Polymer, film, composition, ink, electronic element, photoelectric conversion element, solar cell module, and image sensor

Abstract

The present invention addresses the problem of providing a polymer that suppresses dark current in a photoelectric conversion element. The present invention relates to a polymer containing a structural unit having a main chain and a side chain, in which the weighted average of the formula amount of the side chain weighted by the molar ratio of the structural unit contained in the polymer is 160 or more, and the absorption limit strength is 0.08 or less.

Description

Technical Field

[0001] The present disclosure relates to polymers, films, compositions, inks, electronic components, photoelectric conversion elements, solar cell modules, and image sensors. Background Art

[0002] Non-Patent Document 1 discloses a light detecting element using PTB7 as a polymer.

[0003] Prior art literature

[0004] Non-patent literature

[0005] Non-patent literature 1: Tiening, W.; Yue, W.; Lijie, Z.; Longfeng, L.; Yufeng, H.; Zhenbo, D.; Qiuhng, C.; Zhidong, L.; Yanbing, H.; Feng, T. Organic Electronics. 2019, 138-145. Summary of the invention

[0006] Problems to be solved by the invention

[0007] Photoelectric conversion elements are extremely useful devices from the viewpoints of energy saving and reduction of carbon dioxide emissions, and thus have attracted attention. Therefore, polymers and the like that can be applied to photoelectric conversion elements have also attracted attention.

[0008] A photoelectric conversion element refers to an element having at least a pair of electrodes consisting of an anode and a cathode and an active layer disposed between the pair of electrodes. In a photoelectric conversion element, one of the electrodes is made of a transparent or translucent material, and light is incident on the active layer from the transparent or translucent electrode side. Charges (holes and electrons) are generated in the active layer by the energy (hν) of the light incident on the active layer, and the generated holes move to the anode, and the electrons move to the cathode.

[0009] Then, the charges reaching the anode and the cathode are taken out of the element.

[0010] Photoelectric conversion elements are used, for example, as light detection elements. Photoelectric conversion elements used as light detection elements are used under the state of applying voltage, and convert the light incident on the element and detect it in the form of current. However, even when light is not incident, a weak current flows through the photoelectric conversion element. This current is known as dark current and is the main reason for reducing the accuracy of light detection.

[0011] Therefore, it is necessary to suppress the dark current of the photoelectric conversion element.

[0012] Therefore, an object of one embodiment of the present disclosure is to provide a polymer that suppresses dark current of a photoelectric conversion element.

[0013] Another embodiment of the present disclosure is to provide a film and a composition including the polymer of the present disclosure.

[0014] Another embodiment of the present disclosure is to provide an ink containing the polymer of the present disclosure.

[0015] Another embodiment of the present disclosure is to provide an electronic device including the polymer of the present disclosure.

[0016] A problem to be solved by another embodiment of the present disclosure is to provide a photoelectric conversion element that suppresses dark current.

[0017] A problem to be solved by another embodiment of the present disclosure is to provide a solar cell module including the photoelectric conversion element of the present disclosure.

[0018] A problem to be solved by another embodiment of the present disclosure is to provide an image sensor including the photoelectric conversion element of the present disclosure.

[0019] Means for solving problems

[0020] Means for solving the above-mentioned problems include the following means.

[0021] <1> A polymer comprising a structural unit having a main chain and a side chain, wherein

[0022] The weighted average of the formula weights of the side chains weighted by the molar ratio of the structural units contained in the polymer is 160 or more,

[0023] The absorption edge intensity is below 0.08.

[0024] <2> like <1> The polymer, wherein the side chain is at least one selected from the group consisting of an alkyl group which may have a substituent, an aryl group which may have a substituent, and a monovalent heterocyclic group which may have a substituent.

[0025] <3> like <1> The polymer comprises at least one selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (Y1).

[0026] [Chemistry 1]

[0027]

[0028] [Chemistry 2]

[0029]

[0030] (In formula (I),

[0031] Z 1 is a divalent group,

[0032] Ar 1 and Ar 2 each independently represents a trivalent aromatic hydrocarbon ring group or a trivalent heterocyclic group,

[0033] In formula (Y1), Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group formed by bonding an arylene group and a divalent heterocyclic group, and these groups may have a substituent.)

[0034] <4> like <3> The polymer comprises two different structural units represented by the above formula (I).

[0035] <5> like <3> or <4> The polymer, wherein in the structural unit shown in formula (I), Z 1 It is a group represented by the following formula (Z-1), the following formula (Z-2), the following formula (Z-3), the following formula (Z-4), the following formula (Z-5), the following formula (Z-6) or the following formula (Z-7).

[0036] [Chemistry 3]

[0037]

[0038] (In formula (Z-1) to formula (Z-7),

[0039] * indicates a bond,

[0040] R 11 and R 12 Each independently represents a hydrogen atom or a monovalent group which may or may not have a substituent, and each may be the same or different.)

[0041] <6> like <3> ~ <5> The polymer described in any one of the preceding claims, wherein the structural unit represented by formula (Y1) is a structural unit represented by the following formula (Y1-B5), the following formula (Y1-B6), the following formula (Y1-B7), the following formula (Y1-B8), the following formula (Y1-B9) or the following formula (Y1-B10).

[0042] [Chemistry 4]

[0043]

[0044] (In formula (Y1-B5) to formula (Y1-B10),

[0045] X 1 and X2 each independently represents a sulfur atom, an oxygen atom or a selenium atom,

[0046] Y 1 and Y 2 Each independently represents a nitrogen atom or =CR 2b - the group shown,

[0047] R 21 , R 22 and R 2b Each independently represents a hydrogen atom or a substituent. )

[0048] <7> like <5> or <6> The polymer, wherein in formula (Z-1) to formula (Z-7), R 11 and R 12 At least one of them is a group represented by the following formula (SC).

[0049] [Chemistry 5]

[0050]

[0051] (In formula (SC),

[0052] m SCA1 represents an integer from 1 to 10.

[0053] Ar SC1 represents an arylene group which may have a substituent,

[0054] T SC represents an aryl group which may or may not have a substituent. )

[0055] <8> like <3> ~ <7> The polymer described in any one of the preceding claims, wherein the structural unit represented by the formula (I) is a structural unit represented by the following formula (I-8).

[0056] [Chemistry 6]

[0057]

[0058] (In formula (I-8), R 31 ~R 34 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, an imide group, an imino group, an amino group, a silyl group, a silyloxy group, a silylthio group, a silylamino group, a heterocyclic group, a heterocyclicoxy group, a heterocyclicthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group or a cyano group, and these groups may have a substituent.)

[0059] <9> like <1> ~ <8> The polymer described above has a weight average molecular weight of 6,000 or more.

[0060] <10> A polymer comprising at least one selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (Y1).

[0061] [Chemistry 7]

[0062]

[0063] [Chemistry 8]

[0064]

[0065] (In formula (I),

[0066] Z 1 is a group represented by the following formula (Z-1), the following formula (Z-2), the following formula (Z-3), the following formula (Z-4), the following formula (Z-5), the following formula (Z-6) or the following formula (Z-7),

[0067] Ar 1 and Ar 2 each independently represents a trivalent aromatic hydrocarbon ring group or a trivalent heterocyclic group,

[0068] In formula (Y1), Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are bonded together,

[0069] In the groups represented by the following formulae (Z-1) to (Z-7), R 11 and R 12 At least one of them is a group represented by the following formula (SC),

[0070] In formula (SC), m SCA1 represents an integer from 1 to 10, Ar SC1 represents an arylene group, T SC represents an aromatic group, which may or may not have a substituent. )

[0071] [Chemistry 9]

[0072]

[0073] [Chemistry 10]

[0074]

[0075] <11> A film comprising <1> ~ <10> The polymer described in any one of the above.

[0076] <12> like <11> The film contains an electron-accepting compound.

[0077] <13> like <11> or <12> The absorption limit intensity of the membrane is below 0.17.

[0078] <14> A composition comprising <1> ~ <10> The polymer and the electron-accepting compound described above.

[0079] <15> An ink comprising <1> ~ <10> The polymer and solvent described above.

[0080] <16> An electronic component comprising <1> ~ <10> The polymer described in any one of the above.

[0081] <17> A photoelectric conversion element, comprising:

[0082] 1st electrode;

[0083] a second electrode; and

[0084] an active layer disposed between the first electrode and the second electrode,

[0085] The active layer contains <1> ~ <10> The polymer described in any one of the above.

[0086] <18> A solar cell module comprising <17> The organic photoelectric conversion element.

[0087] <19> An image sensor comprising <17> The organic photoelectric conversion element.

[0088] Effects of the Invention

[0089] According to one embodiment of the present disclosure, there is provided a polymer that suppresses dark current of a photoelectric conversion element.

[0090] According to another embodiment of the present disclosure, a film and a composition including the polymer of the present disclosure are provided.

[0091] According to another embodiment of the present disclosure, an ink including the polymer of the present disclosure is provided.

[0092] According to another embodiment of the present disclosure, an electronic component including the polymer of the present disclosure is provided.

[0093] According to another embodiment of the present disclosure, there is provided a photoelectric conversion element that suppresses dark current.

[0094] According to another embodiment of the present disclosure, there is provided a solar cell module including the photoelectric conversion element of the present disclosure.

[0095] According to another embodiment of the present disclosure, there is provided an image sensor including the photoelectric conversion element of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0096] Figure 1 This is an example of the UV-visible-near infrared absorption spectrum of the polymer disclosed in the present invention.

[0097] Figure 2 is a schematic cross-sectional view of one embodiment of the photoelectric conversion element disclosed herein.

[0098] Figure 3 This is a graph that plots the predicted dark current against the measured dark current. DETAILED DESCRIPTION

[0099] Hereinafter, an embodiment as an example of the present disclosure will be described. These descriptions and examples illustrate the embodiment and do not limit the scope of the invention.

[0100] In the numerical range recorded in stages in this manual, the upper limit or lower limit recorded by a numerical range can also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this manual, the upper limit or lower limit of this numerical range can also be replaced by the value shown in the embodiment.

[0101] Each component may contain two or more corresponding substances.

[0102] When referring to the amount of each component in a composition, if two or more substances corresponding to each component are present in the composition, unless otherwise specified, it refers to the total amount of the two or more substances present in the composition.

[0103] The main chain refers to the chain that forms the longest backbone in the polymer molecular structure.

[0104] The side chain refers to a monovalent group branched from the main chain.

[0105] "Aromatic hydrocarbon ring group" refers to an atomic group remaining after removing one or more hydrogen atoms directly bonded to carbon atoms constituting an aromatic hydrocarbon ring, and the aromatic hydrocarbon ring may be unsubstituted or may have a substituent, and two or more rings may be condensed. For example, it is sometimes referred to as a "p-valent aromatic hydrocarbon ring group" (p represents an integer greater than 1), in which case it refers to an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting an aromatic hydrocarbon ring that may or may not have a substituent.

[0106] In addition, it may be referred to as "an aromatic hydrocarbon ring group in which q rings are condensed" (q represents an integer of 2 or more), and in this case, it means an aromatic hydrocarbon ring group in which q rings are condensed.

[0107] "Heterocyclic group" refers to an atomic group remaining after removing one or more hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting a heterocyclic ring, and the heterocyclic ring may be unsubstituted or may have a substituent, and two or more rings may be fused. For example, it is sometimes referred to as a "p-valent heterocyclic group" (p represents an integer greater than 1), in which case it refers to an atomic group remaining after removing p hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting a heterocyclic ring which may or may not have a substituent.

[0108] In addition, it may be referred to as a "heterocyclic group in which q rings are condensed" (q represents an integer of 2 or more), and in this case, it means an aromatic heterocyclic group in which q rings are condensed.

[0109] Examples of "substituent A" include halogen atoms, alkyl groups (including cycloalkyl groups), alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, monovalent heterocyclic groups, substituted amino groups, acyl groups, imide residues, amide groups, imido groups, substituted oxycarbonyl groups, cyano groups, alkylsulfonyl groups, and nitro groups. It should be noted that when the number of carbon atoms is mentioned in this specification, the number of carbon atoms generally does not include the number of carbon atoms of substituent A.

[0110] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0111] The number of carbon atoms in the alkyl group is preferably 1 to 50, more preferably 1 to 30, and even more preferably 1 to 20.

[0112] Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, cyclohexylmethyl, cyclohexylethyl, n-octyl, 2-ethylhexyl, 3-n-propylheptyl, adamantyl, n-decyl, 3,7-dimethyloctyl, 2-ethyloctyl, 2-n-hexyldecyl, n-dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl.

[0113] The number of carbon atoms in the alkenyl group is preferably 2 or more and 30 or less, more preferably 3 or more and 20 or less.

[0114] Examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl and 7-octenyl.

[0115] The number of carbon atoms in the alkynyl group is preferably 2 or more and 20 or less, more preferably 3 or more and 20 or less.

[0116] Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, and 5-hexynyl.

[0117] The number of carbon atoms in the alkoxy group is preferably 1 or more and 40 or less, more preferably 1 or more and 10 or less.

[0118] Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3,7-dimethyloctyloxy, 3-heptyldodecyloxy and lauryloxy.

[0119] The number of carbon atoms in the alkylthio group is preferably 1 or more and 40 or less, more preferably 1 or more and 10 or less.

[0120] Examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, tert-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio and trifluoromethylthio.

[0121] The aryl group is a monovalent aromatic hydrocarbon ring group.

[0122] The number of carbon atoms in the aryl group is preferably 6 or more and 30 or less, more preferably 6 or more and 20 or less.

[0123] Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, and 4-phenylphenyl.

[0124] The number of carbon atoms in the aryloxy group is preferably 6 or more and 60 or less, and more preferably 6 or more and 48 or less.

[0125] Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthryloxy group, a 9-anthryloxy group, and a 1-pyreneoxy group.

[0126] The number of carbon atoms in the arylthio group is preferably 6 or more and 60 or less, more preferably 6 or more and 48 or less.

[0127] Examples of the arylthio group include phenylthio, C1-C12 alkoxyphenylthio (C1-C12 means that the number of carbon atoms of the group immediately following it is 1 to 12. The same shall apply hereinafter), C1-C12 alkylphenylthio, 1-naphthylthio, 2-naphthylthio, pentafluorophenylthio and the like.

[0128] The number of carbon atoms in the monovalent heterocyclic group is preferably 2 or more and 60 or less, more preferably 4 or more and 20 or less.

[0129] Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group, and a triazinyl group.

[0130] The substituted amino group refers to 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.

[0131] The substituted amino group preferably has 2 to 30 carbon atoms.

[0132] Examples of the substituted amino group include dialkylamino groups such as dimethylamino and diethylamino; and diarylamino groups such as diphenylamino, bis(4-methylphenyl)amino, bis(4-tert-butylphenyl)amino and bis(3,5-di-tert-butylphenyl)amino.

[0133] The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 18.

[0134] Examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl, and pentafluorobenzoyl.

[0135] An imine residue refers to an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or a nitrogen atom constituting a carbon-nitrogen double bond from an imine compound. An "imine compound" refers to an organic compound having a carbon-nitrogen double bond in a molecule. Examples of imine compounds include aldimines, ketimines, and compounds in which the hydrogen atom bonded to a nitrogen atom constituting a carbon-nitrogen double bond in aldimines is substituted with an alkyl group or the like.

[0136] The number of carbon atoms of the imine residue is preferably 2 or more and 20 or less, more preferably 2 or more and 18 or less.

[0137] Examples of the imine residue include groups represented by the following structural formulas: In the following structural formula, * represents a bond.

[0138] In the following structural formulas, "Me" represents a methyl group.

[0139] [Chemistry 11]

[0140]

[0141] The number of carbon atoms in the amide group is preferably 1 to 20, more preferably 1 to 18.

[0142] Examples of the amide group include formamide, acetamide, propionamide, butyramide, benzamide, trifluoroacetamide, pentafluorobenzamide, diformamide, diacetamide, dipropionamide, dibutyramide, dibenzamide, bis(trifluoroacetamide), bis(pentafluorobenzamide) and the like.

[0143] The imide group refers to an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from imide.

[0144] The number of carbon atoms in the imide group is preferably 4 or more and 20 or less.

[0145] Examples of the imide group include groups represented by the following structural formula: In the following structural formula, * represents a bond.

[0146] In the following structural formulas, "Me" represents a methyl group.

[0147] [Chemistry 12]

[0148]

[0149] The substituted oxycarbonyl group refers to a group represented by R'-O-(C=O)-, wherein R' represents an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group.

[0150] The number of carbon atoms in the substituted oxycarbonyl group is preferably 2 or more and 60 or less, more preferably 2 or more and 48 or less.

[0151] Examples of the substituted oxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, 3,7-dimethyloctyloxycarbonyl, dodecyloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluorooctyloxycarbonyl, phenoxycarbonyl, naphthyloxycarbonyl and pyridyloxycarbonyl.

[0152] The alkylsulfonyl group preferably has 1 to 30 carbon atoms.

[0153] Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.

[0154] <Polymer>

[0155] The polymer disclosed herein is a polymer including structural units having a main chain and side chains, wherein the weighted average of the formula weights of the side chains weighted by the molar ratio of the structural units included in the polymer is 160 or more, and the absorption edge strength is 0.08 or less.

[0156] The polymer disclosed in the present invention suppresses the dark current of the photoelectric conversion element by the above-mentioned configuration. The reason for this is presumably as follows.

[0157] When the polymer disclosed in the present invention is used to manufacture a photoelectric conversion element, the generation of carriers due to thermal excitation can be suppressed by making the weighted average of the formula weight of the above-mentioned side chain greater than 160. In addition, the energy level of the polymer having an absorption edge strength of less than 0.08 is small, and the generation of carriers due to thermal excitation can also be suppressed.

[0158] From the above, it is estimated that the polymer disclosed in the present invention can suppress the dark current of the photoelectric conversion element.

[0159] (Structure of polymer)

[0160] The polymer of the present disclosure includes a structural unit having a main chain and a side chain.

[0161] In the structural unit, the structure of the main chain is not particularly limited, but is preferably a structure including a condensed ring.

[0162] The structure of the main chain is more preferably a structure in which repeating units including a condensed ring are linked to each other by bonding, and the repeating units including a condensed ring may be of two or more types.

[0163] From the perspective of suppressing dark current, in the structural unit, the side chain is preferably at least one selected from the group consisting of an alkyl group with or without a substituent, an aryl group with or without a substituent and a monovalent heterocyclic group with or without a substituent, and more preferably at least one selected from the group consisting of an alkyl group with or without a substituent and an aryl group with or without a substituent.

[0164] The alkyl group as a side chain may be linear or branched, or may be a cycloalkyl group.

[0165] The alkyl group as a side chain preferably has 1 to 30 carbon atoms.

[0166] The alkyl group as a side chain may have a substituent, and examples of the substituent include the substituent A described above.

[0167] Specific examples of the alkyl group in the side chain include chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 3,7-dimethyloctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like, and cycloalkyl groups such as cyclopentyl, cyclohexyl and adamantyl.

[0168] The aryl group as a side chain has the same meaning as the monovalent aromatic hydrocarbon ring group, and preferably has 6 to 60 carbon atoms.

[0169] The aryl group as a side chain may have a substituent, and examples of the substituent include the substituent A described above.

[0170] Specific examples of the aryl group in the side chain include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, and 4-phenylphenyl.

[0171] The number of carbon atoms in the monovalent heterocyclic group as a side chain is preferably 2 to 60, more preferably 4 to 20.

[0172] Examples of the monovalent heterocyclic group in the side chain include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, a pyrimidinyl group, and a triazinyl group.

[0173] The monovalent heterocyclic group as a side chain may have a substituent, and examples of the substituent include the substituent A described above.

[0174] From the viewpoint of suppressing dark current, the polymer disclosed herein preferably includes at least one selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (Y1).

[0175] [Chemistry 13]

[0176]

[0177] In formula (I), Z 1 is a divalent group, Ar 1 and Ar 2 Each independently represents a trivalent aromatic hydrocarbon ring group or a trivalent heterocyclic group, and these groups may have a substituent.

[0178] [Chemistry 14]

[0179]

[0180] In formula (Y1), Ar Y1 It represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are bonded to each other, and these groups may have a substituent.

[0181] -Structural unit represented by formula (I)-

[0182] In formula (I), as Ar 1 and Ar 2The trivalent aromatic hydrocarbon ring group represented by may be, for example, an atomic group remaining after removing three hydrogen atoms directly bonded to carbon atoms constituting the aromatic hydrocarbon ring described below.

[0183] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.

[0184] In formula (I), as Ar 1 and Ar 2 The trivalent heterocyclic group represented by may be, for example, an atomic group remaining after removing three hydrogen atoms directly bonded to carbon atoms or hetero atoms constituting the aromatic heterocycle described below.

[0185] Examples of the aromatic heterocyclic 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, a dibenzophosphole ring, a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring.

[0186] By Ar 1 and Ar 2 The trivalent aromatic hydrocarbon ring group represented by may have a substituent, and the substituent A mentioned above can be mentioned.

[0187] From the perspective of suppressing dark current, in the structural unit represented by formula (I), Z 1 Preferably, it is a group represented by the following formula (Z-1), the following formula (Z-2), the following formula (Z-3), the following formula (Z-4), the following formula (Z-5), the following formula (Z-6) or the following formula (Z-7).

[0188] [Chemistry 15]

[0189]

[0190] In formula (Z-1) to formula (Z-7), * represents a bond, R 11 and R 12 Each independently represents a hydrogen atom or a monovalent group, and may be the same or different.

[0191] The polymer disclosed herein comprises a structural unit represented by formula (I), wherein Z 1 When it is a group represented by the following formula (Z-1), the following formula (Z-2), the following formula (Z-3), the following formula (Z-4), the following formula (Z-5), the following formula (Z-6) or the following formula (Z-7), R in formula (Z-1) to formula (Z-7) 11 and R 12 The monovalent groups shown correspond to the side chains, and the other parts correspond to the main chain.

[0192] Examples of the monovalent group include a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, an imide group, an imino group, an amino group, a silyl group, a silyloxy group, a silylthio group, a silylamino group, a heterocyclic group, a heterocyclicoxy group, a heterocyclicthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, and a cyano group.

[0193] The monovalent group may have a substituent, and examples of the substituent include the substituent A described above.

[0194] From the viewpoint of suppressing dark current, the monovalent group is preferably at least one selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic group.

[0195] As R 11 and R 12 The alkyl group shown may be the same as the alkyl group as the side chain of the polymer of the present disclosure described above, and preferred aspects are also the same.

[0196] As R 11 and R 12 Examples of the aryl group shown include the same aryl groups as those mentioned above as the side chain of the polymer of the present disclosure, and preferred embodiments are also the same.

[0197] As R 11 and R 12 Examples of the heterocyclic group include the same ones as the monovalent heterocyclic groups as the side chains of the polymer of the present disclosure, and preferred embodiments are also the same.

[0198] From the perspective of suppressing dark current, it is preferred that R in formula (Z-1) to formula (Z-7) 11 and R 12 At least one of them is a group represented by the following formula (SC).

[0199] [Chemistry 16]

[0200]

[0201] In formula (SC), m SCA1 represents an integer from 1 to 10, Ar SC1 represents an arylene group which may have a substituent, T SC It represents an aryl group which may have a substituent.

[0202] m SCA1 It is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably an integer of 1 to 2.

[0203] The arylene group is a divalent aromatic hydrocarbon ring group.

[0204] As Ar SC1 The number of carbon atoms of the arylene group represented by is preferably 6 or more and 60 or less, more preferably 6 or more and 20 or less.

[0205] Examples of the arylene group include an atomic group remaining after removing two hydrogen atoms directly bonded to carbon atoms constituting the aromatic hydrocarbon ring described below.

[0206] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a pyrene ring.

[0207] Ar SC1 The arylene group shown may have a substituent, and examples of the substituent include the substituent A described above.

[0208] As T SC The number of carbon atoms of the aryl group represented by is preferably 6 or more and 30 or less, more preferably 6 or more and 20 or less.

[0209] Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-pyrenyl, 2-pyrenyl, 4-pyrenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, 2-phenylphenyl, 3-phenylphenyl, and 4-phenylphenyl.

[0210] T SC The aryl group shown may have a substituent, and examples of the substituent include the substituent A described above.

[0211] Examples of the structural unit represented by the formula (I) include structural units represented by the following formulae (I-1) to (I-9).

[0212] [Chemistry 17]

[0213]

[0214] In formula (I-1) to formula (I-9), R 31 , R 32 , R 33 and R 34 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, an imide group, an imino group, an amino group, a silyl group, a silyloxy group, a silylthio group, a silylamino group, a heterocyclic group, a heterocyclicoxy group, a heterocyclicthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group or a cyano group, and these groups may have a substituent. As the substituent, the above-mentioned substituent A can be mentioned.

[0215] From the perspective of suppressing dark current, R 31 , R32 , R 33 and R 34 , preferably at least one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group and a heterocyclic group.

[0216] When the structural unit represented by formula (I) is a structural unit represented by formula (I-1) to formula (I-9), R in formula (I-1) to formula (I-9) 31 ~R 34 When they are other than hydrogen atoms, they correspond to side chains.

[0217] From the viewpoint of suppressing dark current, the structural unit represented by formula (I) is preferably a structural unit represented by formula (I-8) above.

[0218] The polymer disclosed in the present invention may contain only one type of structural unit represented by formula (I), or may contain two or more different types of structural units represented by formula (I).

[0219] From the viewpoint of suppressing dark current, the polymer of the present disclosure preferably includes two different structural units represented by formula (I).

[0220] -Structural unit represented by formula (Y1)-

[0221] In formula (Y1), Ar Y1 It represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are bonded to each other, and these groups may have a substituent.

[0222] As Ar Y1 The number of carbon atoms of the arylene group (ie, divalent aromatic hydrocarbon ring group) shown is preferably 6 or more and 60 or less, more preferably 6 or more and 20 or less.

[0223] Ar Y1 In the case of an arylene group, the structural unit represented by formula (Y1) is preferably the following formula (Y1-A1), the following formula (Y1-A2), the following formula (Y1-A3), the following formula (Y1-A4), the following formula (Y1-A5) or the following formula (Y1-A6).

[0224] [Chemistry 18]

[0225]

[0226] In formula (Y1-A1) to formula (Y1-A6), R 21 ~R 28 and R a1 ~R a4 Each independently represents a hydrogen atom or a substituent. a1 ~R a4 They may bond to each other to form a ring together with the atoms to which they are bonded.

[0227] As the substituent, the substituent A mentioned above can be mentioned.

[0228] When the structural unit represented by formula (Y1) is a structural unit represented by formula (Y1-A1) to formula (Y1-A6), R in formula (Y1-A1) to formula (Y1-A6) 21 ~R 28 and R a1 ~R a4 When they are other than hydrogen atoms, they correspond to side chains.

[0229] As Ar Y1 The divalent heterocyclic group shown here includes, for example, an atomic group remaining after removing two hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting the heterocycle described below.

[0230] Examples of the heterocyclic ring include a pyridine ring, a diazine benzene ring, a triazine ring, a naphthylene ring, a naphthylene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, a dibenzosilole ring, a phenoxazine ring, a phenothiazine ring, an acridine ring, a dihydroacridine ring, a furan ring, a thiophene ring, an azole ring, a diazole ring, a triazole ring, and a heterocyclic ring in which two or more of these heterocyclic rings are condensed.

[0231] Ar Y1 In the case of a divalent heterocyclic group, the structural unit represented by the formula (Y1) is preferably the following formula (Y1-B1), the following formula (Y1-B2), the following formula (Y1-B3), the following formula (Y1-B4), the following formula (Y1-B5), the following formula (Y1-B6), the following formula (Y1-B7), the following formula (Y1-B8), the following formula (Y1-B9) or the following formula (Y1-B10).

[0232] [Chemistry 19]

[0233]

[0234] In formula (Y1-B1) to formula (Y1-B10), X 21 ~X 26 Each independently represents a sulfur atom, an oxygen atom or a selenium atom, and Y 1 ~Y 8 Each independently represents a nitrogen atom or =CR 2b - the group shown, R 21 ~R 28 and R 2b Each independently represents a hydrogen atom or a substituent.

[0235] As the substituent, the substituent A mentioned above can be mentioned.

[0236] When the structural unit represented by formula (Y1) is a structural unit represented by formula (Y1-B1) to formula (Y1-B10), R in formula (Y1-B1) to formula (Y1-B10) 21 ~R 25 and R 2b When they are other than hydrogen atoms, they correspond to side chains.

[0237] Ar Y1 In the case of a divalent group formed by bonding an arylene group to a divalent heterocyclic group, the structural unit represented by formula (Y1) is preferably the following formula (Y1-C1), the following formula (Y1-C2), the following formula (Y1-C3) or the following formula (Y1-C4).

[0238] [Chemistry 20]

[0239]

[0240] In formula (Y1-C1) to formula (Y1-C4), R 21 represents a hydrogen atom or a substituent.

[0241] As the substituent, the substituent A mentioned above can be mentioned.

[0242] When the structural unit represented by formula (Y1) is a structural unit represented by formula (Y1-C3), R in formula (Y1-C3) 21 When they are other than hydrogen atoms, they correspond to side chains.

[0243] When the structural unit represented by formula (Y1) is a structural unit represented by formula (Y1-C1), formula (Y1-C2) or formula (Y1-C4), it does not contain a side chain.

[0244] From the perspective of suppressing dark current, the structural unit represented by formula (Y1) is preferably a structural unit represented by formula (Y1-B5), the following formula (Y1-B6), the following formula (Y1-B7), the following formula (Y1-B8), the following formula (Y1-B9) or the following formula (Y1-B10).

[0245] -mol% of structural unit-

[0246] In the polymer disclosed herein, the total content of the structural unit represented by formula (I) and the structural unit represented by formula (Y1), relative to the total content of the structural units contained in the polymer, is from 1 mol % to 100 mol %, preferably from 10 mol % to 100 mol %, more preferably from 30 mol % to 100 mol %, further preferably from 50 mol % to 100 mol %, particularly preferably from 70 mol % to 100 mol %, and most preferably from 90 mol % to 100 mol %.

[0247] In the polymer disclosed herein, the content of the structural unit represented by formula (I) is 1 mol% to 90 mol%, preferably 10 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, and further preferably 50 mol% to 60 mol%, relative to the total content of the structural units contained in the polymer.

[0248] When the polymer disclosed herein contains two different structural units represented by formula (I), when one structural unit represented by formula (I) is set as the structural unit represented by formula (I) and the other structural unit represented by formula (I) is set as the structural unit represented by formula (I'), the content of the structural unit represented by formula (I') relative to the total content of the structural unit represented by formula (I) and the structural unit represented by formula (I') is 1 mol% to 90 mol%, preferably 10 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, and further preferably 50 mol% to 60 mol%.

[0249] In the polymer disclosed herein, the content of the structural unit represented by formula (Y1) is 1 mol% to 90 mol%, preferably 10 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, and further preferably 50 mol% to 60 mol%, relative to the total content of the structural units contained in the polymer.

[0250] The polymer of the present disclosure may include other structural units besides the structural unit represented by formula (I) and the structural unit represented by formula (Y1).

[0251] When the polymer of the present disclosure contains other structural units, the content of the other structural units is 0 mol% to 30 mol%, preferably 0 mol% to 20 mol%, more preferably 0 mol% to 10 mol%, and even more preferably 0 mol%, relative to the total content of the structural units contained in the polymer.

[0252] Examples of the polymer of the present disclosure include polymer P-1 and polymer P-2 shown in Table 1.

[0253] Here, in Table 1, "Formula (I)" refers to the structural unit represented by formula (I).

[0254] In Table 1, “Formula (I′)” refers to a structural unit represented by a formula (I) different from “Formula (I)” in Table 1 when the polymer contains two different structural units represented by the formula (I).

[0255] In Table 1, "Formula (Y1)" refers to the structural unit represented by Formula (Y1).

[0256] In Table 1, "other" refers to structural units other than the structural unit represented by formula (I) and the structural unit represented by formula (Y1).

[0257] In Table 1, "p", "q", "r" and "s" represent the molar ratio (mol %) of each structural unit. p+q+r+s=100, 70≤p+q+r+s≤100.

[0258] [Table 1]

[0259]

[0260] Specific examples of the polymer disclosed in the present invention are described in Tables 2-1 to 2-10 below, but the present invention is not limited thereto.

[0261] It should be noted that Table 2-1 to Table 2-10 may be collectively referred to as Table 2 below.

[0262] [Table 2-1]

[0263]

[0264] [Table 2-2]

[0265]

[0266] [Table 2-3]

[0267]

[0268] [Table 2-4]

[0269]

[0270] [Table 2-5]

[0271]

[0272] [Table 2-6]

[0273]

[0274] [Table 2-7]

[0275]

[0276] [Table 2-8]

[0277]

[0278] [Table 2-9]

[0279]

[0280] [Table 2-10]

[0281]

[0282] -Weight average molecular weight of polymer-

[0283] From the viewpoint of suppressing dark current, the weight average molecular weight of the polymer disclosed herein is preferably 6,000 or more, more preferably 6,000 or more and 100,000 or less, more preferably 7,000 or more and 90,000 or less, and even more preferably 8,000 or more and 80,000 or less.

[0284] The weight average molecular weight is a polystyrene-equivalent weight average molecular weight determined by size exclusion chromatography (SEC).

[0285] -Weighted average of sidechains-

[0286] The weighted average of the formula weights of the side chains of the polymer disclosed in the present invention weighted by the molar ratio of the structural units contained in the polymer (hereinafter also referred to as the "specific side chain average formula weight") is 160 or more. From the perspective of suppressing dark current, it is preferably 160 to 300, more preferably 165 to 250, and further preferably 170 to 230.

[0287] The specific side chain average formula weight is calculated as follows.

[0288] The side chains are specified for each structural unit contained in the polymer. Then, the total formula weight of the side chains specified for each structural unit is calculated. Next, the weighted average of the total formula weight of the side chains weighted by the molar ratio of the structural units is calculated, and this value is used as the specific side chain average formula weight.

[0289] Hereinafter, the calculation method of the average formula weight of the specific side chain will be described in more detail.

[0290] For example, a polymer comprising a structural unit represented by formula (I), a structural unit represented by formula (I'), and a structural unit represented by formula (Y1) is described. Here, the structural unit represented by formula (I) comprises a side chain A and a side chain B. Furthermore, the structural unit represented by formula (I') comprises a side chain C. The structural unit represented by formula (Y1) does not comprise a side chain.

[0291] · Sidechain specific

[0292] First, the side chain is identified for each structural unit included in the polymer. In the structural unit represented by formula (I), the side chain is side chain A and side chain B. In the structural unit represented by formula (I'), the side chain is side chain C.

[0293] ·Total value of calculated quantity

[0294] Next, the total value of the formula weight of the side chain specified for each structural unit is calculated. In the structural unit represented by formula (I), the total value of the formula weight of side chain A and the formula weight of side chain B is calculated (hereinafter, this value is referred to as "side chain AB formula weight"). In the structural unit represented by formula (I'), the formula weight of side chain C is calculated (hereinafter, this value is referred to as "side chain C formula weight").

[0295] · Calculation of weighted average of the total value of the side chain formula weight

[0296] Next, the weighted average of the total values ​​of the formula weights of the side chains weighted by the molar ratio of the structural units is calculated. The calculation formula is as follows.

[0297] Formula 1: Specific side chain average formula weight = ((side chain AB formula weight × molar ratio of the structural unit represented by formula (I)) + (side chain C formula weight × molar ratio of the structural unit represented by formula (I'))) ÷ 100

[0298] In addition, in the above formula, the molar ratio of each structural unit is the percentage of the molar number of each structural unit relative to the total molar number of the structural units contained in the polymer.

[0299] Here, for example, when the polymer contains 25 mol % of the structural unit represented by formula (I), 25 mol % of the structural unit represented by formula (I') and 50 mol % of the structural unit represented by formula (Y1), the above formula is as shown in the following formula 2.

[0300] Formula 2: Average formula weight of specific side chain = ((formula weight of side chain AB × 25) + (formula weight of side chain C × 25)) ÷ 100

[0301] -Absorption limit strength-

[0302] The absorption edge strength of the polymer disclosed in the present invention is 0.08 or less, and from the viewpoint of suppressing dark current, is preferably 0.01 or more and 0.08 or less, more preferably 0.03 or more and 0.079 or less, and further preferably 0.04 or more and 0.075 or less.

[0303] Determination of the absorption limit intensity of polymers

[0304] The absorption intensity was measured using a UV-visible infrared spectrophotometer.

[0305] As the ultraviolet-visible-infrared spectrophotometer, for example, Varian Cary 5E Uv-vis-IR spectrometry apparatus can be used.

[0306] Below, refer to Figure 1 The method for determining the absorption limit strength is described below. Figure 1 This is an example of the UV-visible-infrared absorption spectrum of the polymer disclosed in the present invention.

[0307] A film with a thickness of 100 nm made of a polymer was prepared. The film was used as a measurement object, and an ultraviolet-visible-infrared absorption spectrum ( Figure 1 ). The measurement wavelength is set to the range of 300nm to 1700nm (scanning rate: 600nm / min). The vertical axis of the ultraviolet-visible-infrared absorption spectrum is the absorption intensity expressed logarithmically. The horizontal axis is the wavelength. The absorption intensity at the intersection C of the extended line A obtained by linear approximation of the baseline of the ultraviolet-visible-infrared absorption spectrum and the extended line B obtained by linear approximation of the tailing part of the absorption existing on the long wavelength side is taken as the absorption limit intensity.

[0308] (Method for producing polymer)

[0309] The method for producing a polymer disclosed herein is preferably obtained by reacting a compound represented by the following formula (IR) with a compound represented by the following formula (Y1-R).

[0310] [Chemistry 21]

[0311]

[0312] In formula (IR), Z 1 ,Ar 1 and Ar 2 With Z in formula (I) 1 ,Ar 1 and Ar 2 The meaning is the same and the preferred method is also the same.

[0313] In formula (IR), X R represents a boron-containing group. Examples of the boron-containing group include an atomic group represented by the following formula (XR-1). In the formula (XR-1), * represents a bond.

[0314] [Chemistry 22]

[0315]

[0316] In the formula (Y1-R), Ar Y1 and Ar in formula (Y1) Y1 The meaning is the same and the preferred method is also the same.

[0317] In the formula (Y1-R), Y R Each independently represents a halogen atom.

[0318] In the method for producing the polymer disclosed herein, the method for reacting the compound represented by the following formula (IR) with the compound represented by the following formula (Y1-R) is not particularly limited, but from the perspective of ease of polymer synthesis, a method using a Suzuki-Miyaura coupling reaction or a Stille coupling reaction is preferred.

[0319] Examples of methods for carrying out the Suzuki-Miyaura coupling reaction and the Stille coupling reaction include a method of carrying out the reaction in the presence of a base using a palladium catalyst as a catalyst in an arbitrary solvent.

[0320] <Composition>

[0321] The composition of the present disclosure comprises the polymer of the present disclosure and an electron accepting compound.

[0322] The composition of the present disclosure may contain a solvent and other components as necessary.

[0323] Preferred embodiments of the polymer contained in the composition of the present disclosure are as described in the description of the polymer of the present disclosure.

[0324] (Electron accepting compounds)

[0325] The electron accepting compound contained in the composition of the present disclosure may be a low molecular weight compound or a high molecular weight compound. Examples of the electron accepting compound include oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, dibenzoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, C 60 Fullerenes such as fullerene and fullerene derivatives as derivatives thereof (hereinafter sometimes referred to as fullerene compounds) and phenanthrene derivatives such as bathocuproine.

[0326] As an electron-accepting compound, it can be C 60 Fullerenes such as fullerene and fullerene derivatives thereof may be non-fullerene compounds. Hereinafter, fullerenes and fullerene derivatives may be referred to as fullerene compounds. Non-fullerene compounds refer to compounds other than fullerenes and fullerene derivatives.

[0327] -Fullerene compounds-

[0328] As fullerene, C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84Fullerene. Examples of fullerene derivatives include derivatives of these fullerenes. Fullerene derivatives refer to compounds in which at least a part of fullerene is modified.

[0329] Examples of the fullerene derivative include compounds represented by the following formula.

[0330] [Chemistry 23]

[0331]

[0332] In the above formula,

[0333] R a represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group or a group having an ester structure, and these groups may have a substituent. a They can be the same or different from each other.

[0334] R b represents an alkyl group, a cycloalkyl group or an aryl group, which may or may not have a substituent. b They can be the same or different from each other.

[0335] As the substituent, the substituent A mentioned above can be mentioned.

[0336] As R a Examples of the group having an ester structure include groups represented by the following formulae.

[0337] [Chemistry 24]

[0338]

[0339] In the above formula, u1 represents an integer of 1 to 6. u2 represents an integer of 0 to 6. e represents an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group, and these groups may have a substituent.

[0340] As the substituent, the substituent A mentioned above can be mentioned.

[0341] As C 60 Examples of fullerene derivatives include the following compounds.

[0342] [Chemistry 25]

[0343]

[0344] As C 70 Examples of fullerene derivatives include the following compounds.

[0345] [Chemistry 26]

[0346]

[0347] Specific examples of fullerene derivatives include [6,6]-phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6]-Phenyl C61 butyric acid methyl ester), [6,6]-phenyl-C71 butyric acid methyl ester (C70PCBM, [6,6]-Phenyl C71 butyric acid methyl ester), [6,6]-phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6]-Phenyl C85 butyric acid methyl ester), and [6,6]-thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).

[0348] -Non-fullerene compounds-

[0349] The non-fullerene compound is not particularly limited, and conventionally known compounds can be used.

[0350] From the viewpoint of suppressing dark current, the non-fullerene compound is preferably a compound containing a perylenetetracarboxylic acid diimide structure or a compound having an ADA type structure represented by the following formula (VI).

[0351] A 1 -B 10 -A 2 (VI)

[0352] In formula (VI),

[0353] A 1 and A 2 Each independently represents an electron-withdrawing group, B 10 It represents a group including a π-conjugated system.

[0354] As A 1 and A 2 Examples of the electron withdrawing group include a group represented by -CH=C(-CN)2 and groups represented by the following formulae (a-1) to (a-9).

[0355] [Chemistry 27]

[0356]

[0357] In formula (a-1) to formula (a-7),

[0358] T represents a carbocyclic ring or a heterocyclic ring. The carbocyclic ring and the heterocyclic ring may be a monocyclic ring or a condensed ring. When these rings have two or more substituents, the two or more substituents may be the same or different. As the substituent, the substituent A mentioned above may be cited.

[0359] As examples of the carbocyclic ring of T, aromatic carbocyclic rings can be cited, preferably aromatic carbocyclic rings. As specific examples of the carbocyclic ring of T, benzene rings, naphthalene rings, anthracene rings, tetracene rings, pentacene rings, pyrene rings and phenanthrene rings can be cited, preferably benzene rings, naphthalene rings and phenanthrene rings, more preferably benzene rings and naphthalene rings, and further preferably benzene rings. The carbocyclic ring may have a substituent, and as a substituent, the above-mentioned substituent A can be cited, preferably at least one selected from the group consisting of a fluorine atom and an alkyl group having 1 to 6 carbon atoms.

[0360] As examples of the heterocyclic ring of T, aromatic heterocyclic rings can be cited, preferably aromatic heterocyclic rings. As specific examples of the heterocyclic ring of T, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring and thienothiophene ring can be cited, preferably thiophene ring, pyridine ring, pyrazine ring, thiazole ring and thienothiophene ring, more preferably thiophene ring. The heterocyclic ring may have a substituent, and as a substituent, the above-mentioned substituent A can be cited, preferably at least one selected from the group consisting of a fluorine atom and an alkyl group having 1 to 6 carbon atoms.

[0361] X 11 , X 12 and X 13 Each independently represents an oxygen atom, a sulfur atom, an alkylene group or a group represented by =C(-CN)2, and is preferably an oxygen atom, a sulfur atom or a group represented by =C(-CN)2.

[0362] X 14 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group or a monovalent heterocyclic group. These groups may have a substituent, and examples of the substituent include the substituent A described above.

[0363] R a11 and R a12 Each independently represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryl group or a monovalent heterocyclic group, and is preferably an alkyl group or an aryl group. These groups may have a substituent, and examples of the substituent include the substituent A described above.

[0364] [Chemistry 28]

[0365]

[0366] In formula (a-8) and formula (a-9), R a11 and R a12 and R in formula (a-1) to formula (a-7)a11 and R a12 The meaning is the same and the preferred method is also the same.

[0367] As A 1 and A 2 The electron-withdrawing group is preferably a group represented by any one of the following formulas (a-1-1) to (a-1-4), (a-6-1) and (a-7-1), and more preferably a group represented by formula (a-1-1). a10 Each independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. a11 and R a12 and R in formula (a-1) to formula (a-7) a11 and R a12 The meaning is the same and the preferred method is also the same.

[0368] [Chemistry 29]

[0369]

[0370] As B 10 Examples of the group containing a π-conjugated system include -(S 1 ) n1 -B 11 -(S 2 ) n2 - the group shown.

[0371] As the non-fullerene compound, a compound represented by the following formula (VII) is preferred.

[0372] A 1 -(S 1 ) n1 -B 11 -(S 2 ) n2 -A 2 (VII)

[0373] In formula (VII), A 1 and A 2 With A in formula (VI) 1 and A 2 The meaning is the same and the preferred method is also the same.

[0374] S 1 and S 2 Each independently represents a divalent carbocyclic group, a divalent heterocyclic group, -C(R s1 )=C(R s2 )-shown group (here, R s1 and Rs2 Each independently represents a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, an alkyl group or a monovalent heterocyclic group), or a group represented by -C≡C-). These groups may have a substituent, and examples of the substituent include the substituent A mentioned above.

[0375] In formula (VII), n1 and n2 each independently represent an integer of 0 or more, preferably each independently represent 0 or 1, and more preferably represent 0 and 1 simultaneously.

[0376] S 1 and S 2 Each independently is preferably a group represented by the following formula (s-1) or (s-2).

[0377] [Chemistry 30]

[0378]

[0379] In formula (s-1) and (s-2),

[0380] X 21 represents an oxygen atom or a sulfur atom.

[0381] R a10 R in formula (a-1-1) to formula (a-1-4) and formula (a-6-1) and formula (a-7-1) a10 The meaning is the same and the preferred method is also the same.

[0382] In formula (VII), B 11 The fused ring group is a fused ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group which does not contain an ortho-peri fused structure and which may have a substituent.

[0383] Here, the fused ring group refers to an atomic group remaining after removing one or more hydrogen atoms directly bonded to a carbon atom or a heteroatom constituting the fused ring.

[0384] As a component of B 11 Examples of the carbocyclic structure of the fused ring group shown include the ring structure shown by the following formula (Cy1) or formula (Cy2).

[0385] [Chemistry 31]

[0386]

[0387] As a component of B 11 Examples of the heterocyclic structure of the fused ring group include ring structures represented by any of the following formulae (Cy3) to (Cy10).

[0388] [Chemistry 32]

[0389]

[0390] In formula (VII), B 11 It is preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by the above formula (Cy1) to (Cy10), and is a fused ring group that does not contain an ortho-peri fused structure and may have a substituent. 11 The structure in which two or more identical structures among the structures represented by formula (Cy1) to formula (Cy10) are fused may also be included.

[0391] B 11 More preferably, it is a fused ring group of two or more structures selected from the group consisting of structures represented by formula (Cy1) to formula (Cy6) and formula (Cy8), and is a fused ring group that does not contain an ortho-peri fused structure. The fused ring group may have a substituent, and as the substituent, the above-mentioned substituent A can be cited.

[0392] As B 11 Examples of fused ring groups include groups represented by the following formulae (b-1) to (b-14) and groups in which hydrogen atoms in these groups are substituted by substituents (preferably an alkyl group which may be substituted, an aryl group which may be substituted, an alkoxy group which may be substituted, or a monovalent heterocyclic group which may be substituted).

[0393] As B 11 The fused ring group is preferably a group represented by the following formula (b-2) or (b-3) or a group in which the hydrogen atoms in these groups are substituted by a substituent (preferably an alkyl group which may be substituted, an aryl group which may be substituted, an alkoxy group which may be substituted, or a monovalent heterocyclic group which may be substituted), and more preferably a group represented by the following formula (b-2) or (b-3).

[0394] [Chemistry 33]

[0395]

[0396] [Chemistry 34]

[0397]

[0398] [Chemistry 35]

[0399]

[0400] In formula (b-1) to formula (b-14), R a10R in formula (a-1-1) to formula (a-1-4) and formula (a-6-1) and formula (a-7-1) a10 The meaning is the same and the preferred method is also the same.

[0401] Examples of the compound represented by formula (VI) or formula (VII) include compounds represented by the following formulas.

[0402] [Chemistry 36]

[0403]

[0404] [Chemistry 37]

[0405]

[0406] In the above formula, R represents a substituent, and examples of the substituent include the substituent A described above.

[0407] In the above formula, X represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.

[0408] In the above formula, R is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group.

[0409] The composition of the present disclosure may contain only a non-fullerene compound or only a fullerene compound as the electron-accepting compound, or may contain a non-fullerene compound and a fullerene compound in combination.

[0410] Preferred specific examples of the electron-accepting compound contained in the composition include compounds represented by the following formulas.

[0411] [Chemistry 38]

[0412]

[0413] In the composition of the present disclosure, the content of the electron-accepting compound is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass, based on the mass of the entire composition.

[0414] In the composition of the present disclosure, the content of the polymer of the present disclosure relative to the content of the electron accepting compound (content of the polymer of the present disclosure / content of the electron accepting compound) is preferably 1 / 9 to 9 / 1, more preferably 1 / 5 to 5 / 1, and even more preferably 1 / 3 to 3 / 1.

[0415] In the composition of the present disclosure, the total content of the polymer of the present disclosure and the electron-accepting compound is preferably 0.01 mass % to 20 mass %, more preferably 0.01 mass % to 10 mass %, further preferably 0.01 mass % to 5 mass %, particularly preferably 0.1 mass % to 5 mass %, relative to the mass of the entire composition.

[0416] (Solvent)

[0417] The composition of the present disclosure may contain a solvent as necessary.

[0418] Examples of the solvent include aromatic hydrocarbons, alkyl halides, aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds.

[0419] The aromatic hydrocarbon is not particularly limited, but is preferably a compound capable of dissolving the polymer of the present disclosure.

[0420] The aromatic hydrocarbon may have a substituent, and examples of the substituent include the substituent A described above.

[0421] Examples of the aromatic hydrocarbons include toluene, xylene (e.g., o-xylene, m-xylene, p-xylene), trimethylbenzenes (e.g., mesitylene, 1,2,4-trimethylbenzene (trimethylol)), butylbenzenes (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1,2,3,4-tetrahydronaphthalene (tetralin), indane, 1-chloronaphthalene, chlorobenzene, and dichlorobenzene (1,2-dichlorobenzene).

[0422] The aromatic hydrocarbon is preferably at least one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).

[0423] Examples of the alkyl halide include chloroform.

[0424] Examples of the aromatic carbonyl compound include acetophenone, propiophenone, butylphenone, cyclohexylphenylketone and benzophenone.

[0425] Examples of the aromatic ester compound include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopropyl benzoate, benzyl benzoate, cyclohexyl benzoate, and phenyl benzoate.

[0426] Examples of the nitrogen-containing heterocyclic compound include pyridine, quinoline, quinoxaline, 1,2,3,4-tetrahydroquinoline, pyrimidine, pyrazine and quinazoline.

[0427] The content of the solvent is preferably 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less, based on the mass of the entire composition.

[0428] The composition of the present disclosure may contain other ingredients as required.

[0429] Examples of other components include ultraviolet absorbers, antioxidants, sensitizers for sensitizing the function of generating charges by absorbing light, and light stabilizers for increasing stability against ultraviolet rays.

[0430] The content of other components is preferably 0 mass % or more and 10 mass % or less relative to the mass of the entire composition, and may be 0 mass %.

[0431] (Method for producing composition)

[0432] The composition can be produced by a conventionally known method. The solvent, the polymer of the present disclosure, and the electron accepting compound can be heated to a temperature below the boiling point of the solvent and mixed.

[0433] The solvent, the polymer of the present disclosure and the electron accepting compound may be mixed, and the resulting mixture may be filtered through a filter to obtain a filtrate as the composition. For example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE) may be used as the filter.

[0434] (Use of the composition)

[0435] The composition can be suitably used as ink for forming a film containing the polymer of the present disclosure and an electron-accepting compound by a coating method.

[0436] In this specification, "ink" refers to a liquid substance used for a coating method, and is not limited to a colored liquid. In addition, "coating method" includes a method of forming a film (layer) using a liquid substance. Examples of coating methods include slit die coating, slit coating, blade coating, casting, micro-gravure coating, gravure coating, rod coating, roller coating, wire rod coating, dip coating, spray coating, screen printing, gravure printing, flexographic printing, offset printing, inkjet coating, dispenser printing, nozzle coating, and capillary coating.

[0437] <Film>

[0438] The films of the present disclosure contain the polymers of the present disclosure.

[0439] The film of the present disclosure preferably comprises the polymer of the present disclosure and an electron accepting compound.

[0440] Preferred embodiments of the polymer contained in the film of the present disclosure are as described in the description of the polymer of the present disclosure.

[0441] When the film of the present disclosure contains an electron accepting compound, examples of the electron accepting compound contained in the film of the present disclosure include the same compounds as the electron accepting compound contained in the composition of the present disclosure, and preferred embodiments are also the same.

[0442] In the film of the present disclosure, the content of the polymer of the present disclosure is preferably 1 mass % to 99 mass %, more preferably 10 mass % to 90 mass %, further preferably 20 mass % to 80 mass %.

[0443] In the film of the present disclosure, the content of the electron accepting compound is preferably 1 mass % to 99 mass %, more preferably 10 mass % to 90 mass %, further preferably 20 mass % to 80 mass %.

[0444] In the film of the present disclosure, the content of the polymer of the present disclosure relative to the content of the electron accepting compound (content of the polymer of the present disclosure / content of the electron accepting compound) is preferably 1 / 9 to 9 / 1, more preferably 1 / 5 to 5 / 1, and further preferably 1 / 3 to 3 / 1.

[0445] The films of the present disclosure may contain a solvent, but preferably contain substantially no solvent.

[0446] In the film of the present disclosure, the content of the solvent is preferably 0 mass % to 1 mass %, more preferably 0 mass % to 0.1 mass %, and even more preferably 0 mass %.

[0447] The absorption edge strength of the film disclosed herein is preferably 0.17 or less, and from the viewpoint of suppressing dark current, is preferably 0.01 or more and 0.17 or less, more preferably 0.03 or more and 0.17 or less, and further preferably 0.04 or more and 0.16 or less.

[0448] Determination of the absorption limit intensity of the membrane

[0449] The absorption intensity of the film was measured using a UV-visible infrared spectrophotometer.

[0450] The method for measuring the absorption edge intensity of the film is the same as the method for measuring the absorption edge intensity of the polymer described above, except that a thin film having a thickness of 100 nm and having the same composition as that of the film is used as the measurement object.

[0451] The method for producing the film of the present disclosure is not particularly limited, and the film can be produced by any method.

[0452] For example, the film of the present disclosure can be produced by a production method including the step (i) of applying the composition of the present disclosure to a coating object to obtain a coating film and the step (ii) of removing the solvent from the obtained coating film.

[0453] (Process (i))

[0454] In step (i), as a method for applying the composition to the coating object, any conventionally known coating method can be used. Specific examples of the coating method are as described above.

[0455] In step (i), the composition is applied to any coating target. In the process of manufacturing a photoelectric conversion element, the composition can be applied to a functional layer that can be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer or a hole transport layer.

[0456] (Step (ii))

[0457] In step (ii), any suitable method can be used as a method for removing the solvent from the coating film of the composition formed by step (i). Examples of methods for removing the solvent include hot air drying, infrared heating drying, flash lamp annealing drying, reduced pressure drying and the like.

[0458] The application of the film of the present disclosure is not particularly limited, and the film can be suitably used as, for example, an active layer included in a photoelectric conversion element.

[0459] <Electronic Components>

[0460] The electronic component of the present disclosure includes the polymer of the present disclosure.

[0461] The electronic component of the present disclosure preferably contains a film comprising the polymer of the present disclosure.

[0462] The polymer disclosed in the present invention can exert high electron or high hole transport properties or both, so when the polymer disclosed in the present invention is used in an electronic component, it can transport electrons, holes injected from an electrode, or charges generated by light absorption. Utilizing these properties, it can be suitable for various electronic components such as photoelectric conversion elements, organic thin film transistors, and organic electroluminescent elements. These components are described below.

[0463] (Photoelectric conversion element)

[0464] The photoelectric conversion element disclosed in the present invention includes a first electrode, a second electrode, and an active layer disposed between the first electrode and the second electrode.

[0465] Furthermore, the active layer contains the polymer disclosed in the present invention.

[0466] Hereinafter, a configuration example of one embodiment of the photoelectric conversion element disclosed in the present invention will be described in detail with reference to the drawings.

[0467] Figure 2 It is a diagram schematically showing a configuration example of a photoelectric conversion element.

[0468] like Figure 2 As shown, the photoelectric conversion element 10 is provided on the supporting substrate 11. The photoelectric conversion element 10 includes: a first electrode 12 provided in contact with the supporting substrate 11; a first intermediate layer 13 provided in contact with the first electrode 12; an active layer 14 provided in contact with the first intermediate layer 13; a second intermediate layer 15 provided in contact with the active layer 14; and a second electrode 16 provided in contact with the second intermediate layer 15. In this configuration example, a sealing member 17 is further provided in contact with the second electrode 16. In this configuration example, both the first intermediate layer 13 and the second intermediate layer 15 are provided, but only one of the first intermediate layer 13 and the second intermediate layer 15 may be provided. For example, the first intermediate layer 13 may not be provided. For example, the second intermediate layer 15 may not be provided.

[0469] Hereinafter, constituent elements that may be included in one embodiment of the photoelectric conversion element of the present disclosure will be described in detail.

[0470] (Substrate)

[0471] The photoelectric conversion element is usually formed on a substrate (support substrate). In addition, the substrate (sealing substrate) is sometimes used for sealing. One of a pair of electrodes consisting of a first electrode and a second electrode is usually formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not undergo chemical changes when forming a layer containing an organic compound.

[0472] As the material of the substrate, for example, glass, plastic, polymer film, silicon can be cited. When an opaque substrate is used, it is preferred that the electrode on the opposite side of the electrode disposed on the opaque substrate side (in other words, the electrode away from the opaque substrate side) is set as a transparent or translucent electrode.

[0473] (electrode)

[0474] The photoelectric conversion element includes a first electrode and a second electrode as a pair of electrodes. At least one of the first electrode and the second electrode is preferably a transparent or semi-transparent electrode for incident light.

[0475] As examples of materials for transparent or translucent electrodes, conductive metal oxide films and translucent metal films can be cited. Specifically, conductive materials such as indium oxide, zinc oxide, tin oxide and indium tin oxide (ITO), indium zinc oxide (IZO), NESA, gold, platinum, silver, and copper as their composites can be cited. As materials for transparent or translucent electrodes, ITO, IZO, and tin oxide are preferred. In addition, as electrodes, transparent conductive films using organic compounds such as polyaniline and derivatives thereof, polythiophene and derivatives thereof as materials can also be used. The transparent or translucent electrode can be the first electrode or the second electrode.

[0476] If one of a pair of electrodes is transparent or translucent, the other electrode may also be an electrode with low light transmittance. Examples of materials for electrodes with low light transmittance include metals and conductive polymers. Specific examples of materials for electrodes 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, and ytterbium, and alloys of two or more of these; or alloys of one or more of these metals with one or more of the 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. As alloys, magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys can be cited.

[0477] (Active layer)

[0478] The photoelectric conversion element of the present disclosure includes an active layer containing the polymer of the present disclosure.

[0479] As the active layer, the above-mentioned film of the present disclosure can be applied.

[0480] The active layer has a bulk heterojunction structure.

[0481] The thickness of the active layer is not particularly limited. The thickness of the active layer can be set to any appropriate thickness, for example, in consideration of the balance between suppressing dark current and extracting the generated photocurrent. In particular, from the perspective of further reducing dark current, the thickness of the active layer is preferably 100 nm to 10 μm, more preferably 150 nm to 5 μm, and further preferably 200 nm to 1 μm.

[0482] (Middle layer)

[0483] like Figure 2As shown, 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) as a component for improving characteristics such as photoelectric conversion efficiency.

[0484] 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).

[0485] The intermediate layer can be formed by any conventionally known appropriate formation method. The intermediate layer can be formed by a vacuum deposition method or a coating method similar to the formation method of the active layer.

[0486] like Figure 2 As shown, the photoelectric conversion element preferably includes an electron transport layer as a first intermediate layer between the first electrode and the active layer. The photoelectric conversion element may or may not include a hole transport layer as a second intermediate layer between the second electrode and the active layer.

[0487] In another embodiment, the photoelectric conversion element preferably includes an electron transport layer as a second intermediate layer between the second electrode and the active layer. In this other embodiment, the photoelectric conversion element may or may not include a hole transport layer as a first intermediate layer between the first electrode and the active layer.

[0488] The electron transport layer has the function of transporting electrons from the active layer to the electrode, and the hole transport layer has the function of transporting holes from the active layer to the electrode.

[0489] In particular, the electron transport layer disposed in contact with the electrode is sometimes referred to as an electron injection layer. The electron transport layer (electron injection layer) disposed in contact with the electrode has the function of promoting the injection of electrons into the electrode. The electron transport layer (electron injection layer) may be in contact with the active layer.

[0490] The electron transport layer contains an electron transport material. Examples of the electron transport material include polyalkylene imine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.

[0491] Examples of polyalkyleneimines and their derivatives include polymers obtained by polymerizing one or more of alkyleneimines having 2 to 8 carbon atoms, particularly alkyleneimines having 2 to 4 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, and octyleneimine by conventional methods, and polymers chemically modified by reacting these with various compounds. Polyalkyleneimines and their derivatives are preferably polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE).

[0492] Examples of the polymer compound containing a fluorene structure include poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-o-2,7-(9,9′-dioctylfluorene)] (PFN) and PFN-P2.

[0493] 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 preferred, and zinc oxide is preferred among them.

[0494] Examples of other electron transporting materials include poly(4-vinylphenol) and perylene diimide.

[0495] In particular, a hole transport layer provided in contact with an electrode is sometimes referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with an electrode has a function of promoting injection of holes generated in the active layer into the electrode.

[0496] The hole transport layer contains a hole transport material. Examples of the hole transport material 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).

[0497] (Sealing member)

[0498] The photoelectric conversion element of the present disclosure preferably further includes a sealing member, and is formed into a sealed body sealed by the sealing member.

[0499] Any suitable conventionally known sealing member can be used as the sealing member. Examples of the sealing member include a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.

[0500] The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.

[0501] 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 materials suitable for the sealing layer include organic materials such as trifluoroethylene, polychlorotrifluoroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.

[0502] The sealing member is generally made of a material that can withstand a heat treatment that is performed when the photoelectric conversion element is incorporated into a device, such as an applicable example described later.

[0503] In other embodiments, both or either of the first intermediate layer 13 and the second intermediate layer 15 may not be provided.

[0504] (Method for manufacturing photoelectric conversion element)

[0505] The photoelectric conversion element can be produced by any suitable production method known in the art. The photoelectric conversion element can be produced by combining processes suitable for materials selected when forming the components.

[0506] Hereinafter, as an example of a method for manufacturing a photoelectric conversion element, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (support substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order will be described.

[0507] (Step of preparing substrate)

[0508] In this step, for example, a support substrate provided with a first electrode is prepared. Alternatively, a substrate provided with a conductive film formed of the electrode material described above can be obtained from the market, and the conductive film can be patterned to form the first electrode as needed, thereby preparing a support substrate provided with a first electrode.

[0509] In the manufacturing method of the photoelectric conversion element disclosed in the present invention, the method for forming the first electrode when forming the first electrode on the supporting substrate is not particularly limited. The first electrode can be formed by any suitable method known in the art such as vacuum evaporation, sputtering, ion plating, plating, coating, etc., by forming the material described above on the structure (e.g., supporting substrate, active layer, hole transport layer) where the first electrode is to be formed.

[0510] (Hole Transport Layer Formation Step)

[0511] 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 first electrode.

[0512] The method for forming the hole transport layer is not particularly limited. From the perspective of making the formation process of the hole transport layer simpler, the hole transport layer is preferably formed by any suitable coating method known in the art. The hole transport layer can be formed, for example, by a coating method using a coating solution containing the material and solvent that can constitute the hole transport layer as described above, or by a vacuum evaporation method.

[0513] (Active Layer Formation Step)

[0514] In the method for manufacturing a photoelectric conversion element, an active layer is formed on the hole transport layer. The active layer can be formed by any suitable conventionally known formation process. The active layer can be manufactured by a coating method using the composition of the present disclosure described above.

[0515] The active layer can be formed in the same manner as the film of the present disclosure described above. The active layer can be formed by the following process, which includes the step of applying a composition comprising the polymer (p-type semiconductor) of the present disclosure, an electron-accepting compound (n-type semiconductor), a surfactant and a solvent on the hole transport layer to form a coating film, and then drying the coating film.

[0516] (Step of Forming Electron Transport Layer)

[0517] The method for manufacturing a photoelectric conversion element may include a step of forming an electron transport layer (electron injection layer) provided so as to be in contact with the active layer.

[0518] The method for forming the electron transport layer is not particularly limited. From the perspective of simplifying the step of forming the electron transport layer, the electron transport layer is preferably formed by any suitable vacuum deposition method known in the art.

[0519] (Second Electrode Formation Step)

[0520] The method for forming the second electrode is not particularly limited. The second electrode can be formed of the material of the electrode exemplified above by any suitable method known in the art, such as coating, vacuum evaporation, sputtering, ion plating, and plating. The photoelectric conversion element of the present disclosure is manufactured through the above steps.

[0521] (Sealing Body Forming Step)

[0522] When forming the sealed body, any suitable sealing material (adhesive) and substrate (sealing substrate) known in the art are used. Specifically, a sealing material such as a UV curable resin is applied to a supporting substrate in a manner that surrounds the periphery of the manufactured photoelectric conversion element, and after seamlessly laminating the sealing material, the photoelectric conversion element is sealed in the gap between the supporting substrate and the sealing substrate by irradiating UV light suitable for the selected sealing material, thereby obtaining a sealed body of the photoelectric conversion element.

[0523] (Application Examples of Photoelectric Conversion Element)

[0524] As uses of the photoelectric conversion element of the present disclosure, a light detection element and a solar cell can be cited. By irradiating the photoelectric conversion element of the present disclosure with light, a photoelectromotive force can be generated between electrodes, and it can operate as a solar cell. A solar cell module can also be fabricated by integrating two or more photoelectric conversion elements.

[0525] When the photoelectric conversion element of the present disclosure is irradiated with light from the transparent or semi-transparent electrode side in a state where a voltage (reverse bias) is applied between the counter electrodes, a photocurrent can flow, and it can operate as a light detection element (photo sensor). In addition, it can be used as an image sensor by integrating two or more light detection elements. The photoelectric conversion element of the present disclosure can be particularly suitably used as a light detection element.

[0526] The photoelectric conversion element of the present disclosure can be suitably used as a light detection element for detection units provided in various electronic devices such as workstations, personal computers, mobile information terminals, access control systems, digital cameras, and medical instruments.

[0527] The photoelectric conversion element of the present disclosure can be suitably used for an image detection unit (such as an image sensor such as an X-ray sensor) for a solid imaging device such as an X-ray imaging device and a CMOS image sensor, a fingerprint detection unit, a face detection unit, a vein detection unit, and an iris detection unit provided in the above-exemplified electronic devices, etc., a detection unit of a biological information authentication device for detecting specific features of a living body (such as a near-infrared sensor), a detection unit of an optical biosensor such as a pulse oximeter, etc.

[0528] Examples

[0529] Examples will be described below, but the present invention is not limited by any of these examples. It should be noted that in the following description, "parts" and "%" are based on mass unless otherwise specified.

[0530] <NMR Measurement>

[0531] For proton NMR measurement (hereinafter referred to as 1 1H-NMR measurement) for confirming the formation of a compound, the compound was dissolved in deuterated chloroform and measured using a nuclear magnetic resonance (NMR: Nuclear Magnetic Resonance) apparatus (manufactured by JEOL Ltd., resonance frequency of protons 400 MHz).

[0532] It should be noted that J HH represents the coupling constant.

[0533] <Synthesis of the Compound Represented by Formula (I-R)>

[0534] (Synthesis of Compound 4)

[0535] Compound 4, a compound represented by formula (IR), was synthesized by the following steps.

[0536] -Synthesis of Compound 2-

[0537] [Chemistry 39]

[0538]

[0539] Magnesium (3.22 g, 0.133 mol), THF (93.7 g), and iodine (63.5 mg) were added to a 1 L four-necked flask purged with nitrogen, and stirred. After the purple color of iodine disappeared, 10% by mass of a solution containing 1-bromo-4-dodecylbenzene (40.7 g, 0.125 mmol) and THF (72.9 g) was added dropwise to the four-necked flask, and heated to 55°C to generate a Grignard reagent. After cooling to 35°C, a solution containing 1-bromo-4-dodecylbenzene and THF was added dropwise to the four-necked flask in a manner not exceeding 45°C. After that, it was stirred at room temperature for 2 hours.

[0540] A solution containing compound 1 (10.4 g, 0.050 mol) and THF (213 g) was added dropwise to the four-necked flask so that the internal temperature did not exceed 35° C. The mixture was then stirred for 1 hour and allowed to stand overnight.

[0541] The reaction solution was quenched by injecting a 6% NH4Cl aqueous solution, and the organic layer was extracted. Toluene was added to the organic layer, and the mixture was washed once with saturated brine, dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate was concentrated by a rotary evaporator to obtain 42.65 g of a crude product of compound 2 as a yellow liquid.

[0542] -Synthesis of Compound 3-

[0543] [Chemistry 40]

[0544]

[0545] The crude product of compound 2 (42.65 g) and heptane (321 g) were placed in a 1 L four-necked flask, and nitrogen was purged for 30 minutes. Trifluoroacetic acid (0.986 g, 0.0087 mmol) was placed in the four-necked flask, and the temperature was raised to 60° C. After reaching 60° C., the mixture was stirred for 30 minutes, and then cooled to room temperature to obtain a reaction solution.

[0546] The reaction solution was washed twice with water, dried over magnesium sulfate, purified using a silica gel column (heptane was used as a developing solvent), and concentrated using a rotary evaporator to obtain 33 g of a crude product of Compound 3 as a yellow liquid.

[0547] -Synthesis of Compound 4-

[0548] [Chemistry 41]

[0549]

[0550] The crude product of compound 3 (8.56 g), tetramethylethylenediamine (1.16 g, 0.010 mol) and dehydrated THF (106 g) were placed in a 300 mL four-necked flask purged with nitrogen and dissolved. After confirming that the oxygen concentration was less than 0.02%, the flask was immersed in a cooling tank containing dry ice and acetone and cooled to an internal temperature of -60°C or less. A 1.6 mol / L nBuLi hexane solution (16 mL, 2.5 eq, 0.025 mmol) was slowly added dropwise to the four-necked flask so that the internal temperature did not exceed -60°C. After keeping the temperature for 2 hours, a solution prepared by diluting isopropyl borate (5.27 g, 2.8 eq, 0.028 mmol) with 9.6 g of dehydrated THF was slowly added dropwise to the four-necked flask so that the internal temperature did not exceed -60°C. After keeping the temperature for 1 hour, the flask was lifted from the bath and naturally heated to room temperature. 75.6 g of 2% hydrochloric acid was added dropwise to a four-necked flask to quench the mixture, and the aqueous layer was removed by separation. Toluene, magnesium sulfate, and trimethylolethane (3.60 g, 0.030 mmol, 3.0 eq.) were added to the organic layer, and the mixture was stirred at room temperature for 1 hour and then allowed to stand overnight. The magnesium sulfate was removed by filtration, and the filtrate was concentrated by an evaporator, toluene was added, and insoluble matter was removed by filtration.

[0551] After concentrating again with an evaporator, ethanol and hexane were added to the concentrate for recrystallization, followed by filtration and washing with cooled hexane. The obtained solid was dried overnight at 40° C. under reduced pressure to obtain 5.19 g of compound 4 as a white solid.

[0552] (Synthesis of Compound 7)

[0553] Compound 7, a compound represented by formula (IR), was synthesized by the following steps.

[0554] -Synthesis of Compound 5-

[0555] [Chemistry 42]

[0556]

[0557] Magnesium (3.28 g, 135 mmol), a small amount (5 grains) of iodine, and THF (110 mL) were added to a 1 L four-necked flask purged with nitrogen, and the temperature was raised in an oil bath so that the internal temperature became 45°C. A solution prepared by dissolving 3,5-dihexyl-bromobenzene in THF (85 mL) was added dropwise to the four-necked flask so that the internal temperature was maintained at about 45°C, thereby preparing a Grignard reagent. The Grignard reagent solution was cooled to room temperature, and a solution prepared by dissolving compound 1 (10.4 g, 50.0 mmol) in THF (250 mL) was added dropwise thereto. After the addition, the mixture was stirred at room temperature for 1 hour, and then a saturated aqueous ammonium chloride solution and hexane were added and stirred, thereby washing the organic layer. The obtained organic layer was further separated and washed once with saturated brine. After drying with anhydrous sodium sulfate, the mixture was filtered, and the solvent was distilled off under reduced pressure, thereby obtaining 46.1 g of a crude product of compound 5 in the form of a yellow-brown oil.

[0558] -Synthesis of Compound 6-

[0559] [Chemistry 43]

[0560]

[0561] The crude product of compound 5 (46.1 g, 50.0 mmol), p-toluenesulfonic acid monohydrate (1.62 g, 8.50 mmol), and toluene (250 mL) were added to a 500 mL three-necked flask replaced with nitrogen, and heated and stirred in an oil bath set at 80 ° C for 2 hours. After confirming the completion of the reaction by liquid chromatography, water was added to the reaction solution to stop the reaction, and then the organic layer was further washed with water once and washed with saturated brine once. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified with a silica gel column (hexane and ethyl acetate were used as the developing solvent), thereby obtaining 33.6 g of compound 6 in the form of a light yellow oil.

[0562] Compound 6 1 The results of H-NMR measurement are as follows.

[0563] δ(ppm):7.00(d,J HH =5.0Hz,1H),6.94(d,J HH =5.5Hz,1H),6.89(s,2H),6.88(s,4H),6.78(d,J HH =5.5Hz,1H),6.45(d,J HH =5.0Hz,1H),2.50(t,J HH=7.5Hz,8H),1.48-1.54(m,8H),1.24-1.29(m,24H),0.84-0.89(m,12H).

[0564] -Synthesis of Compound 7-

[0565] [Chemistry 44]

[0566]

[0567] Compound 6 (10.3 g, 15.0 mmol), tetraethylethylenediamine (1.74 g, 15 mmol), and dehydrated THF (150 mL) were added to a 500 mL four-necked flask purged with nitrogen, and stirred to dissolve. Next, the solution was cooled to -78°C in a cooling tank containing dry ice and acetone, and a 1.6 mol / L nBuLi hexane solution (24.0 mL) was added dropwise, and stirred at -78°C for 2 hours. While maintaining -78°C, a solution prepared by dissolving triisopropoxyborane (7.90 g, 42.0 mmol) in tetrahydrofuran (17 mL) was added dropwise to the four-necked flask, and stirred at -78°C for 1 hour, and then heated to room temperature. Next, 122 g of 2% mp hydrochloric acid was added to the reaction solution, and the organic layer was extracted for separation and washing. Anhydrous magnesium sulfate was added to the organic layer, and after stirring for 5 minutes, 2-hydroxymethylene-2-methyl-1,3-propanediol (5.41 g, 45.0 mmol) was added and stirred for 30 minutes. After filtering, the solvent was distilled off under reduced pressure, toluene was added, and filtered again. The solvent of the obtained solution was distilled off under reduced pressure, thereby obtaining 16.05 g of a crude product of compound 7 in the form of a light yellow-green oil (containing toluene, crude product yield 114%, liquid chromatography purity 99.4%).

[0568] Compound 7 1 The results of H-NMR measurement are as follows.

[0569] δ(ppm): 7.14(s,1H),6.88(s,2H),6.87(s,1H),6.84(s,4H),3.62-3.95(br,12H),2.48(t,J HH =7.8Hz,8H),1.51(br,8H),1.24-1.31(br,24H),0.97(s,3H),0.96(s,3H),0.85(t,J HH =7.2Hz,12H).

[0570] (Synthesis of Compound 10)

[0571] Compound 10, a compound represented by formula (IR), was synthesized by the following steps.

[0572] -Synthesis of Compound 8-

[0573] [Chemistry 45]

[0574]

[0575] Magnesium (8.21 g, 338 mmol), a small amount (3 grains) of iodine, and tetrahydrofuran (270 mL) were added to a 2L four-necked flask purged with nitrogen. A solution of 2-hexyl-1-bromodecane (94.9 g, 31 mmol) dissolved in THF (200 mL) was added dropwise thereto while maintaining the internal temperature below 30°C, thereby preparing the Grignard reagent. The Grignard reagent solution was cooled to room temperature, and a solution of compound 1 (10.3 g, 49.2 mmol) dissolved in THF (197 mL) was added dropwise thereto. After the addition, the mixture was stirred at room temperature for 1 hour, and a saturated aqueous ammonium chloride solution and hexane were added and stirred, thereby washing the organic layer. Next, the obtained organic layer was separated and washed once with saturated brine. After drying with anhydrous magnesium sulfate, the mixture was filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified using a silica gel column (hexane and ethyl acetate were used as the developing solvent) to obtain 22.4 g of Compound 8 as a light yellow oil.

[0576] Compound 8 1 The results of H-NMR measurement are as follows.

[0577] δ(ppm):7.56(s,1H),7.25(d,J HH =4.8Hz,1H),7.16(d,J HH =5.5Hz,1H),6.84(t,J HH =4.8Hz,1H),6.74(d,J HH =5.5Hz,1H),2.34(s,1H),1.77(m,4H),1.10-1.31(m,50H),0.84-0.90(m,12H)

[0578] -Synthesis of Compound 9-

[0579] [Chemistry 46]

[0580]

[0581] Compound 8 (22.4 g, 34.0 mmol) and heptane (230 mL) were added to a 500 mL three-necked flask replaced with nitrogen, and cooled to 0°C. Trifluoroacetic acid (19.4 g, 170 mmol) was added dropwise thereto, and stirred at 0°C for 5 hours. After the reaction was stopped by adding water, the organic layer was further washed with water once and with saturated brine once. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified with a silica gel column (hexane and ethyl acetate were used as the developing solvent), thereby obtaining 15.3 g of compound 9 in the form of a light yellow oil.

[0582] Compound 9 1 The results of H-NMR measurement are as follows.

[0583] δ(ppm):6.97(d,J HH =5.0Hz,1H),6.92(d,J HH =5.0Hz,1H),6.65(d,J HH =5.0Hz,1H),6.57(d,J HH =5.0Hz,1H),1.73-1.82(m,4H),1.04-1.29(m,50H),0.83-0.90(m,12H)

[0584] -Synthesis of Compound 10-

[0585] [Chemistry 47]

[0586]

[0587] Compound 9 (10.08 g), tetramethylethylenediamine (1.82 g) and dehydrated THF (141 g) were placed in a 500 mL four-necked flask purged with nitrogen and dissolved. After confirming that the oxygen concentration was less than 0.02%, the flask was immersed in a cooling tank containing dry ice and acetone and cooled to an internal temperature of less than -60°C. 1.6 mol / L nBuLi hexane solution (24.97 mL, 2.5 eq) was slowly dripped into the four-necked flask so that the internal temperature did not exceed -60°C. After keeping warm for 2 hours, a solution prepared by diluting isopropyl borate (10.06 ml, 2.8 eq) with dehydrated THF (16 mL) was slowly dripped so that the internal temperature did not exceed -60°C. After keeping warm for 1 hour, the flask was lifted from the cooling tank and naturally heated to room temperature. 136 g of a 2% hydrochloric acid solution was dripped to quench the mixture, and the aqueous layer was removed by separation. Toluene, magnesium sulfate and trimethylolethane (5.65 g, 3.0 eq.) were added to the organic layer, stirred at room temperature for 1 hour, and then allowed to stand overnight. Magnesium sulfate was removed by filtration, and the filtrate was concentrated by an evaporator, toluene was added, and trimethylolethane was removed by filtration.

[0588] After concentration with an evaporator, the mixture was recrystallized with heptane, filtered, and washed with cooled hexane. The obtained solid was dried overnight at 40°C under reduced pressure to obtain 9.1 g of Compound 10 as a white solid.

[0589] (Synthesis of Compound 13)

[0590] Compound 13, a compound represented by formula (IR), was synthesized by the following steps.

[0591] -Synthesis of Compound 11-

[0592] [Chemistry 48]

[0593]

[0594] Magnesium (9.79 g), THF (316 mL), and iodine (2 grains) were added to a 2 L four-necked flask purged with nitrogen, and stirred. After the purple color of iodine disappeared, a THF (221 mL) solution of 1-bromo-3-hexylbenzene (91.6 g) was added dropwise over 30 minutes. Then, the temperature was raised to 30°C and stirred for 1 hour.

[0595] A solution containing Compound 1 (31.6 g) and THF (649 mL) was added dropwise to the four-necked flask so that the internal temperature did not exceed 35° C. The mixture was then stirred overnight.

[0596] The reaction solution was quenched by injecting a 10% NH4Cl aqueous solution, and the organic layer was extracted. Toluene was added to the organic layer, washed once with water, dehydrated with magnesium sulfate, filtered to remove magnesium sulfate, and the filtrate was concentrated with a rotary evaporator. The obtained crude product was purified with a silica gel column (hexane and ethyl acetate were used as the developing solvent) to obtain 78.5 g of compound 11.

[0597] -Synthesis of Compound 12-

[0598] [Chemistry 49]

[0599]

[0600] Compound 11 (78.5 g), p-toluenesulfonic acid monohydrate (4.67 g) and toluene (785 mL) were added to a 2 L four-necked flask substituted with nitrogen, heated to 100 ° C, stirred for 1.5 hours, and then cooled. After adding water to stop the reaction, the organic layer was further washed with water once. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained crude product was purified with a silica gel column (hexane was used as the developing solvent) to obtain 71.8 g of compound 12.

[0601] -Synthesis of Compound 13-

[0602] [Chemistry 50]

[0603]

[0604] Compound 12 (42.9 g), tetramethylethylenediamine (12.4 mL) and dehydrated THF (1073 mL) were placed in a 2L four-necked flask purged with nitrogen and dissolved. After confirming that the oxygen concentration was less than 0.02%, the flask was immersed in a cooling tank containing dry ice and acetone and cooled to an internal temperature of -60°C or less. 1.6 mol / L nBuLi hexane solution (132 mL, 2.5 eq) was slowly added dropwise so that the internal temperature did not exceed -60°C. After keeping the temperature for 2 hours, a solution prepared by diluting isopropyl borate (43.88 g, 2.8 eq) with 27 mL of dehydrated THF was slowly added dropwise to the four-necked flask so that the internal temperature did not exceed -60°C. After keeping the temperature for 1 hour, the flask was lifted from the bath and naturally heated to room temperature. 629 mL of a 2% hydrochloric acid solution was added dropwise to quench the mixture. After adding 536 mL of THF, the aqueous layer was removed by separation. Magnesium sulfate and trimethylolethane (30.4 g, 3.0 eq.) were added to the organic layer, stirred at room temperature for 1 hour, and then allowed to stand overnight. Magnesium sulfate was removed by filtration, and the filtrate was concentrated by an evaporator, toluene was added, and insoluble matter was removed by filtration.

[0605] After concentration using an evaporator, hexane was added for recrystallization, followed by filtration and washing with cooled hexane. The obtained solid was dried overnight at 40°C under reduced pressure to obtain 53.7 g of Compound 13.

[0606] (Synthesis of Compound 17)

[0607] Compound 17, a compound represented by formula (IR), was synthesized by the following steps.

[0608] -Synthesis of Compound 14-

[0609] [Chemistry 51]

[0610]

[0611] Magnesium (65.2 g, 2.68 mol), THF (275 mL), and iodine (2 grains) were added to a flask replaced with nitrogen and stirred. After the purple color of iodine disappeared, a THF (4730 mL) solution of 1-bromo-3-hexylbenzene (612.9 g, 2.54 mol) was added dropwise to generate a Grignard reagent.

[0612] In another flask, 1,3-dibromobenzene (550 g, 2.33 mol), THF (2783 mL), PdCl2 (dppf)·CH2Cl2 (7.62 g, 9.33 mmol) were added, stirred, and cooled to 10°C. The prepared Grignard reagent was added dropwise to the flask so that the internal temperature did not exceed 10°C to obtain a reaction solution. After stirring for 1 hour, water was injected into the reaction solution to stop the reaction and separate the liquids. The organic layer was dehydrated with magnesium sulfate, and after removing the magnesium sulfate by filtration, the filtrate was concentrated using a rotary evaporator.

[0613] The product was purified by silica gel column chromatography (hexane solvent) to obtain 532.2 g (1.68 mol, yield 67%) of Compound 14.

[0614] Compound 14 1 The results of H-NMR measurement are as follows.

[0615] δ(ppm):7.73(t,1H),7.52-7.50(dt,1H),7.48-7.45(dq,1H),7.38-7.28(m,4H), 7.21-7.18(m,1H),2.67(t,2H),1.69-1.58(m,2H),1.40-1.28(m,6H),0.89(t,3H)

[0616] -Synthesis of Compound 15-

[0617] [Chemistry 52]

[0618]

[0619] Magnesium (1.61 g, 0.066 mol), THF (47 g), and iodine (32 mg) were added to a 1 L four-necked flask purged with nitrogen and stirred. After the purple color of iodine disappeared, a THF (36 g) solution of compound 14 (19.8 g, 0.063 mmol) was added dropwise to generate a Grignard reagent.

[0620] A solution containing compound 1 (5.21 g, 0.025 mol) synthesized by the method described in International Publication No. 2011 / 136311 and THF (107 g) was added dropwise to a four-necked flask at an internal temperature not exceeding 40° C. to obtain a reaction solution. The mixture was stirred for 1 hour, and an aqueous ammonium chloride solution was injected into the reaction solution to stop the reaction and separate the liquids. The organic layer was dehydrated with magnesium sulfate, and after removing the magnesium sulfate by filtration, the filtrate was concentrated by a rotary evaporator.

[0621] The product was purified by silica gel column chromatography (hexane and ethyl acetate were used as developing solvents) to obtain 14.21 g (20.7 mmol, yield 83%) of Compound 15.

[0622] Compound 15 1 The results of H-NMR measurement are as follows.

[0623] 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)

[0624] -Synthesis of Compound 16-

[0625] [Chemistry 53]

[0626]

[0627] Compound 15 (14.21 g, 0.0208 mmol) and heptane (130 g) were placed in a 500 mL four-necked flask. After nitrogen substitution in the reaction container, trifluoroacetic acid (0.409 g, 0.0036 mmol) was added, the temperature was raised to 60° C., stirred for 30 minutes, and then cooled to room temperature to obtain a reaction solution.

[0628] The reaction solution was washed twice with water, and the organic layer was dehydrated with magnesium sulfate and passed into a Kiriyama funnel filled with silica gel. The filtrate was concentrated with a rotary evaporator to obtain 13.37 g (yield 96.6%) of Compound 16.

[0629] Compound 16 1 The results of H-NMR measurement are as follows.

[0630] 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)

[0631] -Synthesis of Compound 17-

[0632] [Chemistry 54]

[0633]

[0634] Compound 16 (25.0 g), tetraethylethylenediamine (5.6 mL), and dehydrated tetrahydrofuran (436 mL) were added to an argon-replaced flask and stirred to dissolve. Subsequently, the solution was cooled to -65°C in a cooling tank containing dry ice and acetone, and 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 further stirring at -65°C for 1 hour, the mixture was warmed to room temperature to obtain a reaction solution. Subsequently, 290 mL of hydrochloric acid at a concentration of 2% was added to the reaction solution for separation. Magnesium sulfate and trimethylolethane (13.5 g) were added to the organic layer and stirred at room temperature for 1 hour. The 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, the precipitated solid was removed by filtration, hexane was added, the supernatant was removed, and the solvent was then removed under reduced pressure to obtain 37.7 g (yield 109%) of Compound 17.

[0635] (Synthesis of Compound 20)

[0636] Compound 20, a compound represented by formula (IR), was synthesized by the following steps.

[0637] -Synthesis of Compound 18-

[0638] [Chemistry 55]

[0639]

[0640] Magnesium (12.37 g), THF (360 mL), and iodine (two grains) were added to a flask replaced with argon, 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.

[0641] A solution of compound 1 (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. The mixture was then stirred overnight, and a 10% aqueous solution of ammonium chloride (450 mL) was injected into the reaction solution to stop the reaction and perform liquid separation. The organic layer was dehydrated with magnesium sulfate, and after removing the magnesium sulfate by filtration, the filtrate was concentrated with a rotary evaporator.

[0642] The product was purified by silica gel column chromatography (hexane and ethyl acetate were used as developing solvents) to obtain 128.6 g (yield 99%) of Compound 18.

[0643] -Synthesis of Compound 19-

[0644] [Chemistry 56]

[0645]

[0646] Compound 18 (128.6 g) and toluene (1376 mL) were added to a flask replaced with argon. After nitrogen replacement in the reaction container, p-toluenesulfonic acid monohydrate (5.39 g) was added, the temperature was raised to 100° C., and the mixture was stirred for 1.5 hours and then cooled to room temperature to obtain a reaction solution.

[0647] After the reaction solution was washed with water, the organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration, and then the filtrate was concentrated with a rotary evaporator.

[0648] Hexane (150 mL) was added to precipitate a solid, and then toluene (50 mL) and hexane (50 mL) were added. After cooling with ice for 60 minutes, the precipitated solid was filtered and dried to obtain 106 g (yield 96%) of Compound 19.

[0649] -Synthesis of Compound 20-

[0650] [Chemistry 57]

[0651]

[0652] Compound 19 (28.38 g), tetraethylethylenediamine (6.5 mL), and dehydrated THF 568 mL were added to an argon-replaced flask, and stirred to dissolve. Then, the solution was cooled to -65°C in a cooling tank containing dry ice and acetone, and 1.6 mol / L nBuLi hexane solution (69.9 mL) was added dropwise, and stirred at -65°C for 1 hour. While maintaining -65°C, a liquid prepared by dissolving triisopropoxyborane (22.96 g) in THF 11.4 mL was added dropwise, and after further stirring at -65°C for 1 hour, the mixture was warmed to room temperature. Then, 329 mL of hydrochloric acid at a concentration of 10% was added to the reaction solution for separation. Magnesium sulfate and trimethylolethane (15.72 g) were added to the organic layer and stirred at room temperature for 1 hour. The 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 refrigerated overnight to remove the precipitated solid, and the solvent was distilled off from the filtrate under reduced pressure to obtain a crude product. The crude product was recrystallized from ethanol and hexane to obtain 36.18 g (yield 91.5%) of Compound 20.

[0653] (Synthesis of Compound 22)

[0654] [Chemistry 58]

[0655]

[0656] Compound 21 (20.27 g), tetraethylethylenediamine (5.87 mL) and dehydrated THF (506 mL) synthesized by the method described in the literature (Dyes and Pigments, 2015, 112, 145.) were added to a flask replaced with argon, and stirred to dissolve. Then, the solution was cooled to -65 ° C in a cooling tank containing dry ice and acetone, and a 1.6 mol / L nBuLi hexane solution (62.7 mL) was added dropwise, and stirred at -65 ° C for 1 hour. While maintaining -65 ° C, a liquid obtained by dissolving triisopropoxyborane (20.73 g) in THF (28.4 mL) was added dropwise, and after further stirring at -65 ° C for 1 hour, the reaction solution was warmed to room temperature to obtain a reaction solution. Then, 296 mL of hydrochloric acid with a concentration of 10% was added to the reaction solution for liquid separation. Magnesium sulfate and trimethylolethane (120.15 g) were added to the organic layer and stirred at room temperature for 1 hour. Magnesium sulfate was removed by filtration. The filtrate was distilled under reduced pressure to remove the solvent, hexane (480 mL) was added, cooled with ice water, and the precipitated solid was filtered out. The obtained solid was dissolved in toluene (480 mL) and the insoluble components were removed by filtration. The filtrate was distilled under reduced pressure to remove the solvent to obtain a crude product. The obtained crude product was recrystallized from ethanol and hexane to obtain 26.94 g (yield 88.8%) of compound 22.

[0657] (Synthesis of Compound 23)

[0658] Compound 23, a compound represented by formula (IR), was synthesized by the procedure described in the document (Japanese Patent No. 6070722).

[0659] [Chemistry 59]

[0660]

[0661] (Synthesis of Compound 24)

[0662] Compound 24, a compound represented by formula (IR), was synthesized by the procedure described in the document (Japanese Patent No. 6070722).

[0663] [Chemistry 60]

[0664]

[0665] <Example 1>

[0666] [Chemistry 61]

[0667]

[0668] First, Compound 25 and Compound 26 were synthesized by the method described in International Publication No. 2014 / 112656.

[0669] Next, in a glass reaction container equipped with a cooling device, compound 26 (1.2 mmol), compound 22 (0.588 mmol), compound 25 (0.588 mmol), water (35.7 g), 40% by mass potassium phosphate aqueous solution (4.3 mL), THF (28 mL), tetralin (12 mL) and bis(tri-tert-butylphosphine)palladium (0) (0.01 mmol) as raw materials were added at room temperature, and stirred at 65° C. for 1 hour. A mixed solution of phenylboric acid (1.2 mmol) and 40% by mass potassium phosphate aqueous solution (6.3 mL) as raw materials was added to the reaction container, and stirred at 65° C. for 1 hour. The generated organic layer was washed with sodium diethyldithiocarbamate aqueous solution, acetic acid water and water, and then the washed organic layer was added to methanol, and the precipitated solid was filtered to recover as a crude polymer.

[0670] The obtained crude polymer was dissolved in tetralin and passed through a 5B (JIS P 3801: 5B) filter paper. Methanol was then added again and the precipitated solid was recovered by filtration to obtain a polymer G-002.

[0671] <Comparative Example 1>

[0672] [Chemistry 62]

[0673]

[0674] The added raw materials were compound 26 (1.6 mmol), compound 22 (1.488 mmol), water (47.6 g), 40% by mass potassium phosphate aqueous solution (5.8 mL), THF (37.3 mL), tetralin (16 mL), bis(tri-tert-butylphosphine)palladium (0) (0.02 mmol), and a mixed solution of phenylboric acid (1.6 mmol) and 40% by mass potassium phosphate aqueous solution (8.4 mL). Except for these, polymer G-006 was synthesized in the same manner as polymer G-002.

[0675] <Comparative Example 2>

[0676] [Chemistry 63]

[0677]

[0678] The added raw materials were compound 26 (1.6 mmol), compound 22 (0.744 mmol), compound 23 (0.744 mmol), water (41.6 g), 40% by mass potassium phosphate aqueous solution (5.0 mL), THF (37.3 mL), tetralin (16 mL), bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol), phenylboric acid (1.6 mmol) and 40% by mass potassium phosphate aqueous solution (8.4 mL). Except for these, polymer G-007 was synthesized in the same manner as polymer G-002.

[0679] <Comparative Example 3>

[0680] [Chemistry 64]

[0681]

[0682] The added raw materials were compound 26 (1.4 mmol), compound 22 (0.6545 mmol), compound 24 (0.6545 mmol), water (41.6 g), 40% by mass potassium phosphate aqueous solution (5.0 mL), THF (32.7 mL), tetralin (16 mL), bis(tri-tert-butylphosphine)palladium (0) (0.01 mmol), and a mixed solution of phenylboric acid (1.4 mmol) and 40% by mass potassium phosphate aqueous solution (7.4 mL). Except for this, polymer G-008 was synthesized in the same manner as polymer G-002.

[0683] <Example 2>

[0684] [Chemistry 65]

[0685]

[0686] The added raw materials were compound 26 (1.5 mmol), compound 22 (1.2555 mmol), compound 25 (0.1395 mmol), water (44.6 g), 40% by mass potassium phosphate aqueous solution (5.4 mL), THF (35 mL), tetralin (15 mL), bis(tri-tert-butylphosphine)palladium (0) (0.02 mmol), and a mixed solution of phenylboric acid (1.5 mmol) and 40% by mass potassium phosphate aqueous solution (7.9 mL). Except for this, polymer G-009 was synthesized in the same manner as polymer G-002.

[0687] <Example 3>

[0688] [Chemistry 66]

[0689]

[0690] The added raw materials were compound 26 (1.5 mmol), compound 22 (1.116 mmol), compound 25 (0.279 mmol), water (44.6 g), 40% by mass potassium phosphate aqueous solution (5.4 mL), THF (35 mL), tetralin (15 mL), bis(tri-tert-butylphosphine)palladium (0) (0.02 mmol), and a mixed solution of phenylboric acid (1.5 mmol) and 40% by mass potassium phosphate aqueous solution (7.9 mL). Except for this, polymer G-010 was synthesized in the same manner as polymer G-002.

[0691] <Example 4>

[0692] [Chemistry 67]

[0693]

[0694] The added raw materials were compound 26 (2.1 mmol), compound 4 (0.987 mmol), compound 23 (0.987 mmol), water (62.4 g), 40% by mass potassium phosphate aqueous solution (7.6 mL), THF (49 mL), tetralin (21 mL), bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol), and a mixed solution of phenylboric acid (2.1 mmol) and 40% by mass potassium phosphate aqueous solution (11.0 mL). Except for this, polymer G-019 was synthesized in the same manner as polymer G-002.

[0695] <Example 5>

[0696] [Chemistry 68]

[0697]

[0698] The added raw materials were compound 26 (2.3 mmol), compound 20 (1.081 mmol), compound 23 (1.081 mmol), water (68.4 g), 40% by mass potassium phosphate aqueous solution (8.3 mL), THF (53.7 mL), tetralin (23 mL), and bis(tri-tert-butylphosphine)palladium (0) (0.02 mmol), and a mixed solution of phenylboric acid (2.3 mmol) and 40% by mass potassium phosphate aqueous solution (12.1 mL). Except for this, polymer G-020 was synthesized in the same manner as polymer G-002.

[0699] <Example 6>

[0700] [Chemistry 69]

[0701]

[0702] The added raw materials were compound 26 (2.3 mmol), compound 20 (1.150 mmol), compound 23 (1.150 mmol), water (68.4 g), 40% by mass potassium phosphate aqueous solution (8.3 mL), THF (53.7 mL), tetralin (23 mL), bis(tri-tert-butylphosphine)palladium(0) (0.02 mmol), and a mixed solution of phenylboric acid (2.3 mmol) and 40% by mass potassium phosphate aqueous solution (12.1 mL). Except for this, polymer G-022 was synthesized in the same manner as polymer G-002.

[0703] <Comparative Example 4>

[0704] [Chemistry 70]

[0705]

[0706] The added raw materials were compound 26 (2.6 mmol), compound 13 (1.235 mmol), compound 23 (1.235 mmol), water (77.3 g), 40% by mass potassium phosphate aqueous solution (9.4 mL), THF (60.7 mL), tetralin (26 mL), bis(tri-tert-butylphosphine)palladium (0) (0.03 mmol), and a mixed solution of phenylboric acid (2.6 mmol) and 40% by mass potassium phosphate aqueous solution (13.7 mL). Except for this, polymer G-026 was synthesized in the same manner as polymer G-002.

[0707] <Example 7>

[0708] [Chemistry 71]

[0709]

[0710] The added raw materials were compound 26 (2.1 mmol), compound 17 (1.029 mmol), compound 23 (1.029 mmol), water (62.5 g), 40% by mass potassium phosphate aqueous solution (7.6 mL), THF (49 mL), tetralin (21 mL), bis(tri-tert-butylphosphine)palladium (0) (0.02 mmol), and a mixed solution of phenylboric acid (2.1 mmol) and 40% by mass potassium phosphate aqueous solution (11.0 mL). Except for this, polymer G-023 was synthesized in the same manner as polymer G-002.

[0711] <Example 8>

[0712] [Chemistry 72]

[0713]

[0714] The added raw materials were compound 26 (2.3 mmol), compound 7 (1.127 mmol), compound 23 (1.127 mmol), water (68.4 g), 40% by mass potassium phosphate aqueous solution (8.3 mL), THF (53.7 mL), tetralin (23 mL), bis(tri-tert-butylphosphine)palladium (0) (0.02 mmol), and a mixed solution of phenylboric acid (2.3 mmol) and 40% by mass potassium phosphate aqueous solution (12.1 mL). Except for this, polymer G-030 was synthesized in the same manner as polymer G-002.

[0715] <Example 9>

[0716] [Chemistry 73]

[0717]

[0718] The added raw materials were compound 26 (1.484 mmol), compound 7 (0.71246 mmol), compound 10 (0.71246 mmol), water (44.1 g), 40% by mass potassium phosphate aqueous solution (5.3 mL), THF (34.6 mL), tetralin (14.8 mL), bis(tri-tert-butylphosphine)palladium (0) (0.01 mmol), and a mixed solution of phenylboric acid (1.484 mmol) and 40% by mass potassium phosphate aqueous solution (7.8 mL). Except for this, polymer G-035 was synthesized in the same manner as polymer G-002.

[0719] <Comparative Example 5>

[0720] [Chemistry 74]

[0721]

[0722] The added raw materials were compound 26 (26.5 mmol), compound 23 (13.05 mmol), compound 24 (13.05 mmol), water (794 g), 40% by mass potassium phosphate aqueous solution (137 g), 1-methylcyclohexanol (410 g), tetralin (424 g), and a mixed solution of phenylboric acid (26.5 mmol) and 40% by mass potassium phosphate aqueous solution (129 mL). Except for these, polymer K-048 was synthesized in the same manner as polymer G-002.

[0723] (Structure of polymer obtained in each example)

[0724] The specific structure of the polymer obtained in each example is shown below.

[0725] [Table 3-1]

[0726]

[0727] [Table 3-2]

[0728]

[0729] <Production of ink and photoelectric conversion element>

[0730] Using the polymer obtained in each example, ink and a photoelectric conversion element were prepared according to the following procedures.

[0731] (Ink production)

[0732] 1,2,4-Trimethylbenzene and butyl benzoate were mixed in an amount of 97% by mass and 3% by mass, respectively, to obtain a mixture (a).

[0733] For the mixture (a), the polymer obtained in each example as a p-type semiconductor and an n-type semiconductor are mixed to obtain a mixture (b). As an n-type semiconductor material (electron accepting compound), the trade name "Guard Surf NC-1010" (manufactured by HARVES) is used. The mixing amount of the p-type semiconductor is 1.5% by mass relative to the total mass of the mixture (b). The mixing amount of the n-type semiconductor is 1.5% by mass relative to the total mass of the mixture (b). The obtained mixture (b) is stirred at 60°C for 8 hours and then filtered with a filter to obtain ink.

[0734] (Manufacturing of photoelectric conversion elements)

[0735] -Substrate Preparation-

[0736] A glass substrate (hereinafter referred to as a glass substrate) on which an ITO film having a thickness of 45 nm as a first electrode was formed by sputtering was prepared. Next, the glass substrate was subjected to a surface treatment using ozone ultraviolet (UV) treatment.

[0737] -Formation of active layer-

[0738] The ink was applied to the ITO film of the glass substrate by spin coating to form a coating. The glass substrate with the coating was placed on a hot plate and dried in the atmosphere at 70°C for 2 minutes. Next, the glass substrate with the coating was placed on a hot plate and further dried at 100°C for 10 minutes in a nitrogen atmosphere. Thus, an active layer was formed on the ITO film. The thickness of the formed active layer was about 250nm.

[0739] -Formation of electron transport layer-

[0740] A 45% by mass isopropanol dispersion of zinc oxide nanoparticles (particle size 20-30 nm) (Tayca, HTD-711Z) was diluted with 10 times the mass of 3-pentanol as the isopropanol dispersion to prepare a coating solution. The coating solution was applied to the active layer formed by spin coating at a thickness of 40 nm and heated at 70° C. for 5 minutes. Thus, an electron transport layer was formed on the active layer.

[0741] - Electrode formation -

[0742] Thereafter, a Ag film as an electrode (second electrode) was formed on the electron transport layer to a thickness of about 80 nm using a resistance heating vapor deposition apparatus.

[0743] - Formation of sealing layer -

[0744] Next, an ultraviolet (UV) curable sealant was applied around the glass substrate on which the electrode (second electrode) was formed, and then the glass plate was bonded to the top of the electrode, and then the sealant was cured by irradiation with UV light to seal the photoelectric conversion element. The shape of the obtained photoelectric conversion element was a 2 mm × 2 mm square.

[0745] By the above-described manufacturing method, a photoelectric conversion element is obtained in which a glass substrate, a first electrode, an active layer, an electron transport layer, and a second electrode are provided in this order.

[0746] <Evaluation>

[0747] (Measurement of dark current)

[0748] The photoelectric conversion element was subjected to JV measurement in a dark place to obtain a dark current (Jd) at -5 V. A source meter (2450 model, manufactured by Keithley) was used for the JV measurement. Hereinafter, the measured dark current value is also referred to as "measured dark current".

[0749] The measurement results are shown in Table 4, "Measured dark current".

[0750] (Dark current prediction)

[0751] A multiple regression analysis was performed with the target variable being "measured dark current" and the explanatory variables being "1000 / average formula weight of specific side chains" and "absorption limit strength of polymer". The multiple regression analysis was performed using the data analysis tool of Microsoft's spreadsheet software Excel. Multiple regression analysis was performed using all 14 data. The predicted value of the dark current was calculated using the coefficients obtained by the multiple regression analysis. Hereinafter, the value of the dark current predicted by the multiple regression analysis will also be referred to as "predicted dark current".

[0752] The prediction results are shown in Table 4, "Predicted Dark Current".

[0753] In addition, "1000 / specific side chain average formula weight" and "absorption edge strength of polymer" used as explanatory variables are as follows.

[0754] In addition, the "HOMO energy level" and "1240 / absorption edge wavelength" described in Table 4 are as follows.

[0755] HOMO energy level: refers to the energy level of the highest occupied molecular orbital (HOMO) of a polymer. The HOMO energy level is calculated as follows.

[0756] The polymer obtained in each example was added to a mixed solvent of 1,2,4-trimethylbenzene and 1,2-dimethoxybenzene (1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 97 / 3 (mass ratio)) in a concentration of 1.5% by weight. The polymer solution was prepared by heating and stirring at 65°C for 4 hours under a nitrogen atmosphere. The polymer solution was filtered with an RC filter (pore size 0.45μm, Minisart RC, hydrophilic, 15mm, manufacturer Sartorius), and the filtrate was used as a coating liquid. The coating liquid was placed on a glass substrate whose surface was cleaned with UV-ozone, and a film was formed by spin coating at a rotation speed to achieve a film thickness of 100nm. The glass substrate with the coating obtained by spin coating was placed on a hot plate and dried under the conditions of 70°C and 5 minutes in the atmosphere. Then, annealing was carried out under nitrogen at 100°C and 10 minutes to obtain a thin film for HOMO level measurement. The HOMO level was measured using AC-2 manufactured by Riken Keiki Co., Ltd.

[0757] 1000 / specific side chain average formula weight: a value calculated from the following formula.

[0758] Formula: 1000÷average formula weight of specific side chains of polymer

[0759] 1240 / absorption edge wavelength: a value calculated by the following formula.

[0760] Formula: 1240÷absorption limit wavelength

[0761] The procedure for measuring the absorption edge wavelength is described in (Measurement of the absorption edge intensity of a polymer) described later.

[0762] · Absorption edge intensity of a polymer: The absorption edge intensity of a polymer measured according to the procedure (Measurement of Absorption Edge Intensity of a Polymer) described later.

[0763] (Determination of the absorption limit strength of polymers)

[0764] The polymer obtained in each example was added to a mixed solvent of 1,2,4-trimethylbenzene and 1,2-dimethoxybenzene (1,2,4-trimethylbenzene / 1,2-dimethoxybenzene = 97 / 3 (mass ratio)) in a concentration of 1.5% by weight. The polymer solution was prepared by heating and stirring at 65°C for 4 hours under a nitrogen atmosphere. The polymer solution was filtered with an RC filter (pore size 0.45μm, Minisart RC, hydrophilic, 15mm, manufacturer Sartorius), and the filtrate was used as a coating liquid. The coating liquid was placed on a glass substrate whose surface was cleaned with UV-ozone, and a film was formed by spin coating at a rotation speed to achieve a film thickness of 100nm. The coating obtained by spin coating was placed on a hot plate and dried under the conditions of 70°C and 5 minutes in the atmosphere. Then, annealing was carried out under nitrogen at 100°C and 10 minutes to obtain a thin film for UV-Vis spectroscopy.

[0765] Using this film, the absorption edge intensity of the polymer was measured according to the procedure described in the above "· Measurement of the absorption edge intensity of the polymer". Figure 1 The wavelength at the intersection point C is taken as the absorption limit wavelength.

[0766] The absorption edge intensity was calculated by normalizing at the peak top of the spectrum and calculating it as a relative value with respect to the peak top.

[0767] (Determination of the absorption limit strength of the active layer)

[0768] The ink prepared in the above (Preparation of ink) was used as a coating liquid. The coating liquid was placed on a glass substrate whose surface was cleaned with UV-ozone, and a film was formed by spin coating at a rotation speed to achieve a film thickness of 100 nm. The coating film obtained by spin coating was placed on a hot plate and dried under the conditions of 70°C for 5 minutes in the atmosphere. Then, annealing was performed under nitrogen at 100°C for 10 minutes to obtain a thin film for UV-Vis spectrum measurement.

[0769] Using this thin film, the absorption edge intensity of the active layer was measured according to the procedure described in the above "Measurement of absorption edge intensity of film".

[0770]

[0771] The above results show that the polymers of Examples can suppress the dark current of the photoelectric conversion element.

[0772] In addition, the predicted dark current is plotted against the measured dark current, and the resulting determination coefficient R 2 The value is as high as 0.84 (ref. Figure 3 ). Thus, it can be seen that the specific side chain average weight and absorption limit strength of the polymer affect the suppression of dark current.

[0773] Explanation of symbols

[0774] 10 photoelectric conversion element, 11 supporting substrate, 12 first electrode, 13 first intermediate layer, 14 active layer, 15 intermediate layer, 16 second electrode, 17 sealing member

Claims

1. A polymer comprising a structural unit having a main chain and a side chain, wherein: The weighted average of the formula weights of the side chains weighted by the molar ratio of the structural units contained in the polymer is 160 or more, The absorption edge intensity is below 0.

08.

2. The polymer according to claim 1, wherein The side chain is at least one selected from the group consisting of an alkyl group which may have a substituent, an aryl group which may have a substituent, and a monovalent heterocyclic group which may have a substituent.

3. The polymer according to claim 1, comprising at least one selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (Y1), [Chemistry 1] [Chemistry 2] In formula (I), Z 1 is a divalent group, Ar 1 and Ar 2 each independently represents a trivalent aromatic hydrocarbon ring group or a trivalent heterocyclic group, In formula (Y1), Ar Y1 It represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are bonded to each other, and these groups may have a substituent. The polymer according to claim 3 , comprising two different structural units represented by formula (I).

5. The polymer according to claim 3, wherein In the structural unit represented by formula (I), Z 1 is a group represented by the following formula (Z-1), the following formula (Z-2), the following formula (Z-3), the following formula (Z-4), the following formula (Z-5), the following formula (Z-6) or the following formula (Z-7), [Chemistry 3] In formula (Z-1) to formula (Z-7), * indicates a bond, R 11 and R 12 Each independently represents a hydrogen atom or a monovalent group which may have a substituent, and may be the same or different.

6. The polymer according to claim 3, wherein The structural unit represented by formula (Y1) is a structural unit represented by the following formula (Y1-B5), the following formula (Y1-B6), the following formula (Y1-B7), the following formula (Y1-B8), the following formula (Y1-B9) or the following formula (Y1-B10), [Chemistry 4] In formula (Y1-B5) to formula (Y1-B10), X 1 and X 2 each independently represents a sulfur atom, an oxygen atom or a selenium atom, Y 1 and Y 2 Each independently represents a nitrogen atom or =CR 2b - the group shown, R 21 , R 22 and R 2b Each independently represents a hydrogen atom or a substituent.

7. The polymer according to claim 5, wherein In formula (Z-1) to formula (Z-7), R 11 and R 12 At least one of them is a group represented by the following formula (SC), [Chemistry 5] In formula (SC), m SCA1 represents an integer from 1 to 10. Ar SC1 represents an arylene group which may have a substituent, T SC It represents an aryl group which may have a substituent.

8. The polymer according to claim 3, wherein The structural unit represented by formula (I) is a structural unit represented by the following formula (I-8), [Chemistry 6] In formula (I-8), R 31 ~R 34 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an acyl group, an acyloxy group, an amide group, an imide group, an imino group, an amino group, a silyl group, a silyloxy group, a silylthio group, a silylamino group, a heterocyclic group, a heterocyclicoxy group, a heterocyclicthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group or a cyano group, and these groups may have a substituent.

9. The polymer according to claim 1, which has a weight average molecular weight of 6,000 or more.

10. A polymer comprising at least one selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (Y1), [Chemistry 7] [Chemistry 8] In formula (I), Z 1 is a group represented by the following formula (Z-1), the following formula (Z-2), the following formula (Z-3), the following formula (Z-4), the following formula (Z-5), the following formula (Z-6) or the following formula (Z-7), Ar 1 and Ar 2 each independently represents a trivalent aromatic hydrocarbon ring group or a trivalent heterocyclic group, In formula (Y1), Ar Y1 represents an arylene group, a divalent heterocyclic group, or a divalent group in which an arylene group and a divalent heterocyclic group are bonded together, In the groups represented by the following formulae (Z-1) to (Z-7), R 11 and R 12 At least one of them is a group represented by the following formula (SC), In formula (SC), m SCA1 represents an integer from 1 to 10, Ar SC1 represents an arylene group, T SC represents an aryl group, these groups may have a substituent or not, [Chemistry 9] [Chemistry 10] 11 . A film comprising the polymer according to claim 1 .

12. The film of claim 11, comprising an electron accepting compound. The film according to claim 12 , which has an absorption edge intensity of 0.17 or less. 14 . A composition comprising the polymer according to claim 1 and an electron-accepting compound. 15 . An ink comprising the polymer according to claim 1 and a solvent. 16 . An electronic component comprising the polymer according to claim 1 .

17. A photoelectric conversion element, comprising: 1st electrode; a second electrode; and an active layer disposed between the first electrode and the second electrode, The active layer contains the polymer according to any one of claims 1 to 10.

18. A solar cell module comprising the photoelectric conversion element according to claim 17. 19 . An image sensor comprising the photoelectric conversion element according to claim 17 .

Images