WO2024181311A1 - 化合物、組成物、膜、光電変換素子及びｃｍｏｓイメージセンサ - Google Patents

化合物、組成物、膜、光電変換素子及びｃｍｏｓイメージセンサ Download PDF

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WO2024181311A1
WO2024181311A1 PCT/JP2024/006586 JP2024006586W WO2024181311A1 WO 2024181311 A1 WO2024181311 A1 WO 2024181311A1 JP 2024006586 W JP2024006586 W JP 2024006586W WO 2024181311 A1 WO2024181311 A1 WO 2024181311A1
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compound
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alkyl group
photoelectric conversion
conversion element
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康生 宮田
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to EP24763791.1A priority Critical patent/EP4674853A1/en
Priority to CN202480011297.3A priority patent/CN120731210A/zh
Priority to JP2025503843A priority patent/JPWO2024181311A1/ja
Priority to KR1020257027927A priority patent/KR20250154383A/ko
Publication of WO2024181311A1 publication Critical patent/WO2024181311A1/ja
Priority to US19/309,756 priority patent/US20250393384A1/en
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    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
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    • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
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    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N25/00—Circuitry of solid-state image sensors [SSIS]; Control thereof
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the present invention relates to a compound, a composition, a film, a photoelectric conversion element, and a CMOS image sensor suitable as a semiconductor material for use in a photoelectric conversion element.
  • This application claims priority based on Japanese Patent Application No. 2023-31591 filed in Japan on March 2, 2023, Japanese Patent Application No. 2023-95405 filed in Japan on June 9, 2023, and Japanese Patent Application No. 2023-221244 filed in Japan on December 27, 2023. The contents of these applications are incorporated herein by reference.
  • CMOS image sensors equipped with photoelectric conversion elements are used as image pickup elements in digital cameras and smartphones, for example.
  • CMOS image sensors include inorganic CMOS image sensors and organic CMOS image sensors, with inorganic CMOS image sensors using silicon photodiodes being the most commonly used.
  • organic CMOS image sensors can achieve high resolution and a wide dynamic range by utilizing the high light absorption ability of organic thin films, while also being equipped with a global shutter that is less likely to distort images.As such, organic CMOS image sensors are believed to be able to solve the problem of achieving both a high dynamic range and a global shutter, which is difficult with inorganic CMOS image sensors, and therefore materials suitable for organic CMOS image sensors are in demand.
  • inorganic photoelectric conversion elements provided in inorganic CMOS image sensors
  • inexpensive silicon semiconductors are generally used for optical responses with absorption wavelengths up to 1000 nm, but when the absorption wavelength exceeds 1000 nm, very expensive indium gallium arsenide (InGaAs) semiconductors are used.
  • InGaAs indium gallium arsenide
  • a photoelectric conversion element (hereinafter also referred to as "organic photoelectric conversion element") provided in an organic CMOS image sensor, the photoelectric conversion ability and the absorption wavelength range can be controlled by molecular design of the p-type semiconductor material and the n-type semiconductor material used in the organic thin film (photoelectric conversion layer) constituting the photoelectric conversion element.
  • high light conversion ability has been reported in elements using non-fullerene acceptors as n-type semiconductor materials.
  • the role of controlling the absorption wavelength range is mainly played by the n-type semiconductor material.
  • n-type semiconductor materials light absorbing materials and electron transporting materials
  • compounds having an electron acceptor (A) moiety and an electron donor (D) moiety so-called ADA type compounds
  • the absorption wavelength of ADA type compounds can be designed by narrowing the HOMO-LUMO gap by selecting the electron-withdrawing property of the A moiety and the electron-donating property of the D moiety.
  • Non-Patent Document 1 discloses a compound represented by the following formula (a) which is an A-D'-D-D'-A type compound, a compound represented by the following formula (b) which is an A-D'-D-D''-A type compound, and a compound represented by the following formula (c) which is an A-D''-D-D''-A type compound.
  • Non-Patent Document 1 states that the compound represented by the following formula (a) is the most capable of achieving a long absorption wavelength.
  • the compound represented by the following formula (a) is a compound in which the alkyl group bonded to the thiophene ring in the D′′ portion of the compound represented by the following formula (b) or (c) is replaced with an alkoxy group, which is a strong electron-donating group, to form the D′ portion.
  • the present invention aims to provide a compound that can lengthen the absorption wavelength while suppressing the dark current of a photoelectric conversion element, and a composition, film, photoelectric conversion element, and CMOS image sensor that use this compound.
  • the present inventors have investigated compounds capable of shifting the absorption wavelength to a longer wavelength while suppressing the dark current of a photoelectric conversion element. Specifically, they have investigated substituents in the A portion of an A-D 1 -D-D 2 -A type compound as shown in Non-Patent Document 1. As a result, they have found that by substituting the terminal of the A portion with a cyano group, it is possible to shift the absorption wavelength to a longer wavelength while suppressing the dark current of a photoelectric conversion element, and have thus completed the present invention.
  • X 1 to X 8 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group, at least one of X 1 to X 8 is a cyano group, Y 1 to Y 4 are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, at least one of Y 1 to Y 4 is an alkyl group, an alkoxy group, or an ester group, Z 1 and Z 2 are each independently an oxygen atom or a dicyanomethylene group, and M is a carbon atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.
  • the present invention provides a compound that can lengthen the absorption wavelength while suppressing the dark current of a photoelectric conversion element, as well as a composition, film, photoelectric conversion element, and CMOS image sensor that use this compound.
  • FIG. 1 is a cross-sectional view illustrating a schematic example of an embodiment of a photoelectric conversion element of the present invention.
  • the compound of the present invention is a compound represented by the following general formula (1) (hereinafter, also referred to as “compound (1)”; the same applies hereinafter).
  • X 1 to X 8 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group, at least one of X 1 to X 8 is a cyano group, Y 1 to Y 4 are each independently a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, at least one of Y 1 to Y 4 is an alkyl group, an alkoxy group, or an ester group, Z 1 and Z 2 are each independently an oxygen atom or a dicyanomethylene group, and M is a carbon atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.
  • the terminal of the A portion of an AD 1 -DD 2 -A type compound is substituted with a cyano group, and therefore, the absorption wavelength can be shifted to a longer wavelength while suppressing the dark current of a photoelectric conversion element.
  • the reason why the compound of the present invention can shift the absorption wavelength to a longer wavelength while suppressing the dark current of the photoelectric conversion element is not clear, but is presumed to be as follows.
  • the compound of the present invention has a substituent on one atom in the center of the D part in the direction of extending above and below the ⁇ -conjugated plane, while the D 1 part and the D 2 part have a substituent extending in the same direction on the ⁇ -conjugated plane. Therefore, in the compound of the present invention, the substituents extending above and below the ⁇ -conjugated plane between molecules tend to slip and not overlap, forming a ⁇ -stack structure.
  • the compound of the present invention is considered to be a compound capable of having a densely packed structure.
  • the terminal of the A portion of the A-D 1 -D-D 2 -A type compound having a densely packed structure is substituted with a cyano group which is more likely to exhibit intermolecular interactions than conventional A-D 1 -D-D 2 -A type compounds.
  • the densely packed structure between the A-D 1 -D-D 2 -A type compounds is promoted even in the direction perpendicular to the lamellar structure (i.e., the long axis direction of the ⁇ -conjugated skeleton of the molecule), and charge separation between the n-type semiconductor material and the p-type semiconductor material under dark conditions can be suppressed.
  • the compound of the present invention is considered to be able to achieve both a longer absorption wavelength due to strong electron-withdrawing properties and suppression of an increase in dark current due to a densely packed structure by substituting the end of the A moiety with a cyano group in addition to a packed structure due to the characteristic direction of the substituent of the D 1 -D-D 2 moiety in the A-D 1 -D-D 2 -A type compound.
  • a cyano group is listed as a substituent that can be substituted at the A terminal, along with a fluorine atom and a chlorine atom.
  • X 1 to X 8 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group, and at least one of X 1 to X 8 is a cyano group. It is considered that the compound (1) can maintain and improve the electron-withdrawing property of the A part by having X 1 to X 8 be a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, or a cyano group.
  • X 1 to X 8 be a cyano group, in addition to the long wavelength of the absorption wavelength due to the strong electron-withdrawing property, the increase in the dark current due to the densely packed structure can be suppressed.
  • X 2 , X 3 , X 6 , and X 7 are preferably cyano groups from the viewpoint of further promoting the densely packed structure between the compounds.
  • X 1 , X 4 , X 5 , and X 8 are preferably hydrogen atoms from the viewpoint of ease of synthesis.
  • X 1 , X 4 , X 5 and X 8 in the compound (1) are hydrogen atoms, and X 2 , X 3 , X 6 and X 7 are cyano groups.
  • X 1 , X 4 , X 5 and X 8 of compound (1) are hydrogen atoms, and X 2 , X 3 , X 6 and X 7 are each independently a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom or a cyano group, and one to three, preferably two or three of X 2 , X 3 , X 6 and X 7 may be cyano groups.
  • the remaining of X 2 , X 3 , X 6 and X 7 are preferably hydrogen atoms, and it is more preferable that one or two of X 2 , X 3 , X 6 and X 7 are hydrogen atoms.
  • Y 1 to Y 4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an ester group, and at least one of Y 1 to Y 4 represents an alkyl group, an alkoxy group, or an ester group.
  • the number of carbon atoms of the alkyl group of Y 1 to Y 4 is preferably small in terms of the electrical conductivity of the material. Therefore, the number of carbon atoms of the alkyl group of Y 1 to Y 4 is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less.
  • the number of carbon atoms of the alkyl group of Y 1 to Y 4 is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 8 or more.
  • the above upper and lower limits can be combined arbitrarily. For example, it may be 2 to 30, 4 to 20, 6 to 15, or 8 to 10.
  • the alkyl groups of Y 1 to Y 4 may be chain-like or cyclic. When the alkyl group is chain-like, it may be linear or branched. In terms of ease of synthesis, it is preferable that the alkyl group is a linear or branched alkyl group in which the carbon atom bonded to the thiophene ring is a primary carbon atom.
  • the alkyl group is a branched alkyl group in which the carbon atom bonded to the thiophene ring is a primary carbon atom, or a linear, branched or cyclic alkyl group in which the carbon atom bonded to the thiophene ring is a secondary carbon atom.
  • the alkyl group is a branched alkyl group in which the carbon atom bonded to the thiophene ring is a primary carbon atom.
  • the number of carbon atoms of the alkoxy groups Y 1 to Y 4 is preferably small in terms of the electrical conductivity of the material. Therefore, the number of carbon atoms of the alkoxy groups Y 1 to Y 4 is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less. In addition, the number of carbon atoms of the alkoxy groups Y 1 to Y 4 is preferably 2 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 8 or more.
  • the above upper and lower limits can be combined arbitrarily. For example, it may be 2 to 30, 4 to 20, 6 to 15, or 8 to 10.
  • An alkoxy group is a structure in which an alkyl group is bonded to an oxygen atom, and the alkyl group bonded to the oxygen atom may be either linear or cyclic. When the alkyl group bonded to the oxygen atom is linear, it may be either linear or branched. In terms of ease of synthesis, it is preferable that the carbon atom bonded to the oxygen atom is a primary carbon atom, and a linear or branched alkyl group is preferably used.
  • the carbon atom bonded to the oxygen atom is a primary carbon atom, and a linear, branched or cyclic alkyl group is preferably used, and the carbon atom bonded to the oxygen atom is a secondary carbon atom, and it is more preferable that the carbon atom bonded to the oxygen atom is a secondary carbon atom, and it is even more preferable that the linear or branched alkyl group is a secondary carbon atom, and it is even more preferable that the carbon atom bonded to the oxygen atom is a secondary carbon atom.
  • the ester group of Y 1 to Y 4 includes a monovalent group having an ester bond, specifically, a group represented by the following general formula (i). -COO-R 1 ...(i)
  • R 1 is an alkyl group or an aryl group.
  • the number of carbon atoms in the alkyl group of R 1 is preferably small in terms of the electrical conductivity of the material. Therefore, the number of carbon atoms in the alkyl group of R 1 is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 10 or less.
  • the number of carbon atoms in the alkyl group of R 1 is preferably 1 or more, more preferably 4 or more, even more preferably 6 or more, and particularly preferably 8 or more.
  • the above upper and lower limits can be combined arbitrarily. For example, it may be 2 to 30, 4 to 20, 6 to 15, or 8 to 10.
  • the alkyl group of R1 may be chain-like or cyclic. When the alkyl group is chain-like, it may be linear or branched. In terms of ease of synthesis, it is preferable that the carbon atom bonded to the oxygen atom is a primary carbon atom, and that the alkyl group is a linear or branched alkyl group.
  • the carbon atom bonded to the oxygen atom is a primary carbon atom, and that the alkyl group is a linear, branched or cyclic alkyl group, and that the carbon atom bonded to the oxygen atom is a secondary carbon atom, and it is more preferable that the carbon atom bonded to the oxygen atom is a secondary carbon atom, and it is even more preferable that the alkyl group is a linear or branched alkyl group, and that the carbon atom bonded to the oxygen atom is a secondary carbon atom.
  • the number of carbon atoms in the aryl group of R 1 is preferably small in terms of the electrical conductivity of the material. Therefore, the number of carbon atoms in the aryl group of R 1 is preferably 18 or less, more preferably 12 or less, even more preferably 10 or less, and particularly preferably 6.
  • the lower limit of the number of carbon atoms in the aryl group of R 1 is 6. For example, it may be 6 to 18, 6 to 12, 6 to 10, or 6.
  • the aryl group of R 1 may or may not have a substituent. That is, the aryl group of R 1 is an unsubstituted or substituted aryl group. Examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, and an amino group.
  • Y 1 to Y 4 may be the same or different.
  • one of Y 1 and Y 3 is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group
  • one of Y 2 and Y 4 is a hydrogen atom and the other is an alkyl group, an alkoxy group, or an ester group.
  • Y1 to Y4 are symmetrical with respect to M, that is, Y1 and Y2 are the same, and it is preferable that Y3 and Y4 are the same.
  • Y3 and Y4 are hydrogen atoms and Y1 and Y2 are alkyl groups, alkoxy groups, or ester groups, and it is even more preferable that Y3 and Y4 are hydrogen atoms and Y1 and Y2 are alkoxy groups.
  • Y1 to Y4 are asymmetric with respect to M, that is, Y2 and Y3 are hydrogen atoms and Y1 and Y4 are each independently an alkyl group, an alkoxy group, or an ester group, more preferably Y2 and Y3 are hydrogen atoms and Y1 and Y4 are each independently an alkyl group or an alkoxy group, and further preferably Y2 and Y3 are hydrogen atoms and one of Y1 and Y4 is an alkyl group and the other is an alkoxy group.
  • Z 1 and Z 2 each independently represent an oxygen atom or a dicyanomethylene group.
  • Z 1 and Z 2 are oxygen atoms or dicyanomethylene groups, and therefore can be electron-withdrawing groups in the acceptor portion.
  • M is a carbon atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group. It is considered that the solubility of the compound (1) can be increased by M being a carbon atom substituted with an alkyl group or an aryl group, a silicon atom substituted with an alkyl group or an aryl group, or a germanium atom substituted with an alkyl group or an aryl group.
  • a carbon atom substituted with an alkyl group or an aryl group is represented by the following general formula (ii):
  • a silicon atom substituted with an alkyl group or an aryl group is represented by the following general formula (iii):
  • a germanium atom substituted with an alkyl group or an aryl group is represented by the following general formula (iv):
  • R 2 to R 7 each independently represent an alkyl group or an aryl group.
  • the alkyl group of R 2 to R 7 include the alkyl group of R 1 exemplified above in the explanation of Y 1 to Y 4 .
  • the aryl group for R 2 to R 7 include the aryl group for R 1 given above in the description of Y 1 to Y 4 .
  • M is preferably a carbon atom substituted with an alkyl group or an aryl group, and more preferably a carbon atom substituted with an alkyl group.
  • the compound (1) is preferably a compound in which X1 , X4 , X5 , and X8 in general formula (1) are hydrogen atoms, X2 , X3 , X6 , and X7 are cyano groups, Y2 and Y3 are hydrogen atoms, Y1 and Y4 are each independently an alkyl group or an alkoxy group, Z1 and Z2 are dicyanomethylene groups, and M is a carbon atom substituted with an alkyl group.
  • compound (1) examples include compounds represented by the following formulas (1-1) to (1-60), but compound (1) is not limited thereto.
  • a compound represented by the following formula (1-1) is also referred to as "compound (1-1).”
  • those in which at least one of Y 1 to Y 4 is an alkoxy group, in which the alkyl group bonded to the oxygen atom in the alkoxy group is linear, branched, or cyclic, and the carbon atom bonded to the oxygen atom is a secondary carbon atom i.e., a compound in which the alkoxy group bonded to the thiophene ring is branched at position 1
  • examples of such compounds include compounds (1-28) to (1-60).
  • Y in compound (A) corresponds to any one of Y1 to Y4 in compound (1)
  • Z in compound (A) corresponds to Z1 or Z2 in compound (1).
  • compound (B) of the following formula is reacted with lithium diisopropylamide (LDA) in a reaction solvent, and then N,N-dimethylformamide is further reacted to obtain compound (C) of the following formula.
  • LDA lithium diisopropylamide
  • the compound (B) may be synthesized by a known method, or a commercially available product may be used.
  • the ratio of the raw materials is preferably 0.9 to 1.5 equivalents of LDA and 0.9 equivalents or more of N,N-dimethylformamide relative to compound (B).
  • N-formylpiperidine may be used instead of N,N-dimethylformamide.
  • the reaction solvent is not particularly limited as long as it is a solvent that does not react with the raw material compounds, and examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene.
  • the reaction temperature is preferably from -78 to 50°C.
  • the reaction time is preferably 10 minutes to 12 hours after the addition of LDA, and 10 minutes to 12 hours after the addition of N,N-dimethylformamide.
  • compound (E) of the following formula may be used instead of compound (C).
  • Compound (E) can be obtained, for example, as follows.
  • the 3-substituted thiophene may be synthesized by a known method, or a commercially available product may be used.
  • the ratio of the raw materials to be charged is preferably 0.9 to 1.5 equivalents of LDA and 0.9 or more equivalents of 1,2-dibromo-1,1,2,2-tetrachloroethane relative to the 3-substituted thiophene.
  • the reaction solvent is not particularly limited as long as it is a solvent that does not react with the raw material compounds, and examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene.
  • the reaction temperature is preferably from -78 to 50°C.
  • the reaction time is preferably from 10 minutes to 12 hours after the addition of LDA, and from 10 minutes to 12 hours after the addition of 1,2-dibromo-1,1,2,2-tetrachloroethane.
  • compound (D) is reacted with lithium diisopropylamide (LDA) in a reaction solvent, and then further reacted with N,N-dimethylformamide to obtain compound (E) of the following formula.
  • LDA lithium diisopropylamide
  • the ratio of the raw materials is preferably 0.9 to 1.5 equivalents of LDA and 0.9 equivalents or more of N,N-dimethylformamide relative to compound (D).
  • N-formylpiperidine may be used instead of N,N-dimethylformamide.
  • the reaction solvent is not particularly limited as long as it is a solvent that does not react with the raw material compounds, and examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as tetrahydrofuran (THF), diethyl ether, cyclopentyl methyl ether, and methyl t-butyl ether; and aromatic hydrocarbon solvents such as toluene and xylene.
  • the reaction temperature is preferably from -78 to 50°C.
  • the reaction time is preferably 10 minutes to 12 hours after the addition of LDA, and 10 minutes to 12 hours after the addition of N,N-dimethylformamide.
  • compound (C) and compound (E) is subjected to a cross-coupling reaction with compound (F) of the following formula in a reaction solvent to obtain compound (G) of the following formula.
  • the method for producing compound (G) is not particularly limited, but for example, Adv. Energy Mater., 2018, Vol. 8, p. 1801212.; J. Mater. Chem. C, 2020, Vol. 8, p. 15175.; ACS Energy Lett., 2019, Vol. 4, p. 1401.
  • Compound (G) can be produced by a method similar to that described in such literature. An example of a specific production condition is as follows.
  • compound (F) may be synthesized by a known method (e.g., Polym. Chem., 2013, Vol. 4, p. 5351-5360; J. Phys. Chem. C, 2011, Vol. 15, p. 2398-2405; Chem. Commun., 2012, Vol. 48, p. 11130-11132), or a commercially available product may be used.
  • compound (F) (wherein "L” in compound (F) is an alkyltin group, boric acid, a borate ester group, a zinc halide, a magnesium halide, or a silyl group, etc.) corresponding to the cross-coupling reaction may be used.
  • the type of cross-coupling reaction between at least one of compound (C) and compound (E) and compound (F) is not particularly limited, and the reaction can be carried out by Stille coupling, Suzuki coupling, Negishi coupling, Kumada coupling, Hiyama coupling, etc.
  • the cross-coupling reaction may be carried out in the presence of a catalyst such as a palladium catalyst, a nickel catalyst, a copper catalyst, etc.
  • a catalyst such as a palladium catalyst, a nickel catalyst, a copper catalyst, etc.
  • the raw material charge ratio is preferably 0.9 to 1.1 equivalents of compound (C) and compound (E) relative to compound (F).
  • a palladium catalyst in the Stille coupling reaction, and the content of palladium in the catalyst is preferably 0.1 to 50 mol%.
  • the reaction solvent is not particularly limited as long as it is a solvent that does not react with the raw material compounds, and examples thereof include saturated aliphatic hydrocarbon solvents such as hexane; ether solvents such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), 1,4-dioxane, etc.; aromatic hydrocarbon solvents such as toluene and xylene; N,N-dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone, etc.
  • the reaction temperature is preferably from 20° C. to the reflux temperature of the reaction solvent.
  • the reaction time is preferably from 1 to 24 hours.
  • compound (G) is reacted with compound (I) in a reaction solvent in the presence of an acid catalyst to obtain compound (A).
  • the method for producing compound (A) is not particularly limited, but for example, compound (A) can be produced by a method similar to the methods described in JP-A-2022-511781 and JP-A-2023-500815.
  • An example of specific production conditions is as follows.
  • compound (I) can be synthesized by a known method (for example, JP-A-2022-511781 and JP-A-2023-500815).
  • An example of the acid catalyst is p-toluenesulfonic acid hydrate (PTSA.H 2 O).
  • the ratio of the raw materials is preferably 1.9 to 10 equivalents of compound (I) relative to compound (G), and 2.1 to 11 equivalents of p-toluenesulfonic acid hydrate.
  • the reaction solvent is not particularly limited as long as it does not react with the raw material compounds.
  • an alcohol solvent such as methanol or ethanol may be mixed with an aromatic hydrocarbon solvent such as toluene or xylene.
  • the reaction temperature is preferably from room temperature to reflux temperature.
  • the reaction time is preferably from 1 to 6 hours.
  • compound (A) can be produced, in which Y in compound (A) is any one of Y 1 to Y 4 in compound (1), and Z in compound (A) is Z 1 or Z 2 in compound (1).
  • the compound of the present invention is suitable as an n-type semiconductor material (light absorbing material and electron transporting material) for use in a photoelectric conversion element, since it can shift the absorption wavelength to a longer wavelength while suppressing the dark current of the photoelectric conversion element.
  • the uses of the compound of the present invention are not limited to those described above.
  • the compound of the present invention since it has excellent luminescence properties, it can also be used in bioimaging, organic electroluminescence, and near-infrared luminescent dyes for wavelength conversion films and compositions.
  • composition of the present invention contains the above-mentioned compound (1).
  • the compound (1) may be used alone or in any combination of two or more kinds in any ratio.
  • the content of compound (1) in the composition of the present invention is not particularly limited. However, when the composition of the present invention is used for forming a photoelectric conversion layer (active layer) of a photoelectric conversion element, the content of compound (1) is preferably high in terms of light absorption, and on the other hand, it is preferable that the content of compound (1) is low in terms of carrier balance. Therefore, the content of compound (1) is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more, relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention.
  • the content of compound (1) is preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 75% by mass or less, and particularly preferably 60% by mass or less, relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention.
  • the upper and lower limits above can be arbitrarily combined. For example, it may be 10 to 100% by mass, 10 to 90% by mass, 25 to 75% by mass, or 40 to 60% by mass.
  • the composition of the present invention may further contain a solvent.
  • the composition containing the compound (1) and a solvent is suitable as an ink (composition for forming an active layer) for forming a photoelectric conversion layer (active layer) of a photoelectric conversion element.
  • the solvent is preferably a liquid that does not react with compound (1) and dissolves compound (1), and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; and halogenated solvents such as dichloromethane and chloroform.
  • the solvent may be used alone or in any combination of two or more kinds in any ratio.
  • the content of compound (1) in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on the total mass of the composition of the present invention.
  • the content of compound (1) is preferably 5% by mass or less, more preferably 3.5% by mass or less, and even more preferably 2% by mass or less, based on the total mass of the composition of the present invention.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 0.1 to 5% by mass, 0.5 to 3.5% by mass, or 1 to 2% by mass.
  • the composition of the present invention when used as a composition for forming an active layer, the composition preferably further contains a p-type semiconductor material in addition to compound (1).
  • the p-type semiconductor material is not particularly limited as long as it is used in the photoelectric conversion layer of the organic photoelectric conversion element, and examples thereof include polymers described in the literature (ACS Energy Lett., 2019, Vol. 4, p. 1401. and Adv. Optical Mater., 2022, Vol. 10, p. 2200747.).
  • the composition of the present invention contains a p-type semiconductor material
  • the p-type semiconductor material may be used alone or in any combination of two or more kinds in any ratio.
  • the mass ratio of compound (1) to the p-type semiconductor material is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 0.75 or more.
  • the mass ratio of compound (1) to the p-type semiconductor material is preferably 3 or less, more preferably 2 or less, and even more preferably 1.5 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it may be 0.1 to 3, 0.5 to 2, or 0.75 to 1.5.
  • composition of the present invention may further contain components (optional components) other than compound (1), a p-type semiconductor material, and a solvent, as necessary, within a range that does not impair the effects of the present invention.
  • Optional components include, for example, 1,8-diiodooctane and 1-chloronaphthalene.
  • the optional components may be used alone or in any combination of two or more kinds in any ratio.
  • the composition of the present invention contains an optional component, it is preferable that the content of the optional component is large in terms of the ease of manifesting the effect of the optional component.
  • the content of compound (1) is large in terms of the ease of maintaining the physical properties suitable for the composition of the present invention as a photoelectric conversion element. Therefore, when the composition of the present invention contains an optional component, the content of the optional component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, based on the total amount (total mass) of all components other than the solvent in the composition of the present invention. In addition, the content of the optional component is preferably 2% by mass or less, more preferably 1% by mass or less, based on the total amount (total mass) of all components other than the solvent in the composition of the present invention. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.1 to 2% by mass, or 0.3 to 1% by mass.
  • composition of the present invention can be obtained, for example, by dissolving compound (1) and, if necessary, one or more of the p-type semiconductor material and optional components in a solvent. In addition, by removing the solvent from the obtained composition, a solvent-free composition of the present invention can be obtained.
  • composition of the present invention is suitable as an ink (composition for forming an active layer) for forming a photoelectric conversion layer (active layer) of a photoelectric conversion element.
  • the film of the present invention is a film containing the above-mentioned compound (1), and is also called an organic thin film.
  • the film of the present invention can be obtained, for example, by removing the solvent from the above-mentioned solvent-containing composition of the present invention. Specifically, the film can be obtained by applying the solvent-containing composition of the present invention onto a substrate and then drying it.
  • the content of compound (1) in the film is the same as the content of compound (1) relative to the total amount (total mass) of all components other than the solvent in the composition of the present invention described above. That is, the content of compound (1) is preferably 10% by mass or more, more preferably 25% by mass or more, and even more preferably 40% by mass or more, relative to the total mass of the film.
  • the content of compound (1) is preferably 100% by mass or less, more preferably 90% by mass or less, even more preferably 75% by mass or less, and particularly preferably 60% by mass or less, relative to the total mass of the film.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 10 to 100% by mass, may be 10 to 90% by mass, may be 25 to 75% by mass, or may be 40 to 60% by mass.
  • the film thickness is preferably thick in terms of the amount of light absorption.
  • the film thickness is preferably thin. Therefore, the film thickness is preferably 10 nm or more, and more preferably 100 nm or more.
  • the film thickness is preferably 2000 nm or less, and more preferably 1000 nm or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it may be 10 to 2000 nm, or 100 to 1000 nm.
  • the film thickness can be adjusted by the amount of the composition applied to the substrate.
  • the method for applying the composition is not particularly limited, but examples thereof include brush coating, bar coating, spray coating, dip coating, spin coating, and curtain coating.
  • the drying temperature after coating is preferably from 20 to 250°C.
  • the drying time is preferably from 10 minutes to 5 hours.
  • the film of the present invention is suitable as a photoelectric conversion layer (active layer) of a photoelectric conversion element.
  • the photoelectric conversion element of the present invention is an element including the above-mentioned film of the present invention, and is also called an organic photoelectric conversion element.
  • the photoelectric conversion element of the present invention includes the film of the present invention as a photoelectric conversion layer (active layer).
  • the structure of the photoelectric conversion element can be that of a known organic photoelectric conversion element.
  • JP 2007-324587 A can be referred to.
  • the specific structure is not particularly limited, but an example thereof is an element having a laminated structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes.
  • a photoelectric conversion element 10 shown in FIG. 1 has a structure in which a transparent electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a metal electrode 16 are laminated in this order on a transparent substrate 11.
  • the positions of the hole transport layer 13 and the electron transport layer 15 may be interchanged. That is, the photoelectric conversion element may have a structure in which a transparent electrode, an electron transport layer, a photoelectric conversion layer (active layer), a hole transport layer, and a metal electrode are laminated in this order on a transparent substrate.
  • the transparent substrate 11 may be a base material having an average transmittance of 80% or more for visible light of 450 nm or more.
  • materials for forming the transparent substrate 11 include glass and plastics such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyethylene sulfide.
  • the transparent electrode 12 may be an electrode having an average transmittance of 80% or more for visible light of 450 nm or more.
  • the material for forming the transparent electrode 12 is not particularly limited as long as it can form the transparent electrode 12, but examples thereof include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc aluminum oxide (AZO), indium oxide (In 2 O 3 ), zinc oxide (ZnO), and titanium oxide (TiO 2 ).
  • the metal electrode 16 is an electrode that forms a pair with the transparent electrode 12 .
  • the material constituting the metal electrode 16 is not particularly limited, but examples thereof include metals such as gold, platinum, silver, aluminum, nickel, titanium, magnesium, calcium, barium, sodium, chromium, copper, and cobalt, or alloys thereof.
  • the metal electrode 16 is preferably a transparent electrode or a reflective electrode. That is, the photoelectric conversion element preferably has a laminated structure in which a photoelectric conversion layer (active layer) is sandwiched between a pair of electrodes (transparent or metal), and more preferably has a laminated structure in which an electron transport layer, a photoelectric conversion layer (active layer), and a hole transport layer are sandwiched between a pair of electrodes (transparent or metal).
  • the materials forming the electrodes may be the same or different.
  • the thickness of the metal electrode 16 is not particularly limited, but is preferably about 10 nm from the viewpoint of enhancing transparency. If transparency is not required, the thickness is preferably 40 nm or more, and more preferably 100 nm or more, taking durability into consideration, for example.
  • the method for forming the transparent electrode 12 and the metal electrode 16 is not particularly limited, but they can be formed, for example, by a dry process such as vacuum deposition or sputtering; or a wet process using conductive ink, etc.
  • the photoelectric conversion layer 14 is a layer that absorbs light and separates charges.
  • the photoelectric conversion layer 14 of the photoelectric conversion element of the present invention is a layer containing the above-mentioned compound (1) of the present invention. More specifically, it is the above-mentioned film of the present invention.
  • the photoelectric conversion layer 14 can be formed, for example, by applying the above-described composition of the present invention onto a layer that will be underneath the photoelectric conversion layer 14, such as the hole transport layer 13, and drying the composition.
  • the photoelectric conversion element 10 can be obtained, for example, by forming a transparent electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a metal electrode 16 in this order on a transparent substrate 11.
  • the photoelectric conversion element of the present invention contains compound (1) in the photoelectric conversion layer 14, so that the absorption wavelength can be extended while suppressing dark current, and the sensor has high sensitivity on the long wavelength side.
  • the CMOS image sensor of the present invention includes the above-mentioned photoelectric conversion element of the present invention.
  • the structure of the CMOS image sensor can adopt the structure of a known CMOS image sensor. Specifically, for example, JP 2021-57422 A can be referred to, and is not particularly limited. More specifically, a CMOS image sensor having a structure in which metal wiring, the photoelectric conversion element of the present invention, a color filter, and a microlens are stacked in this order on a substrate such as a silicon substrate can be mentioned.
  • the compound (I-1) of the following formula was synthesized by the method described in JP-A-2023-500815.
  • 0.070 g (0.08 mmol) of compound (G-3) and 0.10 g (0.40 mmol) of compound (I-1) were placed in a reaction vessel, and 6.0 mL of toluene and 8 mL of ethanol were added to dissolve the compound.
  • 0.120 g (0.60 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 65° C. for 3 hours. After cooling, an aqueous sodium hydrogen carbonate solution was added. The organic layer was extracted by a separation operation, and the extract was dried with sodium sulfate.
  • a compound (F-1) of the following formula was synthesized by a method described in a known literature (Macromolecules, 2007, Vol. 40, p. 1981.). With reference to the method described in JP 2022-030124 A, 1.46 g (2.0 mmol) of compound (F-1) was reacted with 1.35 g (4.2 mmol) of compound (C-2). After that, the solvent was removed under reduced pressure, and the mixture was purified by silica gel column chromatography to obtain a compound (yield 85%). The obtained compound was confirmed to be compound (G-4) by 1 H-NMR analysis. The 1 H-NMR measurement data is shown below.
  • the compound (I-1) of the following formula was synthesized by the method described in JP-A-2023-500815.
  • 0.294 g (0.33 mmol) of compound (G-4) and 0.408 g (1.67 mmol) of compound (I-1) were placed in a reaction vessel, and 8.2 mL of toluene and 16.3 mL of ethanol were added to dissolve the mixture.
  • 0.477 g (2.51 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 65° C. for 2 hours. After cooling, the organic layer was extracted with ethyl acetate and water, and the extract was dried over sodium sulfate.
  • Example 1 ⁇ Production of photoelectric conversion element> (Formation of Hole Transport Layer)
  • ITO indium tin oxide
  • a surface of an ITO substrate having a transparent conductive film of indium tin oxide (ITO) formed as a transparent electrode on a glass substrate was subjected to ozone treatment for 10 minutes using an ultraviolet ozone cleaner (manufactured by Japan Laser Electronics Co., Ltd., product name "NL-UV253").
  • an ultraviolet ozone cleaner manufactured by Japan Laser Electronics Co., Ltd., product name "NL-UV253”
  • 60 mg of a polytriarylamine compound (hole transporting polymer) represented by the following formula (H-1) was dissolved in 1 mL of anisole to prepare a composition for forming a hole transport layer.
  • the composition for forming a hole transport layer was spin-coated on the transparent electrode of the ozone-treated ITO substrate at 1000 rpm for 60 seconds and dried by heating at 240° C. for 30 minutes to form a hole transport layer with a thickness of 300 nm.
  • a compound represented by the following formula (P-1) weight average molecular weight: 80,000
  • the compound (1-2) was used.
  • 0.11 g of p-type semiconductor material and 0.13 g of n-type semiconductor material were dissolved in 9.68 mL of o-xylene to prepare an active layer forming composition, which is an organic semiconductor ink.
  • the mass ratio of the n-type semiconductor material to the p-type semiconductor material was 1.2.
  • the solid content concentration of the active layer forming composition was 25 mg/mL.
  • the obtained composition for forming an active layer was spin-coated onto the hole transport layer at 1000 rpm, and then heat-treated (thermal annealing treatment) at 120° C. for 10 minutes to form a photoelectric conversion layer (active layer) made of an organic thin film having a thickness of 150 nm.
  • C60 fullerene manufactured by Frontier Carbon Corporation
  • aluminum was deposited as a metal electrode material on the electron transport layer in a vacuum to form a metal electrode having a thickness of 100 nm, thereby obtaining a photoelectric conversion element.
  • the obtained photoelectric conversion element was evaluated as follows.
  • Example 2 A photoelectric conversion element was produced in the same manner as in Example 1, except that compound (1-28) was used as the n-type semiconductor material, and the external quantum efficiency was measured when a voltage of -5 V was applied.
  • the results of the external quantum efficiency at a wavelength of 1100 nm are shown in Table 1.
  • the values shown in Table 1 are relative values (relative EQE values) when the external quantum efficiency at a wavelength of 1100 nm in the photoelectric conversion element obtained in Comparative Example 1 described later is taken as 1.0.
  • the dark current of the obtained photoelectric conversion element was measured when ⁇ 5 V was applied in the same manner as in Example 1.
  • the results are shown in Table 1.
  • the values shown in Table 1 are relative values (relative dark current values) when the dark current of the photoelectric conversion element obtained in Comparative Example 1 described later is taken as 1.00.
  • Example 1 A photoelectric conversion element was produced in the same manner as in Example 1, except that a compound represented by the following formula (N-1) was used as the n-type semiconductor material, and the external quantum efficiency when ⁇ 5 V was applied and the dark current when ⁇ 5 V was applied were measured.
  • the photoelectric conversion elements obtained in Examples 1 and 2 had significantly higher EQE at 1100 nm, 2.7 times or 2.4 times, than the photoelectric conversion element obtained in Comparative Example 1, and had higher sensor sensitivity on the longer wavelength side. Furthermore, the photoelectric conversion elements obtained in Examples 1 and 2 had lower dark current, 0.28 times or 0.18 times, than the photoelectric conversion element obtained in Comparative Example 1, and had significantly smaller noise. These results demonstrate that the compound (1) of the present invention can achieve both high sensor sensitivity and low dark current reduction in the long-wavelength region of absorption wavelength.
  • Example 3 A photoelectric conversion element was produced in the same manner as in Example 1, except that compound (1-5) was used as the n-type semiconductor material, and the external quantum efficiency was measured when ⁇ 5 V was applied.
  • the results of the external quantum efficiency at a wavelength of 940 nm are shown in Table 2.
  • the values shown in Table 2 are relative values (relative EQE values) when the external quantum efficiency at a wavelength of 940 nm in the photoelectric conversion element obtained in Comparative Example 2 described below is taken as 1.0.
  • the dark current of the obtained photoelectric conversion element was measured when ⁇ 5 V was applied in the same manner as in Example 1.
  • the results are shown in Table 2.
  • the values shown in Table 2 are relative values (relative dark current values) when the dark current of the photoelectric conversion element obtained in Comparative Example 2 described later is taken as 1.00.
  • Example 2 A photoelectric conversion element was produced in the same manner as in Example 1, except that the compound (N-2) was used as the n-type semiconductor material, and the external quantum efficiency when ⁇ 5 V was applied and the dark current when ⁇ 5 V was applied were measured.
  • the photoelectric conversion element obtained in Example 3 had a significantly higher EQE at 940 nm of 1.1 times that of the photoelectric conversion element obtained in Comparative Example 2, and had a higher sensor sensitivity on the longer wavelength side.
  • the photoelectric conversion element obtained in Example 3 had a lower dark current of 0.80 times that of the photoelectric conversion element obtained in Comparative Example 2, and had significantly smaller noise.
  • the compound of the present invention can suppress the dark current of a photoelectric conversion element while shifting the absorption wavelength to a longer wavelength, and is useful as a semiconductor material for use in the photoelectric conversion element.

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