Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • 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
  • C07D495/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• the present invention relates to compounds that are useful as organic optical semiconductors.
• Organic optical semiconductors are used in optoelectronic devices such as organic solar cells (OSCs) and organic photodetectors (OPDs), and various p-type materials (donor materials) and n-type materials (acceptor materials) are used.
• OSCs organic solar cells
• OPDs organic photodetectors
• various p-type materials (donor materials) and n-type materials (acceptor materials) are used.
• narrow band gap n-type small molecule materials have been attracting attention in the field of infrared optoelectronic devices, and COI-4Cl, COTIC-4F, and other non-fullerene type acceptor materials are known (Patent Documents 1 and 2, etc.).
• the present invention has been made in view of the above-mentioned circumstances, and has an object to achieve at least one of the following: increasing the infrared absorption wavelength, improving the external quantum efficiency, reducing the dark current Id , and improving the ON/OFF ratio of photodetection.
• the present inventors have adopted a new compound having a specific structure as a non-fullerene acceptor material, thereby achieving at least one of the following: longer infrared absorption wavelength, improved external quantum efficiency, reduced dark current Id , and improved ON/OFF ratio of photodetection, thereby completing the present invention.
• a compound represented by formula (1) (In the formula, X1 is a carbon atom or a silicon atom. A1 is a benzene ring which may have a substituent or a thiophene ring which may have a substituent. R1 is C(CN) 2 or O. However, when A1 is a benzene ring which may have a substituent, R1 is C(CN) 2 . A2 is a benzene ring which may have a substituent. R11 , R12 , R21 , and R22 each independently represent an alkyl group having 6 to 30 carbon atoms.
• R31 and R32 each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.
• n1 and n2 each independently represent 0 or 1.
• An organic thin film comprising the compound according to [1] or [2] above.
• An organic photodetector having the organic thin film according to [3] above in a light receiving section.
• At least one of the following can be achieved: longer infrared absorption wavelength, improved external quantum efficiency, reduced dark current Id , and improved ON/OFF ratio of photodetection.
• Compound The compound of the present invention is a compound represented by the following formula (1).
• X1 is a carbon atom or a silicon atom.
• A1 is a benzene ring which may have a substituent or a thiophene ring which may have a substituent.
• R1 is C(CN) 2 or O. However, when A1 is a benzene ring which may have a substituent, R1 is C(CN) 2 .
• A2 is a benzene ring which may have a substituent.
• R11 , R12 , R21 , and R22 each independently represent an alkyl group having 6 to 30 carbon atoms.
• R31 and R32 each independently represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.
• n1 and n2 each independently represent 0 or 1.
• X 1 may be a carbon atom or a silicon atom, and is more preferably a carbon atom.
• R 11 , R 12 , R 21 and R 22 are each independently preferably an alkyl group having 6 to 25 carbon atoms, more preferably an alkyl group having 7 to 20 carbon atoms, further preferably an alkyl group having 8 to 15 carbon atoms, and particularly preferably an alkyl group having 8 to 12 carbon atoms. It is more preferable that R 11 and R 12 are the same as each other. It is also more preferable that R 21 and R 22 are the same as each other.
• R 11 , R 12 , R 21 , and R 22 are each independently preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, even more preferably a branched alkyl group, even more preferably a group in which a linear alkyl group is bonded to a linear alkyl group (n-alkyl-n-alkyl group), and particularly preferably an alkyl group branched at the 1st or 2nd position of a linear alkyl group (1- or 2-alkylalkyl group such as 1-n-alkyl-n-alkyl group, 2-n-alkyl-n-alkyl group, etc.).
• the number of carbon atoms in the backbone alkyl group is one more than the alkyl group bonded to the 1st position (i.e., 1-C x alkyl-C x+1 alkyl group; C x indicates that the number of carbon atoms in the alkyl is x).
• R 11 , R 12 , R 21 , and R Specific examples of 22 include alkyl groups having 6 carbon atoms, such as an n-hexyl group; alkyl groups having 7 carbon atoms, such as an n-heptyl group; an n-octyl group, a 1-n-butyl-n-butyl group, a 1-n-propyl-n-pentyl group, a 1-ethyl-n-hexyl group, a 2-ethyl-n-hexyl group, a 3-ethylhexyl group, a 4-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 6-methylheptyl group, and a 2,4,4-trimethylpentyl group.
• alkyl groups having 6 carbon atoms such as an n-hexyl group
• alkyl groups having 7 carbon atoms such as an n-h
• alkyl groups having 19 carbon atoms such as n-eicosyl group and 2-n-octyldodecyl group
• alkyl groups having 20 carbon atoms such as n-heneicosyl group and 1-n-decyl-n-undecyl group
• alkyl groups having 21 carbon atoms such as n-docosyl group
• alkyl groups having 22 carbon atoms such as n-tricosyl group and 1-n-undecyl-n-dodecyl group
• alkyl groups having 25 carbon atoms such as n-dodecyl-n-tridecyl groups, and n-cosyl
• alkyl groups having 26 carbon atoms such as n-hexacosyl
• alkyl groups having 27 carbon atoms such as n-
• R 31 and R 32 each independently represent hydrogen or an alkyl group having 1 to 30 carbon atoms.
• Examples of the alkyl group having 6 to 30 carbon atoms in R 31 and R 32 are the same as those of R 11 , R 12 , R 21 , R 22 , etc.
• alkyl group having 1 to 5 carbon atoms include an alkyl group having 1 carbon atom, such as a methyl group; an alkyl group having 2 carbon atoms, such as an ethyl group; an alkyl group having 3 carbon atoms, such as an n-propyl group; an alkyl group having 4 carbon atoms, such as an n-butyl group; an alkyl group having 5 carbon atoms, such as an n-pentyl group; and the like.
• a 1 represents a benzene ring which may have a substituent or a thiophene ring which may have a substituent.
• a 2 represents a benzene ring which may have a substituent.
• the substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. Among them, a halogen atom is preferable, and a fluorine atom or a chlorine atom is more preferable. In addition, it is preferable that A 1 and A 2 each independently have 0 to 2 halogen atoms bonded.
• a 1 is preferably a thiophene ring which may have a substituent, and from the viewpoint of lengthening the infrared absorption wavelength, A 1 is preferably a benzene ring which may have a substituent.
• “lengthening the infrared absorption wavelength” means increasing the value of the wavelength ⁇ max showing the maximum absorption in the ultraviolet-visible absorption spectrum. The measurement method of the wavelength ⁇ max will be described later.
• R 1 represents C(CN) 2 or O.
• a 1 is a thiophene ring, it may be C(CN) 2 or O, but from the viewpoint of improving the external quantum efficiency, reducing the dark current I d , or improving the ON/OFF ratio of photodetection, R 1 is preferably O.
• R 1 is C(CN) 2 .
• a 1 is a benzene ring which may have a substituent, and R 1 is C(CN) 2.
• R 1 is C(CN) 2.
• a 1 is a thiophene ring which may have a substituent, and R 1 is O.
• n1 and n2 are each independently 0 or 1, and it is preferable that at least one of n1 and n2 is 1, and it is more preferable that both n1 and n2 are 1.
• Combinations of X 1 , A 1 , R 1 , n1, and n2 in the above formula (1) can include, for example, (A-1) to (A-12) in Table 1 below. From the viewpoint of increasing the infrared absorption wavelength, (A-1), (A-2), (A-7), or (A-8) are more preferable, and (A-2) or (A-8) is even more preferable.
• any of (A-3) to (A-6), (A-9) to (A-12) are more preferable, (A-5), (A-6), (A-11), or (A-12) are even more preferable, and (A-5) or (A-6) is particularly preferable.
• the benzene ring and thiophene ring described in the A 1 column in Table 1 also include those having a substituent.
• the molecular weight of the compound of the present invention is preferably 500 to 5000, more preferably 700 to 3500, and even more preferably 1000 to 2000.
• X 1 , A 1 , A 2 , R 1 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , n1 and n2 are each as defined above, Y 1 and Y 2 each independently represent a hydrogen atom or a halogen atom, and Z represents an alkyl group having 1 to 4 carbon atoms.
• the three Z's may be the same or different from each other, but from the viewpoint of ease of synthesis, they are preferably the same, and it is more preferable that all three Z's are butyl groups.
• X2 is preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.
• the compound represented by formula (4) is produced by reacting the tin compound represented by formula (3) with a compound represented by formula (5) and a compound represented by formula (6).
• the amount of compound (5) is preferably 0.6 to 10 mol, more preferably 0.8 to 7 mol, and even more preferably 1 to 3 mol, relative to 1 mol of compound (3).
• the amount of compound (6) is preferably 0.4 to 5 mol, more preferably 0.5 to 3 mol, and even more preferably 0.6 to 2 mol, relative to 1 mol of compound (3).
• a 1 , R 1 , R 11 and n1 are each defined as above, and X 3 represents a halogen atom.
• a catalyst When reacting compound (3) with compound (5) and compound (6), a catalyst may be present.
• the catalyst in step B include metal catalysts, and preferred examples include metal catalysts such as palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Among these, palladium-based catalysts are more preferred.
• the palladium in the palladium-based catalyst may be zero-valent or divalent.
• catalysts may be used alone or in combination of two or more.
• tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), dichlorobis(triphenylphosphine)palladium(II), and tris(dibenzylideneacetone)dipalladium(0) chloroform adduct are particularly preferred.
• a specific ligand may be coordinated to the catalyst.
• the ligand include trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis(tert-butyl)methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenylphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl)phosphine, tris(2-methoxyphenyl ...
• phyno)ferrocene 1,2-ethylenediamine, N,N,N',N'-tetramethylethylenediamine, 2,2'-bipyridyl, 1,3-diphenyldihydroimidazolylidene, 1,3-dimethyldihydroimidazolylidene, diethyldihydroimidazolylidene, 1,3-bis(2,4,6-trimethylphenyl)dihydroimidazolylidene, 1,3-bis(2,6-diisopropylphenyl)dihydroimidazolylidene, 1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, and bathophenanthroline can be used alone or in combination.
• triphenylphosphine, tris(o-tolyl)phosphine, and tris(2-methoxyphenyl)phosphine are preferred.
• the solvent used in step B may be any solvent that does not affect the reaction, such as ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogenated solvents, ketone solvents, and amide solvents.
• ether solvents include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane.
• Examples of the aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene.
• Examples of the ester solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate.
• Examples of the hydrocarbon solvents include pentane, hexane, and heptane.
• Examples of the halogenated solvents include dichloromethane, chloroform, dichloroethane, and dichloropropane.
• Examples of the ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
• amide solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidine.
• nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used.
• aromatic solvents are preferred, toluene or xylene are more preferred, and toluene is even more preferred.
• the amount of the solvent is generally about 1 mL or more and 100 mL or less per 1 g of compound (3), and from the viewpoint of yield and reaction efficiency, it is preferably 3 mL or more and 70 mL or less, and more preferably 5 mL or more and 40 mL or less.
• the reaction temperature is preferably 40°C or higher and 200°C or lower, more preferably 60°C or higher and 170°C or lower, and even more preferably 80°C or higher and 140°C or lower, in order to increase the reaction efficiency.
• the reaction temperature may be adjusted using microwaves.
• the compound represented by formula (1) is produced by reacting the compound represented by formula (4) with the compound represented by formula (7) below.
• the amount of the compound (7) is preferably 0.4 to 5 mol, more preferably 0.5 to 3 mol, and even more preferably 0.6 to 2 mol, per mol of the compound (4).
• the solvent used in step C may be any solvent that does not affect the reaction, including those listed above as solvents in step B, with chloroform being more preferred.
• the amount of the solvent is generally about 1 mL or more and 200 mL or less per 1 g of compound (4), and from the viewpoint of yield and reaction efficiency, it is preferably 10 mL or more and 150 mL or less, and more preferably 25 mL or more and 120 mL or less.
• the reaction temperature is preferably 10°C or higher and 100°C or lower, more preferably 20°C or higher and 60°C or lower, and even more preferably room temperature (about 20 to 25°C).
• the reaction temperature may be adjusted using microwaves.
• the compound of the present invention (the compound represented by the above formula (1)) may be produced by the following steps D and E. Since the compounds used in the reaction differ depending on the scheme, it is only necessary to appropriately select whether to adopt steps B and C or steps D and E in consideration of the reactivity of the compounds used.
• X 1 , A 1 , A 2 , R 1 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , n1 and n2 are each as defined above, Y 1 and Y 2 each independently represent a hydrogen atom or a halogen atom, and Z represents an alkyl group having 1 to 4 carbon atoms.
• a compound represented by formula (8) is produced by reacting a compound represented by formula (9) and a compound represented by formula (10) with a tin compound represented by formula (3).
• the process is the same as step B, except that the tin compound represented by formula (3) is reacted with the following compounds (9) and (10) instead of the compounds (5) and (6).
• a 2 , R 12 and n2 are each defined as above, and X 5 represents a halogen atom.
• R 11 and n1 are defined as above, and X 6 represents a halogen atom.
• the catalyst in step D may be any of the catalysts listed as catalysts in step B above, and preferably includes metal catalysts such as palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, and ruthenium-based catalysts. Among these, palladium-based catalysts are more preferred.
• tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), dichlorobis(triphenylphosphine)palladium(II), and tris(dibenzylideneacetone)dipalladium(0) chloroform adduct are particularly preferred.
• a specific ligand may be coordinated to the catalyst, and among these, triphenylphosphine, tris(o-tolyl)phosphine, and tris(2-methoxyphenyl)phosphine are preferred.
• any solvent that does not affect the reaction can be used, and any of the solvents listed as solvents in step B above can be used.
• aromatic solvents are preferred, toluene or xylene are more preferred, and toluene is even more preferred.
• the amount of the solvent is generally about 1 mL or more and 200 mL or less per 1 g of compound (3), and from the viewpoint of yield and reaction efficiency, it is preferably 5 mL or more and 100 mL or less, and more preferably 10 mL or more and 50 mL or less.
• the reaction temperature is preferably 40°C or higher and 200°C or lower, more preferably 60°C or higher and 180°C or lower, and even more preferably 80°C or higher and 160°C or lower, in order to increase the reaction efficiency.
• the reaction temperature may be adjusted using microwaves.
• the compound represented by formula (1) is produced by reacting the compound represented by formula (8) with the compound represented by formula (11) below.
• the amount of the compound (11) is preferably 0.4 to 5 mol, more preferably 0.5 to 3 mol, and even more preferably 0.6 to 2 mol, per mol of the compound (8).
• the solvent used in step E may be any solvent that does not affect the reaction, including those listed as solvents in step B above, with acetic anhydride being preferred.
• the amount of the solvent is generally about 1 mL or more and 200 mL or less per 1 g of compound (8), and from the viewpoint of yield and reaction efficiency, it is preferably 10 mL or more and 150 mL or less, and more preferably 25 mL or more and 120 mL or less.
• the reaction temperature is preferably 20°C or higher and 160°C or lower, more preferably 40°C or higher and 140°C or lower, and even more preferably 60°C or higher and 120°C or lower.
• the reaction temperature may be adjusted using microwaves.
• the method for producing the compound represented by formula (1) above is not limited to the above two schemes, and the compound may be produced by a scheme other than the above two schemes. Although it is desirable that only the compound represented by formula (1) above is ultimately obtained (100% purity), a composition containing compounds other than the compound represented by formula (1) above may be obtained. For example, a composition containing a compound of the following formula in addition to the compound represented by formula (1) above may be obtained.
• the purity of the compound represented by formula (1) in the composition may be, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more.
• the compound represented by the above formula (1) can be used as an acceptor material.
• electronic devices containing the compound represented by the above formula (1) include organic photodetectors (e.g., sensors such as image sensors), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting diodes (OLEDs), organic light emitting transistors (OLETs), organic photovoltaic devices (OPVs), organic solar cells, dye-sensitized solar cells (DSSCs), perovskite solar cells, solar cells, laser diodes, Schottky diodes, photoconductors, and thermoelectric devices.
• organic photodetectors e.g., sensors such as image sensors
• OFETs organic field effect transistors
• OFTs organic thin film transistors
• OLEDs organic light emitting diodes
• OLETs organic light emitting transistors
• OLEDs organic photovoltaic devices
• organic solar cells dye-sensitized solar cells (DSSCs), perovskite solar
• the donor material and the compound of the present invention may be in contact with each other, and a layer containing a donor material and a layer containing an acceptor material may be laminated, or a mixed layer containing a donor material and an acceptor material may be used.
• the present invention also includes an organic thin film containing the compound represented by formula (1) above.
• the present invention also includes an organic light detection element and an organic light detector having an organic light detection element, and the organic light detection element has an organic thin film in the light receiving section.
• Example 1 Synthesis of EHCyDTh-2OEHTh-TCN-CI
• EHCyDTh-2OEHThCHO-TCN 106 mg
• CI 34 mg
• chloroform 10 mL
• pyridine 1 mL
• Example 3 Synthesis of EHCyDTh-2OEHTh-CI-CNI
• EHCyDTh-2OEHThCHO-CI 90 mg
• CNI 23 mg
• acetic anhydride 4 mL
• Comparative Examples 1 and 2 As comparative examples, COI-4Cl and COTIC-4F described in Patent Documents 1 and 2 were used as Comparative Examples 1 and 2.
• the compounds of Comparative Examples 1 and 2 and Examples 1 to 3 (hereinafter referred to as low molecular weight compounds) were used to evaluate various physical properties by the following measurement methods. The measurement results are shown in Table 2. In Table 2, for example, 5.02E-08 means 5.02 ⁇ 10 ⁇ 8 .
• ⁇ Calculation method of wavelength ⁇ max > The low molecular weight compound was dissolved in chlorobenzene to a concentration of 8 mg/mL, and the resulting solution was spin-coated onto a glass substrate to form an organic thin film. This thin film was subjected to UV measurement using an ultraviolet-visible spectrometer (Shimadzu UV-3600i Plus) at room temperature and pressure. The peak showing maximum absorption in the ultraviolet-visible absorption spectrum measured in the range of 200 nm to 1500 nm by the above UV measurement was taken as ⁇ max [nm].
• EQE ⁇ External quantum efficiency (EQE)>
• the external quantum efficiency was measured by using a spectral sensitivity measuring device (SM-250GDR manufactured by Bunkoukeiki Co., Ltd.) when the organic light detecting element produced by the production method described below was irradiated with light having a wavelength of 1000 nm.
• SM-250GDR manufactured by Bunkoukeiki Co., Ltd.
• ⁇ Dark current I d > A 0.05027 mm square metal mask was attached to an organic photodetector element produced by the manufacturing method described below, and a solar simulator (OTENTO-SUN III, AM1.5G filter, radiant intensity 100 mW/cm 2 , manufactured by Bunkoukeiki Co., Ltd.) was used as an irradiation light source.
• An IV curve (A) was obtained with an applied voltage of -2 V to 2 V under light irradiation
• an IV curve (B) was obtained with an applied voltage of -2 V to 2 V in the dark (light-shielded state) using a source meter (Model 2400, manufactured by Keithley). From the IV curve (B), the dark current I d (unit: A), which is the current at an applied voltage of ⁇ 2 V in a dark place (light-shielded state), was calculated.
• the solution was stirred and mixed on a hot stirrer at a temperature of 100° C. for 2 hours or more, and then filtered through a 0.45 ⁇ m filter to obtain a mixed solution of the p-type semiconductor compound and the n-type semiconductor compound.
• the manufacturing methods described in (1) to (4) below were carried out in order to obtain an organic photodetector having an inverted structure in which a transparent electrode layer, an electron transport layer, an active layer, a hole transport layer, and an electrode layer were laminated in this order.
• the organic photodetector has an active layer, which is an organic thin film, in the light receiving section.
• a glass substrate manufactured by Geomatec Co., Ltd.
• ITO indium tin oxide
• anode transparent conductive film
• the glass substrate was subjected to UV-ozone treatment.
• a 0.5M zinc acetate/0.5M aminoethanol/2-methoxyethanol solution was applied to the surface of the ITO using a spin coater (3000 rpm, 40 seconds), and then annealed at 175° C. for 30 minutes to obtain a laminate in which an electron transport layer was laminated on a transparent electrode layer.
• the laminate was carried into a glove box, and the mixed liquid of the p-type semiconductor compound and the n-type semiconductor compound produced by the above-mentioned production method was spin-coated on the surface of the electron transport layer under an inert gas atmosphere, and then annealed on a hot plate at 110° C. for 15 minutes to produce an active layer on the electron transport layer.
• molybdenum oxide was deposited on the surface of the active layer to form a hole transport layer on the active layer.
• silver was deposited on the surface of the hole transport layer to form an electrode, thereby obtaining an organic light-detecting element.
• Example 1 and 2 in which A 1 is a thiophene ring and R 1 is O are used, the external quantum efficiency and the ON/OFF ratio of photodetection are increased and the dark current I d is reduced compared to the cases in which Comparative Examples 1 and 2 are used.
• the wavelength ⁇ max is longer than that of Comparative Examples 1 and 2, that is, the infrared absorption wavelength is longer.

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