] Compound 54 (25.0 g), tetraethylethylenediamine (5.6 mL), and dehydrated tetrahydrofuran (436 mL) were placed in a flask substituted with argon and stirred until dissolved. Next, the solution was cooled to -65 °C in a cooling bath containing dry ice and acetone, and then a 1.6 mol / L nBuLi hexane solution (58.9 mL) was added dropwise to the flask and stirred at -65 °C for 2 hours. While maintaining -65 °C, a solution prepared by dissolving triisopropoxyborane (19.74 g) in 40 mL of THF was added dropwise to the flask, and after stirring at -65 °C for an additional 1 hour, the temperature was raised to room temperature to obtain a reaction solution. Next, 290 mL of 2% hydrochloric acid was added to the reaction solution, and liquid separation was performed. Magnesium sulfate and trimethylolethane (13.5 g) were added to the organic layer and stirred at room temperature for 1 hour. Magnesium sulfate was removed by filtration to obtain a filtrate. The solvent was distilled off from the filtrate under reduced pressure, toluene (700 mL) was added, and the precipitated solid was removed by filtration. After adding hexane and removing the supernatant, the solvent was removed under reduced pressure to obtain 37.7 g (yield 109%) of compound 55.

[0629] Compound 56 was synthesized using compound 51.

[0630]

Chemical formula

[0631] Magnesium (12.37 g), THF (360 mL), and two grains of iodine were added to an argon-substituted flask and stirred. After the purple color of iodine disappeared, a solution containing 1-bromo-3,5-diphenylbenzene (148.48 g) and THF (280 mL) was added dropwise to generate a Grignard reagent. A solution of compound 51 (35.88 g) synthesized by the method described in International Publication No. 2011 / 136311 in THF (820 mL) was added dropwise so that the internal temperature did not exceed 40 °C to obtain a reaction solution. Then, it was stirred overnight, and a 10% aqueous ammonium chloride solution (450 mL) was poured into the reaction solution to stop the reaction, followed by liquid separation. The organic layer was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and then the filtrate was concentrated using a rotary evaporator. By purification using silica gel column chromatography (the developing solvent used was hexane and ethyl acetate), 128.6 g (yield 99%) of compound 56 was obtained.

[0632] Compound 57 was synthesized using compound 56.

[0633]

Chemical formula

[0634] Compound 56 (128.6 g) and toluene (1376 mL) were charged into an argon-substituted flask. After replacing the inside of the reaction vessel with nitrogen, p-toluenesulfonic acid monohydrate (5.39 g) was charged and the temperature was raised to 100 °C. After stirring for 1.5 hours, it was cooled to room temperature to obtain a reaction solution. After washing the reaction solution with water, the organic layer was dehydrated with magnesium sulfate, the magnesium sulfate was removed by filtration, and then the filtrate was concentrated using a rotary evaporator. After adding hexane (150 mL) to precipitate a solid, toluene (50 mL) and hexane (50 mL) were added, and after ice-cooling for 60 minutes, the precipitated solid was filtered and dried to obtain 106 g (yield 96%) of compound 57.

[0635] Compound 58 was synthesized using compound 57.

[0636]

Chemical formula

[0637] Compound 57 (28.38 g), tetraethylethylenediamine (6.5 mL), and 568 mL of dehydrated THF were placed in a flask substituted with argon and stirred until dissolved. Subsequently, the solution was cooled to -65 °C in a cooling bath containing dry ice and acetone, and then a 1.6 mol / L nBuLi hexane solution (69.9 mL) was added dropwise, followed by stirring at -65 °C for 1 hour. While maintaining -65 °C, a solution prepared by dissolving triisopropoxyborane (22.96 g) in 11.4 mL of THF was added dropwise, and after stirring at -65 °C for an additional 1 hour, the temperature was raised to room temperature. Next, 329 mL of 10% hydrochloric acid was added to the reaction solution, and liquid separation was performed. Magnesium sulfate and trimethylolethane (15.72 g) were added to the organic layer, and the mixture was stirred at room temperature for 1 hour. Magnesium sulfate was removed by filtration. The solvent was distilled off from the filtrate under reduced pressure, chloroform (480 mL) was added, and the mixture was stored refrigerated overnight. After removing the precipitated solid, the solvent was distilled off from the filtrate under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from ethanol and hexane to obtain 36.18 g (yield 91.5%) of Compound 58.

[0638] Compound 59 was synthesized according to the procedure described in the literature (Patent No. 6070722).

[0639]

Chemical formula

[0640] Into a glass reaction vessel equipped with a cooling device at room temperature, as raw materials, compound 55 (0.39 mmol), compound 58 (0.39 mmol), compound 59 (1.18 mmol), 4,7-dibromo-5,6-difluoro-2,1,3-benzothiadiazole (0.40 mmol), 4,7-dibromo[1,2,5]thiadiazolo[3,4-c]pyridine (1.60 mmol), water (59.5 g), 40 mass% aqueous potassium phosphate solution (10.5 mL), THF (42 mL), tetralin (20 mL), and bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol) were added and stirred at 65 °C for 1 hour. A mixed solution of phenylboronic acid (2 mmol) and 40 mass% aqueous potassium phosphate solution (7.2 mL) was added as a raw material to the reaction vessel and stirred at 65 °C for 1 hour. The resulting organic layer was washed with an aqueous sodium diethyldithiocarbamate solution, aqueous acetic acid, and water, and then the washed organic layer was added to methanol and the precipitated solid was recovered by filtration to obtain a crude polymer. The obtained crude polymer was dissolved in tetralin, passed through a 5B (JIS P 3801: Type 5 B) filter paper, and then added to methanol again, and the precipitated solid was recovered by filtration to obtain the polymer compound P-21.

[0641] <Preparation of Ink> [Preparation of Ink (I-1)] The following components were mixed and stirred at 60 °C for 8 hours. The resulting mixed solution was filtered using a filter to obtain Ink (I-1). · p-type semiconductor material: Polymer compound P-19 … 0.8 mass% · n-type semiconductor material: Compound N-1 … 0.56 mass% · n-type semiconductor material: C60PCBM … 0.24 mass% · Solvent: Chloroform / 1-chloronaphthalene = 97 wt% / 3 wt% … The remaining amount to make 100 mass% of the whole ink

[0642] C60PCBM ([6,6]-Phenyl C61 butyric acid methyl ester) was obtained from the market under the trade name "E100" manufactured by Frontier Carbon Corporation and used.

[0643] [Preparation of Ink (I-2) to (I-3)] Ink (I-2) or Ink (I-3) was obtained in the same manner as the preparation of Ink (I-1), except that Compound N-1 was changed to Compound RN-1 or Compound RN-2.

[0644] [Preparation of Ink (I-4)] Ink (I-4) was obtained in the same manner as the preparation of Ink (I-1), except that the polymer compound P-19 was changed to the polymer compound P-20.

[0645] [Preparation of Ink (I-5) to (I-7)] Ink (I-5) to Ink (I-7) were obtained in the same manner as the preparation of Ink (I-1), except that Compound N-1 was changed to Compounds N-2 to N-4.

[0646] [Preparation of Ink (I-8)] The following components were mixed and stirred at 60 °C for 8 hours. The resulting mixture was filtered using a filter to obtain Ink (I-8). · p-type semiconductor material: Polymer compound P-2... 2.4% by mass · n-type semiconductor material: Compound N-5... 1.7% by mass · Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 1 wt%... The remaining amount to make 100% by mass of the whole ink

[0647] [Preparation of Ink (I-9)] The following components were mixed and stirred at 60 °C for 8 hours. The resulting mixture was filtered using a filter to obtain Ink (I-9). · p-type semiconductor material: Polymer compound P-21... 2.3% by mass · n-type semiconductor material: Compound N-6... 2.3% by mass · Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 1 wt%... The remaining amount to make 100% by mass of the whole ink

[0648] [Preparation of Ink (I-10)] The following components were mixed and stirred at 60 °C for 8 hours. The resulting mixture was filtered using a filter to obtain Ink (I-10). · p-type semiconductor material: Polymer compound P-2 … 2.3 mass% · n-type semiconductor material: Compound N-7 … 2.3 mass% · Solvent: 1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 90 wt% / 1 wt% … The remaining amount to make 100 mass% of the whole ink

[0649] [Preparation of Ink (I-11)] Ink (I-11) was obtained in the same manner as the preparation of Ink (I-10), except that Compound N-7 was changed to Compound N-8.

[0650] [Preparation of Inks (I-12) to (I-14)] Inks (I-12) to (I-14) were obtained in the same manner as the preparation of Ink (I-9), except that Compound N-6 was changed to Compounds N-9 to N-11.

[0651] [Preparation of Ink (I-15)] Ink (I-15) was obtained in the same manner as the preparation of Ink (I-14), except that Compound P-21 was changed to Compound P-1.

[0652] [Example 1] [Manufacture of Photovoltaic Element and Its Encapsulant] A glass substrate on which a thin film (anode) of ITO with a thickness of 45 nm was formed by sputtering was prepared, and this glass substrate was subjected to ozone UV treatment as a surface treatment.

[0653] Next, the cleaned glass substrate was coated with a zinc oxide dispersion by spin coating to form a coating film, and then placed on a hot plate and dried in the air at 120 °C for 10 minutes to use the coating film as an electron transport layer.

[0654] Next, after applying ink (I-1) onto the electron transport layer by spin coating to form a coating film, it was heat-treated for 5 minutes using a hot plate heated to 70 °C under the atmosphere to dry it (pre-bake process). Then, it was heat-treated at 100 °C for 10 minutes on a hot plate under a nitrogen atmosphere (post-bake process) to form an active layer. The thickness of the formed active layer was about 350 nm.

[0655] Next, a molybdenum oxide (MoO3) layer was formed with a thickness of about 30 nm on the formed active layer to serve as a hole transport layer.

[0656] Next, a silver (Ag) layer was formed with a thickness of about 60 nm on the formed hole transport layer to serve as a cathode. Through the above steps, a photoelectric conversion element was manufactured on a glass substrate.

[0657] Next, a UV curable sealant, which is a sealing material, was applied to the outer periphery of a glass substrate that is a sealing substrate. After bonding the glass substrate that is a sealing substrate to the center of a glass substrate that is a support substrate, by irradiating UV light, the photoelectric conversion element was sealed in the gap between the support substrate and the sealing substrate to obtain a sealed body of the photoelectric conversion element. The planar shape when viewed from the thickness direction of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate was a square of 2 mm × 2 mm. The obtained sealed body was designated as Sample 1.

[0658] [Evaluation of Photoelectric Conversion Element (Dark Current)] For the manufactured Sample 1, in a dark state without light irradiation, a voltage from -10 V to 2 V was applied to the sealed body of the photodetector, and the current value when a reverse bias voltage of -3 V was applied, which was measured using a known method, was obtained as the value of the dark current. The results are shown in Table 1 below.

[0659] [Examples 2 to 12, Comparative Example 1, and Comparative Example 2] Instead of ink (I-1), inks (I-2) to (I-14) were used, and in the same manner as in Example 1 already described, sealed bodies of photoelectric conversion elements were manufactured and evaluated. The results are shown in Table 1 below.

[0660]

Table 1

[0661] As shown in Table 1, according to the photoelectric conversion device using the compound of the present disclosure as an n-type semiconductor material, the value of the dark current could be reduced to about 1 / 100 to 1 / 2 compared with the photoelectric conversion device using the conventional n-type semiconductor material.

[0662] [Evaluation of Photodetector] A reverse bias voltage of -3V was applied to the package of the manufactured photodetector, and the external quantum efficiency (EQE) and the dark current at this applied voltage were measured and evaluated using a solar simulator (CEP-2000, manufactured by Spectral Instruments) and a source meter (KEITHLEY 2450 Source Meter, manufactured by Keithley Instruments), respectively.

[0663] Regarding EQE, first, with a reverse bias voltage of -3V applied to the package of the photodetector, the current value of the current generated when irradiated with light of 1300nm was measured, and the value of EQE at a wavelength of 1300nm was calculated by a known method.

[0664] Next, the specific detectivity (D*) (Jones) at an applied voltage of -3V was calculated based on the obtained measurement values and the calculation formula represented by the following mathematical formula.

[0665] (Equation 1) D * =(λ / 1240)×(EQE) / (2eJd) 0.5

[0666] In the above mathematical formula, EQE is the external quantum efficiency, representing the EQE at wavelength λ, and Jd represents the dark current.

[0667]

Table 2

[0668] In Table 2, N-6 and N-11 have acceptors containing a quinoxaline skeleton.

[0669] As shown in Table 2, a composition using an n-type semiconductor material which is a compound of the present disclosure having a predetermined acceptor group and using a polymer compound containing at least one selected from the group consisting of the structural unit represented by the predetermined formula (3) and the structural unit represented by the formula (4) is used. According to the photoelectric conversion element manufactured thereby, in addition to reducing the dark current as shown in Table 1, an element showing a high D * was obtained.

Explanation of Signs

[0670] 10 Photoelectric conversion element 11 Support substrate 12 Anode 13 Hole transport layer 14 Active layer 15 Electron transport layer 16 Cathode 17 Sealing member

Claims

1. A compound represented by the following formula (1): 【Chemistry 1】 (In formula (1), D's each independently represent a polycyclic aromatic group having two bonds, and a conjugated structure connecting the two bonds via a shortest distance contains four or more double bonds, L1 and L1' each independently represent an aromatic group having two bonds, and a conjugated structure connecting the two bonds in a shortest distance contains three or less double bonds, L2 is not the same chemical structure as D, but is an aromatic group having two bonds; n is 1 or 2, m is 0 or 1, and n+m=2; A1 and A2 are acceptor groups.

2. The compound according to claim 1, represented by the following formula (2): 【Chemistry 2】 (In formula (2), D is a polycyclic aromatic group having two bonds, and a conjugated structure connecting the two bonds in the shortest distance contains four or more double bonds, L1 and L1' each independently represent an aromatic group having two bonds, and a conjugated structure connecting the two bonds in a shortest distance contains three or less double bonds, L2 is not the same chemical structure as D, but is an aromatic group having two bonds; A1 and A2 are acceptor groups.

3. 3. The compound according to claim 1 or 2, wherein the polycyclic aromatic group comprises a five-membered ring structure, and the two bonds of the polycyclic aromatic group each extend from the five-membered ring structure.

4. The compound according to claim 1 or 2, wherein the conjugated structure connecting the two bonds in L2 via the shortest distance contains three or less double bonds.

5. 3. The compound according to claim 1 or 2, wherein L1, L1' and L2 each independently have a conjugated structure connecting the two bonds in the shortest distance that contains two or less double bonds.

6. In D, the polycyclic aromatic group has a side chain, and a carbon to which the side chain is bonded is an sp3 carbon or an sp2 carbon; The compound according to claim 1 or claim 2, wherein the side chain has an aromatic ring or a branched chain.

7. The compound according to claim 1 or 2, wherein L1, L1' and L2 are all different chemical structures from each other, or any two of L1, L1' and L2 are the same chemical structure.

8. The compound according to claim 1 or 2, wherein D is a donor group having a side chain having 6 or more carbon atoms.

9. The compound according to claim 1 or 2, wherein D, L1, L1' and L2 each have a sulfur-containing heterocycle.

10. The compound according to claim 1 or 2, wherein D is each independently any group represented by the following formula (D-1) to the following formula (D-7). 【Chemistry 3】 In formulas (D-1), (D-2), (D-6) and (D-7), X is any of groups represented by the following formulas (X-1) to (X-6). 【Chemistry 4】 In formulae (D-3) to (D-7) and formulae (X-1) to (X-6), R Ｄ１ are each independently Hydrogen atoms, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an alkylthio group which may have a substituent; a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents a nitro group, Ar １ and Ar ２ are each independently an aromatic carbocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures, or an aromatic heterocyclic ring which may have a substituent and may be further condensed with a plurality of ring structures. １ and Ar ２ Either one of them may not be present.)

11. The compound according to claim 1 or 2, wherein L1 and L1′ are each independently any of groups represented by the following formulae (L1-1) to (L1-9): 【Chemistry 5】 (In formulas (L1-1) to (L1-9), R Ｌ１ are each independently Hydrogen atoms, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents a nitro group.

12. The compound according to claim 1 or 2, wherein L2 is each independently any of groups represented by the following formulas (L2-1) to (L2-9): 【Chemistry 6】 (In formulas (L2-1) to (L2-9), R Ｌ２ are each independently Hydrogen atoms, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents a nitro group.

13. The compound according to claim 1 or 2, wherein A1 and A2 are each independently any group represented by the following formula (a-1) to formula (a-8): 【Chemistry 7】 (In formula (a-1) to formula (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

14. A composition comprising a p-type semiconductor material and an n-type semiconductor material, the n-type semiconductor material comprising the compound according to claim 1 or 2.

15. The composition according to claim 14, wherein the p-type semiconductor material is a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): 【Chemistry 8】 (In formula (3), Ar ３ and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7): 【Chemistry 9】 In formulas (Z-1) to (Z-7), Each R is independently Hydrogen atoms, Halogen atoms, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an optionally substituted aryl group, an alkyloxy group which may have a substituent; a cycloalkyloxy group which may be substituted; an optionally substituted aryloxy group, an optionally substituted alkylthio group, a cycloalkylthio group which may be substituted; an optionally substituted arylthio group; a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent; an optionally substituted acyl group, an imine residue which may have a substituent; an amide group which may have a substituent; an acid imide group which may have a substituent; a substituted carbonyl group which may have a substituent; a substituted oxycarbonyl group which may have a substituent; a substituted sulfonyl group which may have a substituent; a substituted oxysulfonyl group which may have a substituent; an alkenyl group which may have a substituent; a cycloalkenyl group which may have a substituent, an optionally substituted alkynyl group, a cycloalkynyl group which may be substituted, a cyano group, or represents a nitro group, In each of formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. In formula (4), Ar ５ represents a divalent aromatic heterocyclic group.

16. An ink comprising a p-type semiconductor material, an n-type semiconductor material, and a solvent, the n-type semiconductor material comprising the compound according to claim 1 or 2.

17. an anode, a cathode, and an active layer provided between the anode and the cathode and including a p-type semiconductor material and an n-type semiconductor material; A photoelectric conversion element comprising the compound according to claim 1 or 2 as the n-type semiconductor material.

18. The photoelectric conversion element according to claim 17 , which is a photodetection element.

19. An optical sensor comprising the photoelectric conversion element according to claim 18.

20. A composition comprising a compound represented by the following formula (1) and a polymer compound containing at least one selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): 【Chemistry 10】 (In formula (1), D's each independently represent a polycyclic aromatic group having two bonds, and a conjugated structure connecting the two bonds via a shortest distance contains four or more double bonds, L1 and L1' each independently represent an aromatic group having two bonds, and a conjugated structure connecting the two bonds in a shortest distance contains three or less double bonds, L2 is not the same chemical structure as D, but is an aromatic group having two bonds; n is 1 or 2, m is 0 or 1, and n+m=2; A1 and A2 each independently represent an acceptor group represented by any one of the following formulas (a-5) to (a-8): 【Chemistry 11】 (In formula (3), Ar ３ and Ar ４ each independently represents a trivalent aromatic heterocyclic group which may have a substituent, and Z represents any of the groups represented by the following formulae (Z-1) to (Z-7): 【Chemistry 12】 In formulas (Z-1) to (Z-7), Each R is independently an optionally substituted aryl group, an optionally substituted monovalent heterocyclic group, or represents an optionally substituted cycloalkyl group, In each of formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. In formula (4), Ar ５ represents a divalent aromatic heterocyclic group. 【Chemistry 13】 (In formula (a-5) to formula (a-8), a plurality of R Ａ１ are each independently a hydrogen atom, a halogen atom, or a cyano group.

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