CN117769897A - Compound, composition, and photoelectric conversion element - Google Patents

Compound, composition, and photoelectric conversion element Download PDF

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Publication number
CN117769897A
CN117769897A CN202280051331.0A CN202280051331A CN117769897A CN 117769897 A CN117769897 A CN 117769897A CN 202280051331 A CN202280051331 A CN 202280051331A CN 117769897 A CN117769897 A CN 117769897A
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group
substituent
optionally
compound
formula
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横井优季
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2022101134A external-priority patent/JP2023020911A/en
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority claimed from PCT/JP2022/028636 external-priority patent/WO2023008376A1/en
Publication of CN117769897A publication Critical patent/CN117769897A/en
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    • 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

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Abstract

The invention aims to reduce dark current. The solution is a composition comprising a p-type semiconductor material and an n-type semiconductor material, wherein the n-type semiconductor material comprises a compound represented by the following formula (I). D (D) 1 ‑B 1 ‑A 1 (I) (in the formula (I), D 1 Represents an electron donating group, A 1 Represents an electron withdrawing group, B 1 Represents a 2-valent group which comprises 1 or more structural units and constitutes a pi-conjugated system. ) The band gap of the n-type semiconductor material is preferably larger than the band gap of the p-type semiconductor material.

Description

Compound, composition, and photoelectric conversion element
Technical Field
The present invention relates to a compound as a semiconductor material, a composition containing the compound, and a photoelectric conversion element using the composition as a material.
Background
The photoelectric conversion element is a device extremely useful from the viewpoints of, for example, energy saving and reduction of carbon dioxide emission, and has been attracting attention.
The photoelectric conversion element is an element including at least a pair of electrodes including an anode and a cathode, and an active layer provided between the pair of electrodes. In the photoelectric conversion element, at least one of the pair of electrodes is made of a transparent or semitransparent material, and light is incident on the active layer from the electrode side that is made transparent or semitransparent. By the energy (hν) of light incident on the active layer, electric charges (holes and electrons) are generated in the active layer, and the generated holes move toward the anode and the electrons move toward the cathode. Then, the charges reaching the anode and the cathode are taken out to the outside of the element.
In the photoelectric conversion element, further improvement in photoelectric conversion efficiency is demanded. Accordingly, various semiconductor materials have been developed and reported (see non-patent document 1).
Prior art literature
Non-patent literature
Non-patent document 1: joule 3, 1140-1151, april 17, 2019
Disclosure of Invention
Problems to be solved by the invention
However, it is reported that: according to the n-type semiconductor material reported in the above non-patent document 1, a photoelectric conversion efficiency of about 15% can be certainly achieved.
However, it is difficult to sufficiently reduce the dark current required for the photoelectric conversion element as the light detection element.
Therefore, a further semiconductor material capable of satisfying the characteristics required for the photoelectric conversion element, in particular, capable of reducing dark current in the light detection element is demanded.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a compound having a predetermined structure and a composition containing the compound, which will be described later, and have completed the present invention.
Accordingly, the present invention provides the following [1] to [13].
[1] A composition comprising a p-type semiconductor material and an n-type semiconductor material,
The n-type semiconductor material includes a compound represented by the following formula (I).
D 1 -B 1 -A 1 (I)
(in the formula (I),
D 1 represents an electron donating group, and is represented by,
A 1 represents an electron-withdrawing group and is represented by,
B 1 represents a 2-valent group which comprises 1 or more structural units and constitutes a pi-conjugated system. )
[2] The composition according to [1], wherein the band gap of the n-type semiconductor material is larger than the band gap of the p-type semiconductor material.
[3]According to [1]]Or [2]]The composition according to, wherein D 1 Energy level (E) D-LUMO ) Constitution B 1 Energy level (E) of LUMO of at least 1 structural unit of more than 1 structural unit π-LUMO ) And A 1 Energy level (E) A-LUMO ) The conditions shown in the following formula are satisfied.
E D-LUMO ＞E B-LUMO ＞E A-LUMO
[4] The composition according to any one of [1] to [3], wherein the p-type semiconductor material is a polymer compound.
[5] The composition according to item [4], wherein the p-type semiconductor material is a polymer compound having an absorption peak wavelength of more than 700 nm.
[6] An ink composition comprising the composition according to any one of [1] to [5] and a solvent.
[7] A film having a bulk heterojunction structure, comprising the composition of any one of [1] to [5 ].
[8] A photoelectric conversion element comprising the film of [7] as an active layer.
[9] The photoelectric conversion element according to claim 8, which is a photodetector.
[10] A compound represented by the following formula (I).
D 1 -B 1 -A 1 (I)
(in the formula (I),
D 1 represents an electron donating group, and is represented by,
A 1 the electron-withdrawing group means an electron-withdrawing group having a ring structure,
B 1 represents a 2-valent group which comprises 1 or more structural units and constitutes a pi-conjugated system,
the 1 st structural unit which is at least 1 of the 1 st structural units is a structural unit represented by the following formula (II), and the remaining 2 nd structural units other than the 1 st structural unit are a 2-valent group including an unsaturated bond, a 2-valent aromatic carbocyclic group, or a 2-valent aromatic heterocyclic group.
In the case where there are 2 or more 1 st structural units, the 2 or more 1 st structural units may be the same or different from each other. In the case where there are 2 or more structural units of the 2 nd structure unit, the 2 nd structure units of the 2 nd structure unit may be the same or different from each other. )
[ chemical formula 1]
(in the formula (II),
Ar 1 and Ar is a group 2 Each independently represents an aromatic carbocyclic ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent,
y represents a group represented by a direct bond, -C (=O) -, or an oxygen atom,
R each independently represents:
a hydrogen atom,
Halogen atom,
An alkyl group which may have a substituent,
Cycloalkyl which may have a substituent, aryl which may have a substituent, alkoxy which may have a substituent, cycloalkoxy which may have a substituent, aryloxy which may have a substituent, alkylthio which may have a substituent, cycloalkylthio which may have a substituent, arylthio which may have a substituent, 1-valent heterocyclic group which may have a substituent, substituted amino which may have a substituent, acyl which may have a substituent, imine residue which may have a substituent, amide group which may have a substituent, imide group which may have a substituent, oxycarbonyl which may have a substituent, alkenyl which may have a substituent, cycloalkenyl which may have a substituent, alkynyl which may have a substituent, cycloalkynyl which may have a substituent, cyano which may have a substituent,
Nitro group,
-C(＝O)-R a The radicals shown, or-SO 2 -R b The radicals are shown in the figures,
R a and R is b Each independently represents:
a hydrogen atom,
An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, or a 1-valent heterocyclic group which may have a substituent.
The plurality of R's present may be the same or different from each other. )
[11] The compound according to [10], wherein the 1 st structural unit is a structural unit represented by the following formula (III).
[ chemical formula 2]
(in the formula (III),
y and R are as defined above,
X 1 and X 2 Each independently represents a sulfur atom or an oxygen atom,
Z 1 and Z 2 Each independently represents a group represented by =c (R) -or a nitrogen atom. )
[12] The compound according to [11], wherein the 1 st structural unit is a structural unit represented by the following formula (IV-1).
[ chemical formula 3]
(in the formula (IV-1),
y represents a group represented by-C (=O) -or an oxygen atom,
r each independently represents:
a hydrogen atom,
Halogen atom,
An alkyl group which may have a substituent,
Cycloalkyl which may have a substituent,
Aryl which may have a substituent,
Alkoxy which may have a substituent,
A cycloalkoxy group which may have a substituent(s),
Aryloxy group which may have a substituent,
Alkylthio which may have a substituent,
A cycloalkylthio group which may have a substituent(s),
Arylthio which may have a substituent,
A 1-valent heterocyclic group which may have a substituent,
Substituted amino group which may have a substituent,
Acyl which may have a substituent,
An imine residue which may have a substituent,
An amide group which may have a substituent,
An imide group which may have a substituent,
A substituted oxycarbonyl group which may have a substituent(s),
Alkenyl group which may have substituent(s),
Cycloalkenyl group which may have substituent(s),
Alkynyl group which may have substituent(s),
A cycloalkynyl group which may have a substituent(s),
Cyano group,
Nitro group,
-C(＝O)-R a A group of the formula
-SO 2 -R b The radicals are shown in the figures,
R a and R is b Each independently represents:
a hydrogen atom,
An alkyl group which may have a substituent,
Aryl which may have a substituent,
Alkoxy which may have a substituent,
Aryloxy group which may have a substituent, or
A 1-valent heterocyclic group which may have a substituent.
The plurality of R's present may be the same or different from each other. )
[13]According to [10 ]]～[12]The compound according to any one of the above, wherein B 1 Is a 2-valent group having any 1 structure selected from the structures represented by the following formulas (VI-1) to (VI-16).
-CU1-(VI-1)
-CU1-CU1-(VI-2)
-CU1-CU2-(VI-3)
-CU1-CU1-CU1-(VI-4)
-CU1-CU2-CU1-(VI-5)
-CU1-CU1-CU2-(VI-6)
-CU1-CU2-CU2-(VI-7)
-CU2-CU1-CU2-(VI-8)
-CU1-CU1-CU1-CU1-(VI-9)
-CU1-CU1-CU1-CU2-(VI-10)
-CU1-CU1-CU2-CU1-(VI-11)
-CU1-CU1-CU2-CU2-(VI-12)
-CU1-CU2-CU1-CU2-(VI-13)
-CU1-CU2-CU2-CU1-(VI-14)
-CU1-CU2-CU2-CU2-(VI-15)
-CU2-CU1-CU2-CU2-(VI-16)
(in the formulae (V-1) to (V-16),
CU1 represents the above-mentioned 1 st structural unit,
CU2 represents the above-mentioned 2 nd structural unit.
When there are 2 or more CUs 1, the 2 or more CUs 1 may be the same or different from each other, and when there are 2 or more CUs 2, the 2 or more CUs 2 may be the same or different from each other. In the formula (VI-8), the case where 2 CUs 2 are identical is not included. )
Effects of the invention
According to the present invention, a compound capable of effectively reducing dark current, a composition containing the compound, and a photoelectric conversion element using the composition as a material of a functional layer can be provided.
Drawings
Fig. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
Fig. 2 is a diagram schematically showing a configuration example of the image detection unit.
Fig. 3 is a diagram schematically showing a configuration example of the fingerprint detection section.
Fig. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging device.
Fig. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein recognition apparatus.
Fig. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF type distance measuring device.
Detailed Description
Hereinafter, a compound according to an embodiment of the present invention will be described, and a photoelectric conversion element using the compound according to the embodiment will be further described with reference to the accompanying drawings. The drawings schematically show the shape, size, and arrangement of the constituent elements to the extent that the invention can be understood. The present invention is not limited to the following description, and each component may be appropriately modified within a range not departing from the gist of the present invention. The configuration of the embodiment of the present invention is not necessarily limited to the configuration shown in the drawings.
First, terms commonly used in the following description will be described.
"non-fullerene compound" refers to a compound that is not either a fullerene or a fullerene derivative.
"pi conjugated system" refers to a system in which pi electrons are delocalized among multiple bonds.
The term "polymer compound" means a polymer having a molecular weight distribution and a number average molecular weight of 1X 10 in terms of polystyrene 3 Above and 1×10 8 The following polymers. The total of the structural units contained in the polymer compound was 100 mol%.
"structural unit" means that 1 or more residues derived from the starting compound (monomer) are present in the compound and the polymer compound of the present embodiment.
The "hydrogen atom" may be a protium atom or a deuterium atom.
Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "optionally substituted" means that all hydrogen atoms constituting the compound or group are not substituted, and that some or all of 1 or more hydrogen atoms are substituted with substituents.
Examples of the "substituent" include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, a 1-valent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an imide group, a substituted oxycarbonyl group, a cyano group, an alkylsulfonyl group and a nitro group. In the present specification, the term "number of carbon atoms" refers to the number of carbon atoms excluding substituents.
In the present specification, the "alkyl group" may be any of a straight chain, a branched chain, and a cyclic one, unless otherwise specified. The number of carbon atoms of the linear alkyl group excluding the substituent is usually 1 to 50, preferably 1 to 30, more preferably 1 to 20. The number of carbon atoms of the branched or cyclic alkyl group excluding the substituent is usually 3 to 50, preferably 3 to 30, more preferably 4 to 20.
Specific 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-hexyl-decyl, n-dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl groups.
The alkyl group may have a substituent. The substituted alkyl group is, for example, a group in which a hydrogen atom in the above-exemplified alkyl group is substituted with a substituent such as an alkoxy group, an aryl group, a fluorine atom, or the like.
Specific examples of the alkyl group having a substituent include trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, 3-phenylpropyl group, 3- (4-methylphenyl) propyl group, 3- (3, 5-dihexylphenyl) propyl group and 6-ethoxyhexyl group.
"cycloalkyl" may be a monocyclic group or a polycyclic group. Cycloalkyl groups may have substituents. The number of carbon atoms of the cycloalkyl group excluding the substituent is usually 3 to 30, preferably 12 to 19.
Examples of cycloalkyl groups include alkyl groups having no substituent such as cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl groups, and groups in which a hydrogen atom is substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, and a fluorine atom.
Specific examples of the cycloalkyl group having a substituent include methylcyclohexyl and ethylcyclohexyl.
"p-valent aromatic carbocyclyl" means an atomic group remaining after p hydrogen atoms directly bonded to carbon atoms constituting a ring are removed from an aromatic hydrocarbon which may have a substituent. The p-valent aromatic carbocyclyl group may further have a substituent.
"aryl" is a 1-valent aromatic carbocyclyl group, and refers to an atomic group remaining after 1 hydrogen atom directly bonded to a carbon atom constituting a ring is removed from an aromatic hydrocarbon which may have a substituent.
The aryl group may have a substituent. Specific examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and groups in which a hydrogen atom is substituted with a substituent such as an alkyl group, an alkoxy group, an aryl group, or a fluorine atom.
The "alkoxy group" may be any of linear, branched, and cyclic. The number of carbon atoms of the straight-chain alkoxy group excluding the substituent is usually 1 to 40, preferably 1 to 10. The number of carbon atoms of the branched or cyclic alkoxy group excluding the substituent is usually 3 to 40, preferably 4 to 10.
The alkoxy group may have a substituent. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, cyclohexyloxy, n-heptyloxy, n-octoxy, 2-ethylhexyloxy, n-nonyloxy, n-decyloxy, 3, 7-dimethyloctoxy, 3-heptyldodecoxy, lauryloxy, and groups in which a hydrogen atom is replaced with an alkoxy group, an aryl group or a fluorine atom.
The cycloalkyl group of the "cycloalkoxy group" may be a monocyclic group or a polycyclic group. The cycloalkoxy group may have a substituent. The number of carbon atoms of the cycloalkoxy group excluding the substituent is usually 3 to 30, preferably 12 to 19.
Examples of the cycloalkoxy group include a cycloalkoxy group having no substituent such as a cyclopentyloxy group, a cyclohexyloxy group, and a cycloheptyloxy group, and a group in which a hydrogen atom of these groups is substituted with a fluorine atom or an alkyl group.
The number of carbon atoms of the "aryloxy group" does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48.
The aryloxy group may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, a 1-anthracenoxy group, a 9-anthracenoxy group, a 1-pyrenyloxy group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyl group, an alkoxy group, or a fluorine atom.
"alkylthio" may be any of linear, branched, and cyclic. The number of carbon atoms of the straight-chain alkylthio group excluding the substituent is usually 1 to 40, preferably 1 to 10. The number of carbon atoms of the branched and cyclic alkylthio groups excluding the substituent is usually 3 to 40, preferably 4 to 10.
Alkylthio groups may have substituents. Specific examples of alkylthio groups include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, t-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio, 2-ethylhexylthio, nonylthio, decylthio, 3, 7-dimethyloctylthio, laurylthio and trifluoromethylthio.
The cycloalkyl group of the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms of the cycloalkylthio group excluding the substituent is usually 3 to 30, preferably 12 to 19.
Examples of the cycloalkylthio group which may have a substituent include cyclohexylthio.
The number of carbon atoms of the "arylthio group" is not inclusive of the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 48.
The arylthio group may have a substituent. Examples of the arylthio group include a phenylthio group, a C1-C12 alkoxyphenylthio group (C1-C12 represents a group having 1-12 carbon atoms which will be described later), a C1-C12 alkylphenylthio group, a 1-naphthylthio group, a 2-naphthylthio group and a pentafluorophenylthio group.
"p-valent heterocyclic group" (p represents an integer of 1 or more) means an atomic group remaining after p hydrogen atoms out of hydrogen atoms directly bonded to carbon atoms or hetero atoms constituting a ring are removed from a heterocyclic compound which may have a substituent.
The p-valent heterocyclic group may further have a substituent. The number of carbon atoms of the p-valent heterocyclic group excluding the substituent is usually 2 to 30, preferably 2 to 6.
Examples of the substituent that the heterocyclic compound may have include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a 1-valent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group. The p-valent heterocyclic group includes "p-valent aromatic heterocyclic group".
The "p-valent aromatic heterocyclic group" means an atomic group remaining after p hydrogen atoms out of hydrogen atoms directly bonded to carbon atoms or hetero atoms constituting a ring are removed from an aromatic heterocyclic compound which may have a substituent. The p-valent aromatic heterocyclic group may further have a substituent.
The aromatic heterocyclic compound includes, in addition to a compound in which the heterocyclic ring itself exhibits aromaticity, a compound in which the heterocyclic ring itself does not exhibit aromaticity but an aromatic ring is condensed on the heterocyclic ring.
Specific examples of the aromatic heterocyclic compound include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole, as a compound having an aromatic nature in the heterocyclic ring itself.
Specific examples of the aromatic heterocyclic compound include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole and benzopyran, as a compound in which an aromatic heterocyclic ring does not exhibit aromaticity and an aromatic ring is condensed on a heterocyclic ring.
The number of carbon atoms of the 1-valent heterocyclic group excluding the substituent is usually 2 to 60, preferably 4 to 20.
The 1-valent heterocyclic group may have a substituent, and specific examples of the 1-valent heterocyclic group include thienyl, pyrrolyl, furyl, pyridyl, piperidyl, quinolyl, isoquinolyl, pyrimidinyl, triazinyl, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkoxy group, or the like.
"substituted amino" 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 1-valent heterocyclic group, and an alkyl group, an aryl group, or a 1-valent heterocyclic group is preferable. The number of carbon atoms of the substituted amino group is usually 2 to 30.
Examples of the substituted amino group include dialkylamino groups such as dimethylamino and diethylamino; diarylamino groups such as diphenylamino group, bis (4-methylphenyl) amino group, bis (4-tert-butylphenyl) amino group, and bis (3, 5-di-tert-butylphenyl) amino group.
The "acyl group" may have a substituent. The number of carbon atoms of the acyl group excluding the substituent is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, benzoyl, trifluoroacetyl and pentafluorobenzoyl.
"imine residue" refers to the radical remaining after removal of 1 hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound. "imine compound" refers to an organic compound having a carbon atom-nitrogen atom double bond within the molecule. Examples of the imine compound include aldimines, ketimines, and compounds in which a hydrogen atom bonded to a nitrogen atom constituting a carbon atom-nitrogen atom double bond in aldimines is substituted with an alkyl group or the like.
The imine residue has usually 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Examples of the imine residue include groups represented by the following structural formulae.
[ chemical formula 4]
"amide" refers to the radical remaining after removal of 1 hydrogen atom bonded to a nitrogen atom from an amide. The number of carbon atoms of the amide group is usually 1 to 20, preferably 1 to 18. Specific examples of the amide group include a carboxamide group, an acetamido group, a propionyl group, a butyrylamino group, a benzamide group, a trifluoroacetamido group, a pentafluorobenzmido group, a dicarboxamide group, a diacetylamino group, a dipropionamide group, a dibutylamino group, a dibenzoylamino group, a di-trifluoroacetamido group and a di-pentafluorobenzamido group.
"imide group" refers to the radical remaining after removal of 1 hydrogen atom bonded to a nitrogen atom from an imide. The number of carbon atoms of the imide group is usually 4 to 20. Specific examples of the imide group include groups represented by the following structural formulae.
[ chemical formula 5]
"substituted oxycarbonyl" refers to the group shown as R' -O- (c=o) -. Here, R' represents an alkyl group, an aryl group, an aralkyl group, or a 1-valent heterocyclic group.
The number of carbon atoms of the substituted oxycarbonyl group excluding the number of carbon atoms of the substituent is usually 2 to 60, preferably 2 to 48.
Specific 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.
The "alkenyl" may be any of straight-chain, branched, and cyclic. The number of carbon atoms of the linear alkenyl group excluding the substituent is usually 2 to 30, preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkenyl group excluding the substituent is usually 3 to 30, preferably 4 to 20.
Alkenyl groups may have substituents. Specific examples of the alkenyl group include vinyl group, 1-propenyl group, 2-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with an alkyl group, an alkoxy group, an aryl group, and a fluorine atom.
"cycloalkenyl" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms of the cycloalkenyl group excluding the substituent is usually 3 to 30, preferably 12 to 19.
Examples of the cycloalkenyl group include a cycloalkenyl group having no substituent such as a cyclohexenyl group, and a group in which a hydrogen atom is substituted with an alkyl group, an alkoxy group, an aryl group, or a fluorine atom.
Examples of the cycloalkenyl group having a substituent include methylcyclohexenyl and ethylcyclohexenyl.
The "alkynyl group" may be any of straight-chain, branched-chain, and cyclic. The number of carbon atoms of the linear alkenyl group excluding the substituent is usually 2 to 20, preferably 3 to 20. The number of carbon atoms of the branched or cyclic alkenyl group excluding the substituent is usually 4 to 30, preferably 4 to 20.
Alkynyl groups may have substituents. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 5-hexynyl group, and a group in which a hydrogen atom is replaced with an alkoxy group, an aryl group, or a fluorine atom.
"cycloalkynyl" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms of the cycloalkynyl group excluding the substituent is usually 4 to 30, preferably 12 to 19.
Examples of the cycloalkynyl group include a cycloalkynyl group having no substituent such as a cyclohexenyl group, and a group in which a hydrogen atom is substituted with an alkyl group, an alkoxy group, an aryl group, or a fluorine atom.
Examples of the substituted cycloalkynyl group include methylcyclohexynyl group and ethylcyclohexynyl group.
The "alkylsulfonyl" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms of the alkylsulfonyl group excluding the number of carbon atoms of the substituent is usually 1 to 30. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group and a dodecylsulfonyl group.
The symbol "" which can be marked in the chemical formula indicates a bond.
The "ink composition" refers to a liquid material used in the coating method, and is not limited to a colored liquid. The "coating method" includes a method of forming a film (layer) using a liquid substance, and examples thereof include a slit die coating method, a slit coating method, a doctor blade coating method, a spin coating method, a casting method, a micro gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, a gravure printing method, a flexographic printing method, an offset printing method, an inkjet coating method, a dispenser printing method, a nozzle coating method, and a capillary coating method.
The ink composition may be a solution, or a dispersion such as a dispersion, emulsion (emulsion), suspension (suspension), or the like.
The "absorption peak wavelength" is a parameter determined based on absorption peaks of an absorption spectrum measured in a predetermined wavelength range, and refers to a wavelength of an absorption peak having the largest absorbance among absorption peaks of the absorption spectrum.
The composition of the embodiment of the present invention is a composition comprising a p-type semiconductor material and an n-type semiconductor material, the n-type semiconductor material comprising a compound represented by the following formula (I).
D 1 -B 1 -A 1 (I)
In the formula (I) of the present invention,
D 1 represents an electron donating group, and is represented by,
A 1 represents an electron-withdrawing group and is represented by,
B 1 represents a 2-valent group which comprises 1 or more structural units and constitutes a pi-conjugated system.
Hereinafter, description will be made specifically.
1. Compound (n-type semiconductor material)
First, the "compound" of the present embodiment will be described. The compound of the present embodiment is generally an n-type semiconductor material, and can be suitably used as a semiconductor material of a photoelectric conversion element, particularly an active layer.
In the active layer, which of the p-type semiconductor material and the n-type semiconductor material the compound according to the present embodiment functions as may be relatively determined according to the value of the energy level of HOMO (Highest Occupied Molecular Orbital: highest occupied molecular orbital) or the value of the energy level of LUMO (Lowest Unoccupied Molecular Orbital: lowest unoccupied molecular orbital) of the selected compound. The compound of the present embodiment can be particularly suitably used as an n-type semiconductor material in an active layer of a photoelectric conversion element.
The relationship between the values of the energy levels of HOMO and LUMO of the p-type semiconductor material contained in the active layer and the values of the energy levels of HOMO and LUMO of the n-type semiconductor material can be appropriately set within the range in which the photoelectric conversion element (light detection element) operates.
The "compound" of the present embodiment is a compound represented by the following formula (I).
D 1 -B 1 -A 1 (I)
In the formula (I) of the present invention,
D 1 represents an electron donating group, and is represented by,
A 1 represents an electron-withdrawing group and is represented by,
B 1 presentation bagAnd a 2-valent group which contains 1 or more structural units and constitutes a pi-conjugated system.
The compound of the present embodiment is a non-fullerene compound represented by the above formula (I), and A is a 1-valent group having electron withdrawing properties 1 And B is connected with 1 D being a 1-valent group having electron donating property and bonded to one end side thereof 1 A compound bonded to the other end side, the compound B 1 Is a 2-valent group which comprises more than 1 structural unit and forms a pi conjugated system. Among the compounds of the present embodiment, D is preferably included 1 And A 1 The whole of the included compounds constitutes pi conjugated system.
In the following, A which can constitute the compound represented by the formula (I) 1 、B 1 And D 1 Specific description will be given.
(1) With respect to A 1
A 1 Is a 1-valent group having electron withdrawing property.
Specifically, A 1 Is a compound having a group B capable of further reducing the number of 2-valent groups constituting a pi-conjugated system 1 A functional 1-valent group of electron density of (c).
A 1 Preferably an electron withdrawing group having a ring structure.
In this embodiment, A is a 1-valent group having electron withdrawing properties 1 Examples of (C) include-CH=C (-CN) 2 A group represented by the following formula (a-1) to (a-10).
[ chemical formula 6]
In the formulas (a-1) to (a-8),
t represents a carbocycle which may have a substituent or a heterocycle which may have a substituent. Carbocycles and heterocycles may be monocyclic or condensed rings. In the case where these rings have a plurality of substituents, the plurality of substituents present may be the same or different from each other.
Examples of the carbocycle which may have a substituent(s) as shown in T include aliphatic carbocycle and aromatic carbocycle, and preferably aromatic carbocycle. Specific examples of the carbocycle which may have a substituent(s) represented by T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring and a phenanthrene ring, and are preferably a benzene ring, a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
Examples of the heterocyclic ring which may have a substituent(s) as shown in T include aliphatic heterocyclic ring and aromatic heterocyclic ring, and preferably an aromatic carbocyclic ring. Specific examples of the heterocyclic ring which may have a substituent(s) shown in T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring and a thienothiophene ring, preferably a thiophene ring and a pyridine ring, a pyrazine ring, a thiazole ring and a thienothiophene ring, and more preferably a thiophene ring. These rings may have a substituent.
Examples of the substituent that the carbocycle or heterocycle represented by T may have include a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group and a 1-valent heterocyclic group, and preferably a fluorine atom, a chlorine atom, an alkoxy group having 1 to 6 carbon atoms and/or an alkyl group having 1 to 6 carbon atoms.
X 4 、X 5 And X 6 Each independently represents an oxygen atom, a sulfur atom, an alkylidene group or=c (-CN) 2 The radicals shown are preferably oxygen atoms, sulfur atoms or =c (-CN) 2 The radicals shown.
X 7 Represents a hydrogen atom or a halogen atom, a cyano group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a 1-valent heterocyclic group. X is X 7 Cyano is preferred.
R a1 、R a2 、R a3 、R a4 、R a5 And R is a6 Each independently represents a hydrogen atom, an alkyl group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a 1-valent heterocyclic group, and is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.
[ chemical formula 7]
In the formula (a-9) and the formula (a-10),
R a7 and R is a8 Each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, a 1-valent aromatic carbocyclic group which may have a substituent, or a 1-valent aromatic heterocyclic group which may have a substituent, and a plurality of R's present a7 And R is a8 May be the same as or different from each other.
As A 1 Specific examples of the electron withdrawing group include groups represented by the following formulas (a-1-1) to (a-1-4), and formulas (a-5-1), formula (a-6-2) and formula (a-7-1).
[ chemical formula 8]
In the formulae (a-1-1) to (a-1-4), and formulae (a-5-1), formula (a-6-1) and formula (a-7-1),
a plurality of R's present a11 Each independently represents a hydrogen atom or a substituent,
R a1 、R a2 、R a3 、R a4 and R is a5 Each independently is as defined above.
R a11 Preferably a hydrogen atom, a halogen atom, an alkoxy group, a cyano group or an alkyl group. R is R a1 、R a2 、R a3 、R a4 And R is a5 Alkyl groups which may have a substituent or aryl groups which may have a substituent are preferable.
As A 1 Preferable examples of the electron withdrawing group include groups represented by the following formula.
[ chemical formula 9]
[ chemical formula 10]
(2) With respect to B 1
B 1 Is a 2-valent group comprising 1 or more structural units and constituting a pi-conjugated system. Specifically, B 1 Is a cloud comprising more than one pair of atoms pi-bonded to each other and pi electrons are extended to B 1 An overall 2-valent group.
B 1 The structural unit of 1 or more of the above-mentioned components preferably comprises a structural unit represented by the following formula (III).
[ chemical formula 11]
In the formula (III) of the present invention,
Ar 1 and Ar is a group 2 Each independently represents an aromatic carbocyclic ring which may have a substituent or an aromatic heterocyclic ring which may have a substituent,
Y represents a group represented by a direct bond, -C (=O) -, or an oxygen atom,
r each independently represents:
a hydrogen atom,
Halogen atom,
An alkyl group which may have a substituent,
Cycloalkyl which may have a substituent,
Aryl which may have a substituent,
Alkoxy which may have a substituent,
A cycloalkoxy group which may have a substituent(s),
Aryloxy group which may have a substituent,
Alkylthio which may have a substituent,
A cycloalkylthio group which may have a substituent(s),
Arylthio which may have a substituent,
A 1-valent heterocyclic group which may have a substituent,
Substituted amino group which may have a substituent,
Acyl which may have a substituent,
An imine residue which may have a substituent,
An amide group which may have a substituent,
An imide group which may have a substituent,
A substituted oxycarbonyl group which may have a substituent(s),
Alkenyl group which may have substituent(s),
Cycloalkenyl group which may have substituent(s),
Alkynyl group which may have substituent(s),
A cycloalkynyl group which may have a substituent(s),
Cyano group,
Nitro group,
-C(＝O)-R a A group of the formula
-SO 2 -R b The radicals are shown in the figures,
R a and R is b Each independently represents:
a hydrogen atom,
An alkyl group which may have a substituent,
Aryl which may have a substituent,
Alkoxy which may have a substituent,
Aryloxy group which may have a substituent, or
A 1-valent heterocyclic group which may have a substituent.
The plurality of R's present may be the same or different from each other.
In the formula (III), ar may be constituted by 1 And Ar is a group 2 The aromatic carbocycle of (a) is preferably a benzene ring and a naphthalene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
Can form Ar 1 And Ar is a group 2 The aromatic heterocyclic ring of (a) is preferably an oxadiazole ring, a thiadiazole ring, a thiazole ring, an oxazole ring, a thiophene ring, a thienothiophene ring, a benzothiophene ring, a pyrrole ring, a phosphole ring, a furan ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, and a dibenzophosphole ring, as well as a phenoxazine ring, a phenothiazine ring, a dibenzoborole ring, a dibenzosilole ring, and a benzopyran ring. These rings may have a substituent.
The halogen atom represented by R is preferably a fluorine atom.
The alkyl group which may have a substituent(s) represented by R is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent(s), more preferably an alkyl group having 1 to 15 carbon atoms which may have a substituent(s), still more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent(s), and still more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent(s).
The substituent that the alkyl group shown by R may have is preferably a halogen atom, more preferably a fluorine atom and/or a chlorine atom.
The cycloalkyl group which may have a substituent(s) represented by R is preferably a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent(s), more preferably a cycloalkyl group having 5 to 6 carbon atoms which may have a substituent(s), and still more preferably a cyclohexyl group which may have a substituent(s).
The aryl group which may have a substituent(s) represented by R is preferably an aryl group having 6 to 15 carbon atoms which may have a substituent(s), and more preferably a phenyl group or a naphthyl group which may have a substituent(s).
The substituent which the aryl group represented by R may have is preferably a halogen atom (e.g., chlorine atom, fluorine atom), an alkyl group having 1 to 12 carbon atoms (e.g., methyl group, trifluoromethyl group, t-butyl group, octyl group, dodecyl group), an alkoxy group having 1 to 12 carbon atoms (e.g., methoxy group, ethoxy group, octoxy group), an alkylsulfonyl group having 1 to 12 carbon atoms (e.g., dodecylsulfonyl group), and/or a cyano group.
The alkoxy group which may have a substituent(s) represented by R is preferably an alkoxy group having 1 to 10 carbon atoms which may have a substituent(s), more preferably an alkoxy group having 1 to 8 carbon atoms which may have a substituent(s), and still more preferably a methoxy group, an ethoxy group, a propoxy group, a 3-methylbutoxy group or a 2-ethylhexyloxy group, and these groups may have a substituent(s).
The aryloxy group which may have a substituent(s) represented by R is preferably an aryloxy group which may have a substituent(s) having 6 to 15 carbon atoms, and more preferably a phenoxy group or an anthracenoxy group which may have a substituent(s).
The substituent that the aryloxy group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
The alkylthio group which may have a substituent(s) represented by R is preferably an alkylthio group having 1 to 6 carbon atoms which may have a substituent(s), more preferably an alkylthio group having 1 to 3 carbon atoms which may have a substituent(s), and still more preferably a methylthio group or a propylthio group which may have a substituent(s).
The arylthio group which may have a substituent(s) represented by R is preferably an arylthio group having 6 to 10 carbon atoms which may have a substituent(s), and more preferably a phenylthio group which may have a substituent(s).
The substituent that the arylthio group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
The 1-valent heterocyclic group which may have a substituent(s) shown in R is preferably a 5-or 6-membered 1-valent heterocyclic group which may have a substituent(s). Examples of the 5-membered 1-valent heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl and pyrrolidinyl. Examples of the 6-membered 1-valent heterocyclic group include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, piperidinyl, piperazinyl, morpholinyl and tetrahydropyranyl.
The 1-valent heterocyclic group which may have a substituent(s) shown in R is more preferably thienyl, furyl, thiazolyl, oxazolyl, pyridyl or pyrazinyl, which may have a substituent(s).
The substituent which the 1-valent heterocyclic group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms (e.g., methyl group, trifluoromethyl group, propyl group, hexyl group, octyl group, dodecyl group).
The alkenyl group which may have a substituent(s) represented by R is preferably an alkenyl group having 2 to 10 carbon atoms which may have a substituent(s), more preferably an alkenyl group having 2 to 6 carbon atoms which may have a substituent(s), and still more preferably a 2-propenyl group or a 5-hexenyl group which may have a substituent(s).
The cycloalkenyl group which may have a substituent(s) represented by R is preferably a cycloalkenyl group which may have a substituent(s) having 3 to 10 carbon atoms, more preferably a cycloalkenyl group which may have a substituent(s) having 6 to 7 carbon atoms, and still more preferably a cyclohexenyl or cycloheptenyl group which may have a substituent(s).
The substituent which the cycloalkenyl group represented by R may have is preferably an alkyl group having 1 to 12 carbon atoms.
The alkynyl group which may have a substituent(s) represented by R is preferably an alkynyl group having 2 to 10 carbon atoms which may have a substituent(s), more preferably an alkynyl group having 5 to 6 carbon atoms which may have a substituent(s), and still more preferably a 5-hexynyl group or a 3-methyl-1-butynyl group which may have a substituent(s).
The cyclic alkynyl group which may have a substituent(s) represented by R is preferably a cyclic alkynyl group having 6 to 10 carbon atoms which may have a substituent(s), more preferably a cyclic alkynyl group having 7 to 8 carbon atoms which may have a substituent(s), and still more preferably a cycloheptyl group or cyclooctyl group which may have a substituent(s).
The substituents which the cycloalkynyl group represented by R may have are preferably C1-C12 alkyl groups.
The plurality of R's are each independently preferably an alkyl group which may have a substituent, more preferably an alkyl group having 1 to 15 carbon atoms which may have a substituent, still more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and still more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent. It is particularly preferable that each of the plurality of R groups is an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R is-C (=O) -R a The radicals shown and-SO 2 -R b In the radicals shown, R a Preferably hydrogen atom, R b Preferably alkyl which may have a substituent or may have a substituentThe substituted alkoxy group is more preferably a substituted alkyl group having 1 to 12 carbon atoms or a substituted alkoxy group having 1 to 12 carbon atoms, still more preferably a substituted alkyl group having 1 to 12 carbon atoms or a substituted alkoxy group having 1 to 6 carbon atoms, still more preferably a methyl group, ethyl group, 2-methylpropyl group, octyl group, dodecyl group or ethoxy group, and these groups may have a substituent.
Examples of the structural unit represented by the formula (III) include structural units represented by the following formula.
[ chemical formula 12]
[ chemical formula 13]
[ chemical formula 14]
In the above formula, R is as described above.
Can be formed into B 1 The structural unit represented by the above formula (III) is preferably a structural unit represented by the following formula (IV).
[ chemical formula 15]
In formula (IV), Y and R are as described above. X is X 1 And X 2 Each independently represents a sulfur atom or an oxygen atom, Z 1 And Z 2 Each independently represents a group represented by =c (R) -or a nitrogen atom.
Examples of the structural unit represented by the formula (IV) include structural units represented by the following formula.
[ chemical formula 16]
Can be formed into B 1 The structural unit represented by the above formula (IV) is preferably a structural unit represented by the following formula (IV-1) which contains 2 or more thiophene rings and contains an sp3 carbon atom as a constituent element and may have a substituent.
[ chemical formula 17]
In formula (IV-1), Y and R are as defined above.
As a preferable specific example of the structural unit represented by the above formula (IV-1), a structural unit represented by the following formula is given.
[ chemical formula 18]
Can be formed into B 1 The structural unit represented by the formula (IV) may be a structural unit represented by the following formula (IV-2).
[ chemical formula 19]
In the formula (IV-2), X 1 And X 2 、Z 1 And Z 2 And R is as described above.
As examples of the structural unit represented by the formula (IV-2), structural units represented by the following formulas (IV-2-1) to (IV-2-16) can be given.
[ chemical formula 20]
As a preferable specific example of the structural unit represented by the formula (IV-2), a structural unit represented by the following formula is given.
[ chemical formula 21]
In the compound of the present embodiment, B 1 Preferably, the composition contains 1 structural unit represented by the above formula (III) or formula (IV) (hereinafter, referred to as the 1 st structural unit CU 1.).
B as a structural unit other than the structural unit represented by the above formula (III) or (IV) 1 Examples of the structural unit (hereinafter referred to as "structural unit 2 CU 2") that may be included include a 2-valent group including an unsaturated bond, a 2-valent aromatic carbocyclyl group, and a 2-valent aromatic heterocyclic group.
The "2-valent group containing an unsaturated bond" as the 2 nd structural unit CU2 is, for example, a group represented by- (cr=cr) n-, where R is defined as above, n is an integer of 1 or more, the value of n is preferably 1 or 2, more preferably 1.+ -.), -c≡c-, and a phenylene group.
Specific examples of the "2-valent group containing an unsaturated bond" include ethylene-1, 2-diyl, 1, 3-butadiene-1, 4-diyl, acetylene-1, 2-diyl and phenylene.
Specific examples of the "2-valent aromatic heterocyclic group" of the 2 nd structural unit CU2 include groups represented by the following formulae (101) to (191). These groups may further have a substituent.
[ chemical formula 22]
[ chemical formula 23]
[ chemical formula 24]
[ chemical formula 25]
In the formulae (101) to (191), R is as defined above.
Specific examples of the "2-valent aromatic carbocyclyl" of the 2 nd structural unit CU2 include phenylene (for example, the following formulae 1 to 3), naphthalene-diyl (for example, the following formulae 4 to 13), anthracene-diyl (for example, the following formulae 14 to 19), biphenyl-diyl (for example, the following formulae 20 to 25), terphenyl-diyl (for example, the following formulae 26 to 28), fused ring compound group (for example, the following formulae 29 to 35), fluorene-diyl (for example, the following formulae 36 to 38), and benzofluorene-diyl (for example, the following formulae 39 to 46).
[ chemical formula 26]
[ chemical formula 27]
[ chemical formula 28]
[ chemical formula 29]
[ chemical formula 30]
[ chemical formula 31]
[ chemical formula 32]
[ chemical formula 33]
In the formulae 1 to 46, R is as defined above.
In the compound of the present embodiment, the 2 nd structural unit CU2 is preferably a structural unit selected from the group consisting of a 2-valent group containing an unsaturated bond and a group represented by the following formulas (V-1) to (V-12), and more preferably a structural unit selected from the group represented by the formulas (V-10) to (V-12).
[ chemical formula 34]
In the formulae (V-1) to (V-12), X 1 、X 2 、Z 1 、Z 2 And R is as defined above.
In the case where there are 2R, the 2R may be the same or different from each other.
More specifically, preferable examples of the 2 nd structural unit CU2 include structural units represented by the following formulas. These structural units may further have a substituent.
[ chemical formula 35]
In the compound of the present embodiment, B 1 Comprises 1 or more structural units, at least 1 of the 1 or more structural units is a 1 st structural unit CU1, and the rest of the structural units except the 1 st structural unit CU1 is a 2 nd structural unit CU2.
B 1 The combination of the 1 st structural unit CU1 and the 2 nd structural unit CU2 and the arrangement thereof are not particularly limited as long as they can constitute a pi-conjugated system.
B 1 Preferably a 2-valent group having any 1 structure selected from the structures represented by the following formulas (VI-1) to (VI-16).
-CU1-(VI-1)
-CU1-CU1-(VI-2)
-CU1-CU2-(VI-3)
-CU1-CU1-CU1-(VI-4)
-CU1-CU2-CU1-(VI-5)
-CU1-CU1-CU2-(VI-6)
-CU1-CU2-CU2-(VI-7)
-CU2-CU1-CU2-(VI-8)
-CU1-CU1-CU1-CU1-(VI-9)
-CU1-CU1-CU1-CU2-(VI-10)
-CU1-CU1-CU2-CU1-(VI-11)
-CU1-CU1-CU2-CU2-(VI-12)
-CU1-CU2-CU1-CU2-(VI-13)
-CU1-CU2-CU2-CU1-(VI-14)
-CU1-CU2-CU2-CU2-(VI-15)
-CU2-CU1-CU2-CU2-(VI-16)
In the formulas (VI-1) to (VI-16),
CU1 represents the 1 st building block CU1,
CU2 represents the 2 nd structural unit CU2.
When there are 2 or more CUs 1, the 2 or more CUs 1 may be the same or different from each other, and when there are 2 or more CUs 2, the 2 or more CUs 2 may be the same or different from each other. Wherein the case where 2 CUs 2 are identical is not included in the formula (VI-8).
Among the above formulae (VI-1) to (VI-16), a 2-valent group having the structures represented by the formulae (VI-1) to (VI-8), the formulae (VI-15) and (VI-16) is preferable, and a 2-valent group having the structures represented by the formulae (VI-1), (VI-3), the formulae (VI-7), the formulae (VI-8), the formulae (VI-15) and (VI-16) is more preferable.
B 1 The total number of the 1 st and 2 nd structural units CU1 and CU2 that can be included in (a) is usually 1 or more, preferably 2 or more, more preferably 3 or more, usually 7 or less, preferably 5 or less, more preferably 4 or less.
B 1 The number of 1 st structural units CU1 that can be included in (a) is usually 5 or less, preferably 3 or less, and more preferably 1.
B 1 The number of the 2 nd structural units CU2 that can be included in (a) is usually 5 or less, preferably 3 or less, and more preferably 1 or less.
As B 1 Specific preferable examples of (a) include a 2-valent group represented by the following formula.
[ chemical formula 36]
[ chemical formula 37]
[ chemical formula 38]
[ chemical formula 39]
[ chemical formula 40]
[ chemical formula 41]
Wherein R is as defined above.
(3) Regarding D 1
In the compound of the present embodiment, D 1 Is a 1-valent group as an electron donating group.
Specifically, D 1 To have B as a 2-valent group constituting a pi-conjugated system 1 A functional 1-valent group having a further increased electron density. In the compound of the present embodiment, D 1 The value of the HOMO energy level of (C) is preferably less than A 1 The value of the HOMO energy level.
In the present embodiment, regarding D 1 Examples of the electron donating group include a 1-valent group having an unsaturated bond, a 1-valent aromatic carbocyclic group, a 1-valent aromatic heterocyclic group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an arylalkoxy group which may have a substituent, and an arylthioalkoxy group which may have a substituent.
Specific examples of the "1-valent group containing an unsaturated bond" of the electron donating group include vinyl group, 1, 3-butadiene-1-yl group, and acetylene group.
Examples of the "1-valent aromatic carbocyclyl" and "1-valent aromatic heterocyclic group" of the electron donating group include those in which 1 hydrogen atom directly bonded to the atom constituting the ring is removed from the triarylamine derivative; aryl, a 5-membered heterocyclic ring such as a thiophene ring, a furan ring, a pyrrole ring, cyclopentadiene, silacyclopentadiene, and the like, and a structure containing them as a condensed ring, and an atomic group remaining after 1 hydrogen atom directly bonded to an atom constituting the ring is removed.
Examples of the triarylamine derivative include triphenylamine, dinaphthylphenylamine, bis (4-alkylphenyl) phenylamine, bis (4-alkoxyphenyl) phenylamine, bis (9, 9-dimethylfluoren-2-yl) phenylamine, diphenylthienyl amine, bis (4-alkylphenyl) thienyl amine, bis (4-alkoxyphenyl) thienyl amine, and bis (9, 9-dimethylfluoren-2-yl) thienyl amine. Preferably triphenylamine, bis (4-alkylphenyl) phenylamine, bis (4-alkoxyphenyl) phenylamine.
Examples of the carbazole derivative include carbazole, 9-alkyl carbazole, and 9-aryl carbazole. Specifically, carbazole, 9-ethylcarbazole, 9-phenylcarbazole, 9-fluorenylcarbazole, and the like are mentioned. Carbazole is preferred.
Examples of the aryl group which may have a substituent(s) include phenyl, 4-alkoxyphenyl, 4-tetraethyleneoxyphenyl, 4-tetropolyl, 3,4, 5-trialkoxyphenyl, dimethylaminophenyl, diethylaminophenyl, pyrrolylphenyl, thienyl, alkylthienyl, alkoxythienyl, ethylenedioxythienyl, phenothiazinyl, thianthrenyl, and (in the Japanese), the use of the aryl group as a substituent(s) is exemplified by 4-track in the Japanese, コ -track in the Japanese, 3,4, 5-trialkoxyphenyl, dimethylaminophenyl, diethylaminophenyl, pyrrolylphenyl, thienyl, alkylthienyl, alkoxythienyl, ethylenedioxythienyl, phenothiazinyl, and thianthrene in the Japanese. Examples of the alkyl group of the alkylthienyl group and the alkoxy group of the alkoxythienyl group include those already described. In addition, a plurality of aryl groups in the aryl group may be linked. As the aryl group, diethylaminophenyl group, 3,4, 5-trialkoxyphenyl group, ethylenedioxythienyl group are preferable.
Examples of the alkylamino group which may have a substituent(s) include alkylamino groups having 1 to 8 carbon atoms such as methylamino, ethylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino and diisopropylamino, and dimethylamino is preferable.
Examples of the arylamino group which may have a substituent include a phenylamino group, a naphthylamino group, a diphenylamino group, a di-4-ethylphenylamino group, and a di-4-methylphenylamino group, and preferably a diphenylamino group.
Examples of the arylalkoxy group which may have a substituent(s) include arylalkoxy groups including phenyl, 4-alkoxyphenyl, 4-hexyloxyphenyl, 4-tetraethyleneoxyphenyl, 3,4, 5-trialkoxyphenyl, dimethylaminophenyl, diethylaminophenyl and pyrrolylphenyl groups as aryl groups which may have a substituent(s). As the arylalkoxy group, preferred is a phenoxy group or a 4-hexyloxyphenoxy group.
Examples of the arylthioalkoxy group which may have a substituent(s) include arylthioalkoxy groups including phenyl, 4-alkoxyphenyl, 4-hexyloxyphenyl, 4-tetraethyleneoxyphenyl, 3,4, 5-trialkoxyphenyl, dimethylaminophenyl, diethylaminophenyl and pyrrolylphenyl groups as aryl groups which may have a substituent(s). The aryl group in the arylthioalkoxy group is preferably 4-hexyloxyphenyl group.
Examples of the 5-membered heterocyclic ring such as a thiophene ring, a furan ring, a pyrrole ring, cyclopentadiene, or silacyclopentadiene, and a structure containing these as a condensed ring include fluorene, silafluorene, dithienocyclopentadiene, dithienosilocene, dithienopyrrole, and benzodithiophene.
Examples of the other 1-valent aromatic heterocyclic group include groups represented by the following formula.
[ chemical formula 42]
In the compound of the present embodiment, specifically, D 1 The preferred examples include an N-carbazolyl group, a diphenylamino group and a phenoxy group, and more preferred examples include an N-carbazolyl group, a diphenylamino group and a group of the following formula.
[ chemical formula 43]
Specific examples of the compound represented by the formula (I) of the present embodiment include compounds represented by the following formula.
[ chemical formula 44]
[ chemical formula 45]
[ chemical formula 46]
[ chemical formula 47]
[ chemical formula 48]
More specific preferable examples of the compound represented by the formula (I) of the present embodiment include compounds represented by the following formula.
[ chemical formula 49]
Among the compounds represented by the formula (I) as the compounds of the present embodiment, D is preferable from the viewpoint of reducing dark current 1 Energy level (E) D-LUMO ) Constitution B 1 Energy level (E) of LUMO of at least 1 structural unit (typically structural unit 1. Sup. CU.) of 1 structural units or more π-LUMO ) And A 1 Energy level (E) A-LUMO ) The conditions shown in the following formula are satisfied.
E D-LUMO ＞E B-LUMO ＞E A-LUMO
In addition, in the compound of the present embodimentOf the compounds of formula (I), the preferred structure B 1 Of the structural units having the lowest energy level of LUMO among 1 or more structural units (E B-LUMO ) min satisfies the condition shown in the following formula.
E D-LUMO ＞(E B-LUMO )min＞E A-LUMO
Among the compounds represented by the formula (I) as the compounds of the present embodiment, it is preferable to construct B 1 Average value (E) of energy levels of LUMO of 1 or more structural units B-LUMO ) ave satisfies the condition shown in the following formula.
E D-LUMO ＞(E B-LUMO )ave＞E A-LUMO
Structural unit (D) contained in the compound represented by formula (I) 1 、B 1 And A 1 ) The value (eV) of the LUMO level of (c) can be calculated by any conventionally known suitable calculation science method. As a method of computational science, for example, the following method can be applied: the structural optimization of the ground state was performed by density functional at the B3LYP level using the quantitative chemometric program Gaussian 03, using 6-31g of ANGSTROM as the basis function.
Specifically, the cutting structure unit (D 1 、B 1 And A 1 ) The structure (compound) of each structural unit in which hydrogen atoms are added to the bond formed by cleavage can be calculated by applying the above-described method to each structural unit.
The compound of the present embodiment can be suitably used as a semiconductor material of an active layer of a photoelectric conversion element, particularly as a non-fullerene compound of an n-type semiconductor material.
In particular, if the compound of the present embodiment is used as an n-type semiconductor material for the active layer, dark current required for a photoelectric conversion element as a light detection element can be effectively reduced.
The compound of the present embodiment used as an n-type semiconductor material may be contained in 2 or more kinds of materials for the active layer.
The active layer of the photoelectric conversion element (described in detail below) may include, in particular, only the compound of the present embodiment as an n-type semiconductor material, or may include, as another n-type semiconductor material, a compound other than the compound of the present embodiment as an n-type semiconductor material. The compounds other than the compounds of the present embodiment, which may be included as other n-type semiconductor materials, may be low-molecular compounds or high-molecular compounds.
Examples of the n-type semiconductor material (electron-accepting compound) other than the "compound of the present embodiment" of the low-molecular compound include oxadiazole derivatives, anthraquinone dimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinone dimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and phenanthrene derivatives such as bathocuproine.
Examples of the n-type semiconductor material other than the "compound of the present embodiment" of the polymer compound include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in a side chain or a main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylacetylene (japanese) and its derivatives, polythiophene acetylene (japanese) and its derivatives, poly (quinoline) and its derivatives, polyquinoxaline and its derivatives, and polyfluorene and its derivatives.
The compound other than the "compound of the present embodiment" may contain a fullerene derivative.
Here, the fullerene derivative means fullerene (C 60 Fullerene, C 70 Fullerene, C 76 Fullerene, C 78 Fullerene and C 84 Fullerene) and a compound in which at least a part of the fullerene is modified. In other words, the term "compound" refers to a compound having 1 or more groups added to a fullerene skeleton. Hereinafter, in particular, C may be mentioned 60 Fullerene derivatives of fullerenes are referred to as "C 60 Fullerene derivative ", C 70 Fullerene derivatives of fullerenes are referred to as "C 70 Fullerene derivatives).
The fullerene derivative which can be used as an n-type semiconductor material other than the "compound of the present embodiment" is not particularly limited as long as the object of the present invention is not impaired.
C which can be used as an n-type semiconductor material other than the "Compound of the present embodiment 60 Specific examples of the fullerene derivative include the following compounds.
[ chemical formula 50]
Wherein R is as defined above. In the case where a plurality of R's exist, the plurality of R's may be the same as or different from each other.
As C 70 Examples of fullerene derivatives include the following compounds.
[ chemical formula 51]
2. Photoelectric conversion element
The photoelectric conversion element of the present embodiment is a photoelectric conversion element as follows: comprises an anode, a cathode, and an active layer which is provided between the anode and the cathode and comprises a p-type semiconductor material and an n-type semiconductor material, and comprises the compound of the present embodiment which has been described as the n-type semiconductor material.
According to the photoelectric conversion element of the present embodiment, the dark current required for the photoelectric conversion element as a light detection element can be effectively reduced by having the above-described configuration.
Here, a description will be given of a configuration example that can be adopted for the photoelectric conversion element of the present embodiment. Fig. 1 is a diagram schematically showing the structure of a photoelectric conversion element according to the present embodiment.
As shown in fig. 1, the photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes: an anode 12 provided in contact with the support substrate 11, a hole transport layer 13 provided in contact with the anode 12, an active layer 14 provided in contact with the hole transport layer 13, an electron transport layer 15 provided in contact with the active layer 14, and a cathode 16 provided in contact with the electron transport layer 15. In this configuration example, a sealing member 17 is further provided so as to be in contact with the cathode 16.
Hereinafter, components that can be included in the photoelectric conversion element of the present embodiment will be specifically described.
(substrate)
The photoelectric conversion element is generally formed on a substrate (supporting substrate). In addition, sealing may be performed by a substrate (sealing substrate). One of a pair of electrodes composed of an anode and a cathode is generally formed on a substrate. The material of the substrate is not particularly limited as long as it is a material that does not undergo chemical change when forming a layer containing an organic compound in particular.
Examples of the material of the substrate include glass, plastic, polymer film, and silicon. In the case of using an opaque substrate, an electrode on the opposite side to an electrode provided on the opaque substrate side (in other words, an electrode on the side away from the opaque substrate) is preferably made transparent or translucent.
(electrode)
The photoelectric conversion element includes an anode and a cathode as a pair of electrodes. For light incidence, at least one of the anode and the cathode is preferably provided as a transparent or semitransparent electrode.
Examples of the material of the transparent or semitransparent electrode include a conductive metal oxide film and a semitransparent metal thin film. Specifically, indium oxide, zinc oxide, tin oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), NESA, and other conductive materials, gold, platinum, silver, and copper, which are composites of these materials, are exemplified. As a material of the transparent or semitransparent electrode, ITO, IZO, and tin oxide are preferable. As the electrode, a transparent conductive film using an organic compound such as polyaniline or a derivative thereof, polythiophene or a derivative thereof as a material can be used. The transparent or semitransparent electrode may be an anode or a cathode.
If one of the pair of electrodes is transparent or translucent, the other electrode may be an electrode having low light transmittance. Examples of the material of the electrode having low light transmittance include metals and conductive polymers. Specific examples of the material of the electrode having low light transmittance include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and alloys of 2 or more thereof; or an alloy of 1 or more of them with 1 or more metals selected from gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin; graphite, graphite intercalation compounds, polyaniline and derivatives thereof, polythiophene and derivatives thereof. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
(active layer)
The active layer provided in the photoelectric conversion element of the present embodiment is assumed to have a bulk heterojunction structure, and includes a p-type semiconductor material and an n-type semiconductor material, and the compound of the present embodiment is included as the n-type semiconductor material (details will be described later).
In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer may be set to any suitable thickness in consideration of the balance between suppression of dark current and extraction of generated photocurrent. In particular, from the viewpoint of further reducing dark current, the thickness of the active layer is preferably 100nm or more, more preferably 150nm or more, and even more preferably 200nm or more. The thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less.
Here, as a material of the active layer of the present embodiment, a p-type semiconductor material which can be suitably used in combination with the n-type semiconductor material which is the compound of the present embodiment described above will be described.
The p-type semiconductor material of the present embodiment is preferably a polymer compound having a predetermined weight average molecular weight in terms of polystyrene.
The p-type semiconductor material of the present embodiment is preferably a polymer compound having an absorption peak wavelength of more than 700 nm.
The "absorption peak wavelength" can be measured by using any conventionally known suitable ultraviolet-visible near-infrared spectrophotometer (for example, "JASCO-V670" manufactured by Japanese Spectroscopy Co.).
The weight average molecular weight in terms of polystyrene herein refers to a weight average molecular weight calculated using Gel Permeation Chromatography (GPC) and using a standard sample of polystyrene.
In particular, from the viewpoint of improving the solubility in a solvent, the weight average molecular weight of the p-type semiconductor material in terms of polystyrene is preferably 3000 or more and 500000 or less.
In this embodiment mode, the p-type semiconductor material is preferably a pi-conjugated polymer compound (also referred to as a D-a conjugated polymer compound or simply conjugated polymer compound) including a donor structural unit (also referred to as a D structural unit) and an acceptor structural unit (also referred to as a structural unit). It should be noted that which is the donor structural unit or the acceptor structural unit may be relatively determined according to the energy level of HOMO or LUMO.
The donor structural unit is a pi electron excess structural unit, and the acceptor structural unit is a pi electron deficiency structural unit.
In this embodiment mode, the structural unit constituting the p-type semiconductor material may further include a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, and a structural unit in which a donor structural unit and an acceptor structural unit are bonded via any suitable spacer (group or structural unit).
Examples of the p-type semiconductor material of the polymer compound include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives having an aromatic amine structure in a side chain or a main chain, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylacetylene and its derivatives, polythiophene acetylene and its derivatives, polyfluorene and its derivatives.
The polymer compound according to the present embodiment containing a structural unit represented by the following formula (VII) is preferable. The structural unit represented by the following formula (VII) is usually a donor structural unit in this embodiment.
[ chemical formula 52]
In the formula (VII), ar 3 And Ar is a group 4 And Z represents a group represented by the following formulas (Z-1) to (Z-7).
[ chemical formula 53]
In the formulas (Z-1) to (Z-7),
r is as defined above.
In the case where 2R groups are present in each of the groups represented by the formulae (Z-1) to (Z-7), 2R groups may be the same or different from each other.
Can form Ar 3 And Ar is a group 4 The aromatic heterocyclic ring of (2) includes, in addition to a single ring and a condensed ring which themselves exhibit aromaticity, a ring in which an aromatic ring is condensed on a heterocyclic ring although the heterocyclic ring itself constituting the ring does not exhibit aromaticity.
Can form Ar 3 And Ar is a group 4 The aromatic heterocyclic ring of (2) may be a single ring or a condensed ring. When the aromatic heterocycle is a condensed ring, all of the rings constituting the condensed ring may be condensed rings having aromaticity, or only a part of the rings may be condensed rings having aromaticity. In the case where these rings have a plurality of substituents, these substituents may be the same or different.
As can constitute Ar 3 And Ar is a group 4 Specific examples of the aromatic carbocycle include a benzene ring,Naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, and phenanthrene ring, preferably benzene ring and naphthalene ring, more preferably benzene ring and naphthalene ring, and further preferably benzene ring. These rings may have a substituent.
Specific examples of the aromatic heterocycle include ring structures of the compounds described as the aromatic heterocyclic compounds, such as oxadiazole ring, thiadiazole ring, thiazole ring, oxazole ring, thiophene ring, pyrrole ring, phosphole ring, furan ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, quinoline ring, isoquinoline ring, carbazole ring and dibenzophosphole ring, and phenoxazine ring, phenothiazine ring, dibenzoborole ring, dibenzosilole ring and benzopyran ring. These rings may have a substituent.
The structural unit represented by the formula (VII) is preferably a structural unit represented by the following formula (VIII) or (IX). In other words, in this embodiment, the p-type semiconductor material is preferably a polymer compound including a structural unit represented by the following formula (VIII) or (IX).
[ chemical formula 54]
Ar in formulae (VIII) and (IX) 3 、Ar 4 And R is as defined above.
Examples of suitable structural units represented by the formulae (VII) and (IX) include structural units represented by the following formulae (VII-1) and (VII-2) and formulae (IX-1) and (IX-2).
[ chemical formula 55]
In the formula (VII-1), the formula (VII-2), the formula (IX-1) and the formula (IX-2),
r is as defined above.
In the case where there are 2R, the 2R may be the same or different.
As more specific preferable examples of the structural unit represented by the formula (VII-1), structural units represented by the following formulas (VII-1-1) and (VII-1-2) can be given.
[ chemical formula 56]
The structural unit represented by the formula (VIII) is preferably a structural unit represented by the following formula (X). In other words, in this embodiment, the p-type semiconductor material may be a polymer compound including a structural unit represented by the following formula (X).
[ chemical formula 57]
In the formula (X), the amino acid sequence of the formula (X),
X 1 and X 2 Each independently is a sulfur atom or an oxygen atom,
Z 1 And Z 2 Each independently is a group represented by =c (R) -or a nitrogen atom,
r is as defined above.
Examples of the preferable structural unit represented by the formula (IX) include structural units represented by the following formulas (X-1) to (X-16).
[ chemical formula 58]
As the structural unit represented by the formula (X), X is preferable 1 And X 2 Is sulfur atom, Z 1 And Z 2 Structural unit of group shown as = C (R) -.
In this embodiment, the polymer compound as the p-type semiconductor material preferably contains a structural unit represented by the following formula (XI). The structural unit represented by the following formula (XI) is usually a receptor structural unit in this embodiment.
[ chemical formula 59]
-Ar 5 -(XⅠ)
In the formula (XI), ar 5 Represents a 2-valent aromatic heterocyclic group.
Ar 5 The number of carbon atoms of the 2-valent aromatic heterocyclic group is usually 2 to 60, preferably 4 to 60, more preferably 4 to 20.
Ar 5 The illustrated 2-valent aromatic heterocyclic group may have a substituent. As Ar 5 Examples of the substituent which the 2-valent aromatic heterocyclic group may have include a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a 1-valent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, an acyl group which may have a substituent, an imine residue which may have a substituent, an amide group which may have a substituent, an imide group which may have a substituent, a substituted oxycarbonyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a cyano group and a nitro group.
As the structural unit represented by the formula (X), structural units represented by the following formulas (X-1) to (X-10) are preferable.
[ chemical formula 60]
In the formulae (X-1) to (X-10),
X 1 、X 2 、Z 1 、Z 2 and R is as defined above.
In the case where there are 2R, the 2R may be the same or different from each other.
X in the formulae (X-1) to (X-10) from the viewpoint of availability of the starting compounds 1 And X 2 Preferably all are sulfur atoms.
The structural units represented by the formulae (X-1) to (X-10) may generally function as acceptor structural units as described above. However, the structural units represented by the formula (X-4), the formula (X-5) and the formula (X-7) are not limited thereto, and may function as donor structural units.
In this embodiment, the p-type semiconductor material is preferably a pi-conjugated polymer compound including a structural unit including a thiophene skeleton and including a pi-conjugated system.
As Ar 5 Specific examples of the 2-valent aromatic heterocyclic group include groups represented by the following formulas (101) to (191). These groups may further have a substituent.
[ chemical formula 61]
[ chemical formula 62]
[ chemical formula 63]
[ chemical formula 64]
In the formulae (101) to (191), R is as defined above. In the case where a plurality of R's exist, the plurality of R's may be the same as or different from each other.
The polymer compound as the p-type semiconductor material of the present embodiment is preferably a pi-conjugated polymer compound containing a structural unit represented by formula (VI) as a donor structural unit and a structural unit represented by formula (X) as an acceptor structural unit.
The polymer compound as the p-type semiconductor material may contain 2 or more structural units represented by the formula (VI), or may contain 2 or more structural units represented by the formula (X).
For example, the polymer compound as the p-type semiconductor material of the present embodiment may contain a structural unit represented by the following formula (XII) from the viewpoint of improving the solubility in a solvent.
[ chemical formula 65]
-Ar 6 -(XII)
In the formula (XII), ar 6 Represents a 2-valent aromatic carbocyclyl group.
Ar 6 The 2-valent aromatic carbocyclyl group shown here means an atomic group remaining after 2 hydrogen atoms are removed from an aromatic hydrocarbon which may have a substituent. The aromatic hydrocarbon also includes a compound having a condensed ring, and a compound in which 2 or more members selected from independent benzene rings and condensed rings are bonded directly or via a 2-valent group such as a vinylidene group.
Examples of the substituent that the aromatic hydrocarbon may have include the same substituents as those exemplified as the substituent that the heterocyclic compound may have.
Ar 6 The number of carbon atoms of the 2-valent aromatic carbocyclic group shown does not include the number of carbon atoms of the substituent, and is usually 6 to 60, preferably 6 to 20. The number of carbon atoms including substituents is usually 6 to 100.
As Ar 6 Examples of the 2-valent aromatic carbocyclyl group include phenylene groups (for example, formula 1 to formula 3 below), naphthalene-diyl groups (for example, formula 4 to formula 13 below), anthracene-diyl groups (for example, formula 14 to formula 19 below), biphenyl-diyl groups (for example, formula 20 to formula 25 below), terphenyl-diyl groups (for example, formula 26 to formula 28 below), condensed ring compounds (for example, formula 29 to formula 35 below), fluorene-diyl groups (for example, formula 36 to formula 38 below), and benzofluorene-diyl groups (for example, formula 39 to formula 46 below).
[ chemical formula 66]
[ chemical formula 67]
[ chemical formula 68]
[ chemical formula 69]
[ chemical formula 70]
[ chemical formula 71]
[ chemical formula 72]
[ chemical formula 73]
Wherein R is as defined above. The plurality of R's present may be the same or different from each other.
The structural unit represented by the formula (XII) is preferably a structural unit represented by the following formula (XIII).
[ chemical formula 74]
In formula (XIII), R is as defined above. The 2R's present may be the same or different from each other.
The structural unit constituting the polymer compound as the p-type semiconductor material may be a structural unit in which 2 or more structural units selected from the above structural units are combined and connected.
When the polymer compound as the p-type semiconductor material contains the structural unit represented by the formula (VI) and/or the structural unit represented by the formula (X), the total amount of the structural unit represented by the formula (VI) and the structural unit represented by the formula (X) is usually 20 to 100 mol%, and is preferably 40 to 100 mol%, and more preferably 50 to 100 mol% for the reason that the charge transport property as the p-type semiconductor material can be improved.
Specific examples of the polymer compound as the P-type semiconductor material of the present embodiment include polymer compounds represented by the following formulas (P-1) to (P-17).
[ chemical formula 75]
[ chemical formula 76]
[ chemical formula 77]
[ chemical formula 78]
[ chemical formula 79]
[ chemical formula 80]
[ chemical formula 81]
Wherein R is as defined above. The plurality of R's present may be the same or different from each other.
When the above-described exemplary polymer compound is used as the p-type semiconductor material, dark current required for the photoelectric conversion element as the light detection element can be effectively reduced in particular.
(intermediate layer)
As shown in fig. 1, the photoelectric conversion element of the present embodiment 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.
Examples of the material used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and mixtures of PEDOT (poly (3, 4-ethylenedioxythiophene)) and PSS (poly (4-styrenesulfonate)) (PEDOT: PSS).
As shown in fig. 1, the photoelectric conversion element preferably includes a hole transport layer between the anode and the active layer. The hole transport layer has a function of transporting holes from the active layer to the electrode.
The hole transport layer provided in contact with the anode is sometimes referred to as a hole injection layer in particular. The hole transport layer (hole injection layer) provided in contact with the anode has a function of promoting injection of holes into the anode. The hole transport layer (hole injection layer) may be in contact with the active layer.
The hole transport layer contains a hole transporting material. Examples of the hole-transporting material include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing a structural unit having an aromatic amine residue, cuSCN, cuI, niO, and tungsten oxide (WO) 3 ) And molybdenum oxide (MoO) 3 )。
The intermediate layer may be formed by any suitable forming method known in the art. The intermediate layer may be formed by vacuum vapor deposition or by a coating method similar to the method for forming the active layer.
The photoelectric conversion element of the present embodiment preferably has a structure in which an intermediate layer is an electron transport layer, and a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are stacked in this order so as to be in contact with each other.
As shown in fig. 1, the photoelectric conversion element of the present embodiment preferably includes an electron transport layer as an intermediate layer between the cathode and the active layer. The electron transport layer has a function of transporting electrons from the active layer to the cathode. The electron transport layer may be in contact with the cathode. The electron transport layer may be in contact with the active layer.
The electron transport layer provided in contact with the cathode is sometimes referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the cathode has a function of promoting injection of electrons generated in the active layer to the cathode.
The electron transport layer comprises an electron transport material. Examples of the electron-transporting material include polyalkyleneimines (japanese) and derivatives thereof, a polymer compound containing a fluorene structure, and a metal such as calcium, and a metal oxide.
Examples of polyalkyleneimines and derivatives thereof include polymers obtained by polymerizing one or more of ethyleneimines, propyleneimines, butyleneimines, dimethylethyleneimines, pentenimines, hexeneimines, hepteneimines, octeneimines and the like having 2 to 8 carbon atoms, particularly, alkylene imines having 2 to 4 carbon atoms by a conventional method, and polymers obtained by chemically modifying these by reacting them with various compounds. As the polyalkyleneimine and its derivative, polyethyleneimine (PEI) and ethoxylated Polyethyleneimine (PEIE) are preferable.
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.
Examples of the metal oxide include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, a metal oxide containing zinc is preferable, and among them, zinc oxide is preferable.
Examples of other electron-transporting materials include poly (4-vinylphenol) and perylene diimide.
(sealing Member)
The photoelectric conversion element of the present embodiment further includes a sealing member, and preferably a sealing body sealed by the sealing member is formed.
Any suitable conventionally known sealing member may be used. As an example of the sealing member, a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin is given.
The sealing member may be a sealing layer of a layer structure of 1 layer or more. Examples of the layer constituting the sealing layer include a gas barrier layer and a gas barrier film.
The sealing layer is preferably formed of a material having a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of suitable materials for the material of the sealing layer include organic materials such as trifluoroethylene, polytrifluoroethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.
The sealing member is generally composed of a material capable of withstanding a heat treatment performed when assembled to a device to which a photoelectric conversion element is applied, for example, the application example described below.
(3) Use of photoelectric conversion element
Examples of the use of the photoelectric conversion element according to the present embodiment include a photodetector and a solar cell.
More specifically, the photoelectric conversion element of the present embodiment can circulate photocurrent by irradiating light from the transparent or translucent electrode side in a state where a voltage (reverse bias voltage) is applied between the electrodes, and can operate as a photodetecting element (photosensor). In addition, it is also possible to use as an image sensor by integrating a plurality of light detection elements. The photoelectric conversion element of the present embodiment can be particularly suitably used as a light detection element.
In addition, the photoelectric conversion element according to the present embodiment can generate a photovoltaic potential between electrodes by being irradiated with light, and can operate as a solar cell. The solar cell module may also be manufactured by integrating a plurality of photoelectric conversion elements.
(4) Application example of photoelectric conversion element
The photoelectric conversion element according to the present embodiment can be suitably applied as a light detection element to detection units included in various electronic devices such as a workstation, a personal computer, a portable information terminal, a room entrance/exit management system, a digital camera, and a medical device.
The photoelectric conversion element according to the present embodiment is suitably applied to an image detection unit (for example, an image sensor such as an X-ray imaging device or a CMOS image sensor) for a solid-state imaging device, a fingerprint detection unit, a face detection unit, a vein detection unit, an iris detection unit, or the like, which are provided in the above-described electronic device, for example, a detection unit (for example, a near infrared sensor) of a biological information recognition device that detects a specific feature of a part of a living body, a detection unit (for example, a pulse oximeter, or the like) of an optical biological sensor such as a pulse oximeter, or the like.
The photoelectric conversion element of the present embodiment can be further suitably applied to a Time-of-flight (TOF) type distance measuring device (TOF type distance measuring device) as an image detecting unit for a solid-state imaging device.
In the TOF type distance measuring device, the distance is measured by receiving reflected light, which is reflected by the object to be measured by the light emitted from the light source, by the photoelectric conversion element. Specifically, the time of flight until the irradiation light emitted from the light source is reflected by the object to be measured and returned as reflected light is detected, and the distance to the object to be measured is obtained. The TOF type exists in a direct TOF mode and an indirect TOF mode. In the direct TOF method, the difference between the time when light is irradiated from the light source and the time when reflected light is received by the photoelectric conversion element is directly measured, and in the indirect TOF method, the distance is measured by converting the change in the charge accumulation amount depending on the time of flight into a time change. Among distance measurement principles for obtaining a time of flight by charge accumulation used in the indirect TOF method, there are a continuous wave (in particular, sine wave) modulation method and a pulse modulation method for obtaining a time of flight from a phase of a reflected light reflected by a measurement object and a radiation light from a light source.
The following describes, with reference to the drawings, a configuration example in which an image detection unit for a solid-state imaging device and an image detection unit for an X-ray imaging device, a fingerprint detection unit and a vein detection unit for a biometric apparatus (for example, a fingerprint recognition apparatus, a vein recognition apparatus, and the like), and an image detection unit of a TOF type distance measuring apparatus (indirect TOF system) are appropriately applied to the detection units of the photoelectric conversion elements of the present embodiment.
(image detection section for solid-state imaging device)
Fig. 2 is a diagram schematically showing a configuration example of an image detection unit for a solid-state imaging device.
The image detection unit 1 includes: a CMOS transistor substrate 20; an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20; the photoelectric conversion element 10 of the embodiment of the present invention provided on the interlayer insulating film 30; an interlayer wiring portion 32 that is provided so as to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10; a sealing layer 40 provided so as to cover the photoelectric conversion element 10; and a color filter 50 disposed on the sealing layer 40.
The CMOS transistor substrate 20 has any conventionally known suitable structure in a manner corresponding to the design.
The CMOS transistor substrate 20 includes functional elements such as CMOS transistor circuits (MOS transistor circuits) including transistors, capacitors, and the like formed within the thickness of the substrate, and for realizing various functions.
Examples of the functional element include a floating diffusion element (a diurnal diffusion element), a reset transistor, an output transistor, and a selection transistor.
A signal readout circuit or the like is fabricated on the CMOS transistor substrate 20 by such functional elements, wirings, and the like.
The interlayer insulating film 30 may be made of any conventionally known insulating material such as silicon oxide or insulating resin. The interlayer wiring portion 32 may be made of any conventionally known conductive material (wiring material), such as copper or tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or may be a buried plug formed separately from the wiring layer.
The sealing layer 40 may be made of any conventionally known suitable material under the condition that permeation of harmful substances such as oxygen and water, which may deteriorate the functionality of the photoelectric conversion element 10, can be prevented or suppressed. The sealing layer 40 may have the same structure as the sealing member 17 described above.
As the color filter 50, for example, a primary color filter which is made of any appropriate material known in the art and which corresponds to the design of the image detection unit 1 can be used. As the color filter 50, a complementary color filter having a reduced thickness compared with the primary color filter may be used. As the complementary color filter, for example, a color filter formed by combining 3 types of (yellow, cyan, magenta), 3 types of (yellow, cyan, transparent), 3 types of (yellow, transparent, magenta), and 3 types of (transparent, cyan, magenta) may be used. These may be provided in any suitable configuration corresponding to the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that color image data can be generated.
The light received by the photoelectric conversion element 10 through the color filter 50 is converted into an electric signal corresponding to the amount of light received by the photoelectric conversion element 10, and is output to the outside of the photoelectric conversion element 10 as a light-receiving signal, that is, an electric signal corresponding to the object to be photographed, through the electrode.
Then, the light receiving signal outputted from the photoelectric conversion element 10 is inputted to the CMOS transistor substrate 20 via the interlayer wiring portion 32, and is read out by a signal reading circuit formed on the CMOS transistor substrate 20, and is subjected to signal processing by any other suitable conventionally known functional portion not shown, thereby generating image information based on the object to be photographed.
(fingerprint detection section)
Fig. 3 is a diagram schematically showing a configuration example of a fingerprint detection section integrally configured with a display device.
The display device 2 of the portable information terminal includes: a fingerprint detection section 100 including the photoelectric conversion element 10 according to the embodiment of the present invention as a main constituent element; and a display panel section 200 provided on the fingerprint detection section 100 and displaying a predetermined image.
In this configuration example, the fingerprint detection section 100 is provided in a region that coincides with the display region 200a of the display panel section 200. In other words, the display panel section 200 is integrally laminated above the fingerprint detection section 100.
In the case where fingerprint detection is performed only in a partial area of the display area 200a, the fingerprint detection section 100 may be provided only in correspondence with the partial area.
The fingerprint detection section 100 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional section that performs a substantial function. The fingerprint detection section 100 may include any suitable conventionally known member such as a protection film (not shown), a support substrate, a sealing member, a blocking film, a band pass filter, and an infrared cut film so as to correspond to a design that obtains desired characteristics. The fingerprint detection section 100 may be configured as the image detection section described above.
The photoelectric conversion element 10 may be included in the display region 200a in any manner. For example, the plurality of photoelectric conversion elements 10 may be arranged in a matrix.
As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the electrodes (first electrodes or second electrodes) are provided on the support substrate 11 in a matrix, for example.
The light received by the photoelectric conversion element 10 is converted into an electric signal corresponding to the amount of light received by the photoelectric conversion element 10, and is output to the outside of the photoelectric conversion element 10 via the electrode in the form of a light-receiving signal, that is, an electric signal corresponding to the captured fingerprint.
In this configuration example, the display panel section 200 is configured as an organic electroluminescence display panel (organic EL display panel) including a touch sensor panel. The display panel section 200 may be configured by a display panel having any suitable conventionally known configuration, such as a liquid crystal display panel including a light source such as a backlight, instead of the organic EL display panel.
The display panel section 200 is provided on the fingerprint detection section 100 already described. The display panel section 200 includes an organic electroluminescent element (organic EL element) 220 as a functional section that performs a substantial function. The display panel section 200 may further include any suitable conventionally known substrate (support substrate 210 or sealing substrate 240) such as a glass substrate, a sealing member, a polarizing plate such as a barrier film or a circularly polarizing plate, or any suitable conventionally known member such as a touch sensor panel 230 so as to correspond to desired characteristics.
In the configuration example described above, the organic EL element 220 is used as a light source for pixels in the display area 200a, and is also used as a light source for capturing a fingerprint in the fingerprint detection section 100.
The operation of the fingerprint detection section 100 will be briefly described.
In performing fingerprint recognition, the fingerprint detection section 100 detects a fingerprint using light emitted from the organic EL element 220 of the display panel section 200. Specifically, the light emitted from the organic EL element 220 is transmitted through the constituent elements existing between the organic EL element 220 and the photoelectric conversion element 10 of the fingerprint detection section 100, and is reflected by the skin (finger surface) of the finger tip of the finger placed in contact with the surface of the display panel section 200 in the display area 200 a. At least a part of the light reflected by the finger surface is received by the photoelectric conversion element 10 through the constituent elements present therebetween, and converted into an electric signal according to the light receiving amount of the photoelectric conversion element 10. Then, image information related to the fingerprint of the finger surface is constructed from the converted electric signals.
The portable information terminal provided with the display device 2 performs fingerprint recognition by comparing the obtained image information with the fingerprint data for the pre-recorded fingerprint recognition by any conventionally known suitable procedure.
(image detection section for X-ray imaging device)
Fig. 4 is a diagram schematically showing a configuration example of an image detection unit for an X-ray imaging device.
The image detection unit 1 for an X-ray imaging device includes: a CMOS transistor substrate 20; an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20; the photoelectric conversion element 10 of the embodiment of the present invention provided on the interlayer insulating film 30; an interlayer wiring portion 32 that is provided so as to penetrate the interlayer insulating film 30 and electrically connects the CMOS transistor substrate 20 and the photoelectric conversion element 10; a sealing layer 40 provided so as to cover the photoelectric conversion element 10; a scintillator 42 disposed on the sealing layer 40; a reflection layer 44 provided so as to cover the scintillator 42; and a protective layer 46 provided so as to cover the reflective layer 44.
The CMOS transistor substrate 20 has any conventionally known suitable structure in a manner corresponding to the design.
The CMOS transistor substrate 20 includes functional elements such as CMOS transistor circuits (MOS transistor circuits) including transistors, capacitors, and the like formed within the thickness of the substrate, and for realizing various functions.
Examples of the functional element include a floating diffusion element, a reset transistor, an output transistor, and a selection transistor.
A signal readout circuit or the like is fabricated on the CMOS transistor substrate 20 by such functional elements, wirings, and the like.
The interlayer insulating film 30 may be made of any conventionally known insulating material such as silicon oxide or insulating resin. The interlayer wiring portion 32 may be made of any conventionally known conductive material (wiring material), such as copper or tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or may be a buried plug formed separately from the wiring layer.
The sealing layer 40 may be made of any conventionally known suitable material under the condition that permeation of harmful substances such as oxygen and water, which may deteriorate the functionality of the photoelectric conversion element 10, can be prevented or suppressed. The sealing layer 40 may have the same structure as the sealing member 17 described above.
The scintillator 42 may be made of any conventionally known suitable material corresponding to the design of the image detection unit 1 for an X-ray imaging device. As examples of suitable materials for the scintillator 42, inorganic crystals of inorganic materials such as CsI (cesium iodide), naI (sodium iodide), znS (zinc sulfide), GOS (gadolinium oxysulfide), GSO (gadolinium silicate) and the like can be used; organic crystals of organic materials such as anthracene, naphthalene, stilbene; an organic liquid obtained by dissolving an organic material such as diphenyl oxazole (PPO) or Terphenyl (TP) in an organic solvent such as toluene, xylene or dioxane; gases such as xenon, helium; plastics, and the like.
The above-described components may be arranged in any suitable manner in accordance with the design of the photoelectric conversion element 10 and the CMOS transistor substrate 20, provided that the scintillator 42 can convert the incident X-rays into light having a wavelength centered on the visible light region to generate image data.
The reflective layer 44 reflects the light converted by the scintillator 42. The reflection layer 44 can reduce loss of converted light and increase detection sensitivity. The reflective layer 44 can also block light directly incident from the outside.
The protective layer 46 may be made of any conventionally known suitable material, provided that it can prevent or inhibit permeation of harmful substances such as oxygen and water, which may deteriorate the functionality of the scintillator 42.
The operation of the image detection unit 1 for an X-ray imaging device having the above-described configuration will be briefly described.
If radiation energy such as X-rays or γ -rays is incident on the scintillator 42, the scintillator 42 absorbs the radiation energy and converts the radiation energy into light (fluorescence) having a wavelength ranging from ultraviolet to infrared with the visible light region as the center. Then, the light converted by the scintillator 42 is received by the photoelectric conversion element 10.
In this way, the light received by the photoelectric conversion element 10 via the scintillator 42 is converted into an electric signal corresponding to the amount of light received by the photoelectric conversion element 10, and is output to the outside of the photoelectric conversion element 10 via the electrode as a light-receiving signal, that is, an electric signal corresponding to the object to be photographed. The radiation energy (X-ray) as the detection target may be incident from any one of the scintillator 42 side and the photoelectric conversion element 10 side.
Then, the light receiving signal outputted from the photoelectric conversion element 10 is inputted to the CMOS transistor substrate 20 via the interlayer wiring portion 32, and is read out by a signal reading circuit formed on the CMOS transistor substrate 20, and is subjected to signal processing by any other suitable conventionally known functional portion not shown, thereby generating image information based on the object to be photographed.
(vein detection section)
Fig. 5 is a diagram schematically showing a configuration example of a vein detection unit for a vein recognition apparatus. The vein detection unit 300 for a vein recognition device is configured by a cover 306, a light source 304, a photoelectric conversion element 10, a support substrate 11, and a glass substrate 302, wherein the cover 306 defines an insertion portion 310 into which a finger (for example, a fingertip, a finger, and a palm of 1 or more fingers) to be measured is inserted during measurement, the light source 304 is provided in the cover 306, light is irradiated to the measurement subject, the photoelectric conversion element 10 receives the light irradiated from the light source 304 via the measurement subject, the support substrate 11 supports the photoelectric conversion element 10, and the glass substrate 302 is disposed so as to face the support substrate 11 with the photoelectric conversion element 10 interposed therebetween, and the insertion portion 306 is defined together with the cover 306 by a predetermined distance.
In this configuration example, the light source unit 304 is shown as a transmission type imaging system configured integrally with the cover unit 306 so as to be separated from the photoelectric conversion element 10 through the measurement object in use, but the light source unit 304 is not necessarily required to be located on the cover unit 306 side.
Provided that the light from the light source unit 304 can be efficiently irradiated to the measurement object, for example, a reflection type imaging system in which the measurement object is irradiated from the photoelectric conversion element 10 side can be used.
The vein detection unit 300 includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs a substantial function. The vein detection unit 300 may include any suitable conventionally known member such as a protection film (not shown), a sealing member, a blocking film, a band pass filter, a near infrared ray transmission filter, a visible light blocking film, and a finger placement guide so as to correspond to a design that obtains desired characteristics. The vein detection unit 300 may be configured as the image detection unit 1 described above.
The photoelectric conversion element 10 may be included in any manner. For example, the plurality of photoelectric conversion elements 10 may be arranged in a matrix.
As described above, the photoelectric conversion element 10 is provided on the support substrate 11, and the electrodes (first electrodes or second electrodes) are provided on the support substrate 11 in a matrix, for example.
The light received by the photoelectric conversion element 10 is converted into an electric signal corresponding to the amount of light received by the photoelectric conversion element 10, and is output to the outside of the photoelectric conversion element 10 via the electrode in the form of a light-receiving signal, that is, an electric signal corresponding to the imaged vein.
In the case of vein detection (in use), the measurement object may or may not be in contact with the glass substrate 302 on the photoelectric conversion element 10 side.
The operation of the vein detector 300 will be briefly described.
In the vein detection, the vein detector 300 detects a vein pattern of a measurement object using light emitted from the light source 304. Specifically, the light emitted from the light source unit 304 is transmitted through the measurement object and converted into an electrical signal according to the light receiving amount of the photoelectric conversion element 10. Then, image information of the vein pattern of the measurement object is constituted by the converted electric signal.
In the vein recognition apparatus, vein recognition is performed by comparing the obtained image information with vein data for vein recognition recorded in advance by any conventionally known suitable procedure.
(image detection part for TOF distance measuring device)
Fig. 6 is a diagram schematically showing a configuration example of an image detection unit for an indirect TOF type distance measuring device.
The image detection unit 400 for a TOF type distance measuring device includes: a CMOS transistor substrate 20; an interlayer insulating film 30 provided so as to cover the CMOS transistor substrate 20; the photoelectric conversion element 10 of the embodiment of the present invention provided on the interlayer insulating film 30; 2 floating diffusion layers 402 arranged apart from each other with the photoelectric conversion element 10 interposed therebetween; an insulating layer 401 provided so as to cover the photoelectric conversion element 10 and the floating diffusion layer 402; and 2 photo gates 404 disposed on the insulating layer 401 and arranged apart from each other.
A part of the insulating layer 401 is exposed from the gaps of the separated 2 photo gates 404, and the remaining region is shielded by the shielding portion 406. The CMOS transistor substrate 20 and the floating diffusion layer 402 are electrically connected to each other through the interlayer wiring portion 32 provided so as to penetrate the interlayer insulating film 30.
The interlayer insulating film 30 may be made of any conventionally known insulating material such as silicon oxide or insulating resin. The interlayer wiring portion 32 may be made of any conventionally known conductive material (wiring material), such as copper or tungsten. The interlayer wiring portion 32 may be, for example, an in-hole wiring formed simultaneously with the formation of the wiring layer, or may be a buried plug formed separately from the wiring layer.
In this configuration example, the insulating layer 401 may be formed of a field oxide film made of silicon oxide or any other conventionally known appropriate structure.
The photogate 404 may be made of any conventionally known suitable material, such as polysilicon.
The image detection unit 400 for a TOF type distance measuring device includes the photoelectric conversion element 10 according to the embodiment of the present invention as a functional unit that performs a substantial function. The image detection unit 400 for a TOF ranging apparatus may include any suitable conventionally known member such as a protection film (not shown), a support substrate, a sealing member, a blocking film, a band-pass filter, and an infrared cut film so as to correspond to a design that obtains desired characteristics.
Here, the operation of the image detection unit 400 for a TOF type distance measuring device will be briefly described.
Light is emitted from the light source, the light from the light source is reflected by the measurement object, and the reflected light is received by the photoelectric conversion element 10. Between the photoelectric conversion element 10 and the floating diffusion layer 402, 2 photoelectric gates 404 are provided, and by alternately applying pulses, signal charges generated by the photoelectric conversion element 10 are transferred to any one of the 2 floating diffusion layers 402, and the charges are accumulated in the floating diffusion layer 402. If the light pulse arrives so as to equally span the timing at which the 2 photogate 404 are opened, the amount of charge accumulated in the 2 floating diffusion layers 402 is equal. If the light pulse is delayed from reaching one of the photogate 404 with respect to the timing at which the light pulse reaches the other photogate 404, a difference occurs in the amount of charge accumulated in the 2 floating diffusion layers 402.
The difference in the amount of charge accumulated in the floating diffusion layer 402 depends on the delay time of the light pulse. Since the distance L to the measurement target is l= (1/2) ctd using the relationship between the round trip time td of the light and the speed c of the light, if the delay time can be estimated from the difference in the charge amounts of the 2 floating diffusion layers 402, the distance to the measurement target can be obtained.
The light receiving amount of the light received by the photoelectric conversion element 10 is converted into an electric signal as a difference in the amounts of electric charges accumulated in the 2 floating diffusion layers 402, and the electric signal is output to the outside of the photoelectric conversion element 10 as a light receiving signal, that is, an electric signal corresponding to the measurement object.
Then, the light receiving signal outputted from the floating diffusion layer 402 is inputted to the CMOS transistor substrate 20 via the interlayer wiring portion 32, and is read out by a signal reading circuit formed on the CMOS transistor substrate 20, and is subjected to signal processing by any other suitable conventionally known functional portion not shown, thereby generating distance information based on the measurement object.
3. Light detecting element
As described above, the photoelectric conversion element of the present embodiment may have a light detection function capable of converting irradiated light into an electrical signal corresponding to the amount of light received, and outputting the electrical signal to an external circuit via an electrode. Therefore, the photoelectric conversion element of the embodiment of the present invention can be particularly suitably used as a light detection element having a light detection function. Here, the light detection element of the present embodiment may be a photoelectric conversion element itself, or may include a functional element for controlling voltage or the like in addition to the photoelectric conversion element.
4. Method for manufacturing photoelectric conversion element
The method of manufacturing the photoelectric conversion element of the present embodiment is not particularly limited. The photoelectric conversion element of the present embodiment can be manufactured by combining formation methods suitable for materials selected at the time of forming the constituent elements.
The method for manufacturing a photoelectric conversion element according to the present embodiment may include a step of performing heating at a heating temperature of 220 ℃. More specifically, the active layer may be formed by a process including a process of heating at a heating temperature of 220 ℃ or higher, and/or a process including a process of heating at a heating temperature of 220 ℃ or higher may be included after the process of forming the active layer.
Hereinafter, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (support substrate), an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are in contact with each other in this order will be described as an embodiment of the present invention.
(step of preparing a substrate)
In this step, for example, a support substrate provided with an anode is prepared. Further, a substrate provided with a conductive thin film formed of the material of the electrode described above is commercially available, and the conductive thin film is patterned as necessary to form an anode, thereby preparing a support substrate provided with an anode.
In the method for manufacturing the photoelectric conversion element of the present embodiment, the method for forming the anode when the anode is formed on the support substrate is not particularly limited. The anode may be formed by any conventionally known suitable method such as vacuum deposition, sputtering, ion plating, coating, etc., on the structure (e.g., support substrate, active layer, hole transport layer) on which the anode is to be formed.
(step of Forming hole transporting layer)
The method for manufacturing the photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the anode.
The method for forming the hole transport layer is not particularly limited. In order to simplify the step of forming the hole transport layer, the hole transport layer is preferably formed by any conventionally known suitable coating method. The hole transport layer can be formed by, for example, a coating method using a coating liquid containing the material of the hole transport layer and a solvent described above, or a vacuum evaporation method.
(active layer Forming step)
In the method for manufacturing a photoelectric conversion element according to the present embodiment, an active layer is formed over a hole transport layer. The active layer as a main component may be formed by any suitable conventionally known forming process.
In this embodiment, the active layer is preferably produced by a coating method using an ink composition (coating liquid).
Hereinafter, the steps (i) and (ii) included in the step of forming an active layer, which is a main component of the photoelectric conversion element of the present invention, will be described.
Working procedure (i)
As a method of applying the ink composition to the object to be coated, any suitable application method may be used. The coating method is preferably a slit coating method, a doctor blade coating method, a spin coating method, a micro gravure coating method, a bar coating method, an inkjet printing method, a nozzle coating method, or a capillary coating method, more preferably a slit coating method, a spin coating method, a capillary coating method, or a bar coating method, and still more preferably a slit coating method or a spin coating method.
The ink composition used in the method for manufacturing a photoelectric conversion element of the present embodiment contains a composition containing a p-type semiconductor material and an n-type semiconductor material, and contains the compound of the present embodiment, which has been described, as the n-type semiconductor material, and a solvent.
Here, according to the composition of the present embodiment, when the p-type semiconductor material and the n-type semiconductor material are selected, the bandgap of the n-type semiconductor material (the difference between the energy level of LUMO and the energy level of HOMO) is preferably selected to be larger than the bandgap of the p-type semiconductor material. If so selected, the dark current of the photoelectric conversion element can be reduced more effectively.
The band gap (Eg) of the p-type semiconductor material and the n-type semiconductor material can be measured by any suitable measurement method known in the art. Specifically, the band gap can be calculated by the following formula using the absorption edge wavelength of the compound.
Eg=hc/absorption end wavelength
Where h represents the planck constant and c represents the speed of light.
Here, the absorption end wavelength may be determined based on the "absorption spectrum" already described. Specifically, in the obtained absorption spectrum, the wavelength at which the base line intersects with the straight line fitted to the falling curve on the long wavelength side of the absorption peak curve can be determined as the absorption edge wavelength.
The ink composition for forming an active layer according to the present embodiment will be described. The ink composition for forming an active layer according to the present embodiment is an ink composition for forming an active layer having a Bulk Heterojunction (BHJ) structure.
Therefore, the active layer included in the photoelectric conversion element of the present embodiment is a (cured) film obtained by curing the ink composition, and is a (cured) film having a bulk heterojunction structure. In other words, the photoelectric conversion element of the present embodiment includes a film having a bulk heterojunction structure as an active layer.
The ink composition for forming an active layer of the present embodiment includes a composition including the p-type semiconductor material described above and the compound of the present embodiment described above as an n-type semiconductor material. The ink composition for forming an active layer of the present embodiment preferably contains the composition and 1 or 2 or more solvents.
According to the ink composition for forming an active layer of the present embodiment, by including the p-type semiconductor material and the "compound of the present embodiment", a dark current required for a photoelectric conversion element, particularly, a light detection element can be effectively reduced.
The ink composition for forming an active layer of the present embodiment is not particularly limited, provided that the active layer can be formed. As the solvent, for example, a mixed solvent in which the 1 st solvent and the 2 nd solvent described later are combined can be used. Specifically, when the ink composition for forming an active layer contains 2 or more solvents, it is preferable to contain a main solvent (1 st solvent) as a main component and another additive solvent (2 nd solvent) added to improve solubility or the like. However, only the 1 st solvent may be used.
Hereinafter, the 1 st solvent and the 2 nd solvent and combinations thereof, which can be suitably used in the ink composition for forming an active layer of the present embodiment, will be described.
(1) 1 st solvent
As the 1 st solvent, a solvent capable of dissolving the p-type semiconductor material is preferable. The 1 st solvent of the present embodiment is an aromatic hydrocarbon.
Examples of the aromatic hydrocarbon as the 1 st solvent include toluene, xylene (e.g., o-xylene, m-xylene, and p-xylene), o-dichlorobenzene, trimethylbenzene (e.g., mesitylene, and 1,2, 4-trimethylbenzene (pseudocumene)), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, and tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), tetrahydronaphthalene, and indane.
The 1 st solvent may be composed of 1 kind of aromatic hydrocarbon or 2 or more kinds of aromatic hydrocarbon. The 1 st solvent is preferably composed of 1 kind of aromatic hydrocarbon.
The 1 st solvent is preferably 1 or more selected from toluene, o-xylene (oXAP), m-xylene, p-xylene, mesitylene, o-dichlorobenzene (ODCB), 1,2, 4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetrahydronaphthalene, and indane, more preferably toluene, o-xylene, m-xylene, p-xylene, o-dichlorobenzene, mesitylene, 1,2, 4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, methylnaphthalene, tetrahydronaphthalene, or indane.
(2) Solvent 2
The 2 nd solvent is a solvent selected from the viewpoints of facilitating the implementation of the manufacturing process and further improving the characteristics of the photoelectric conversion element. Examples of the 2 nd solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, acetophenone, and propiophenone, and ester solvents such as ethyl acetate, butyl acetate, phenyl acetate, ethyl cellosolve acetate, methyl Benzoate (MBZ), butyl benzoate, and benzyl benzoate.
From the viewpoint of, for example, further reducing dark current, acetophenone, propiophenone, methyl benzoate, or butyl benzoate is preferably used as the 2 nd solvent.
(3) Combination of the 1 st solvent and the 2 nd solvent
Examples of suitable combinations of the 1 st and 2 nd solvents include a combination of o-xylene and methyl benzoate, tetralin and ethyl benzoate, tetralin and propyl benzoate, and tetralin and butyl benzoate.
(4) The weight ratio of the 1 st solvent to the 2 nd solvent
From the viewpoint of further improving the solubility of the p-type semiconductor material and the n-type semiconductor material, the weight ratio of the 1 st solvent as the main solvent to the 2 nd solvent as the additive solvent (1 st solvent: 2 nd solvent) is preferably set to 85: 15-99: 1.
(5) Optionally other solvents
The solvent may contain any other solvent than the 1 st solvent and the 2 nd solvent. When the total weight of all solvents contained in the ink composition is set to 100 wt%, the content of any other solvent is preferably 5 wt% or less, more preferably 3 wt% or less, and still more preferably 1 wt% or less. As any other solvent, a solvent having a boiling point higher than that of the 2 nd solvent is preferable.
(6) Arbitrary components
The ink composition may contain, in addition to the 1 st solvent, the 2 nd solvent, the p-type semiconductor material, and the n-type semiconductor material, any component such as a surfactant, an ultraviolet absorber, an antioxidant, a sensitizer for sensitizing a function of generating electric charges by absorbed light, and a light stabilizer for increasing stability against ultraviolet light, as far as the object and effect of the present invention are not impaired.
(7) Concentration of p-type semiconductor material and n-type semiconductor material
The concentration of the p-type semiconductor material and the n-type semiconductor material in the ink composition may be any suitable concentration within a range that does not impair the object of the present invention, considering the solubility in a solvent and the like.
The weight ratio (polymer/non-fullerene compound) of the "p-type semiconductor material" to the "n-type semiconductor material" in the ink composition is usually in the range of 1/0.1 to 1/10, preferably in the range of 1/0.5 to 1/2, more preferably 1/1.5.
The total concentration of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink composition is usually 0.01 wt% or more, more preferably 0.02 wt% or more, and still more preferably 0.25 wt% or more. The total concentration of the "p-type semiconductor material" and the "n-type semiconductor material" in the ink composition is usually 20 wt% or less, preferably 10 wt% or less, and more preferably 7.50 wt% or less.
The concentration of the "p-type semiconductor material" in the ink composition is usually 0.01% by weight or more, more preferably 0.02% by weight or more, and still more preferably 0.10% by weight or more. The concentration of the "p-type semiconductor material" in the ink composition is usually 10 wt% or less, more preferably 5.00 wt% or less, and still more preferably 3.00 wt% or less.
The concentration of the "n-type semiconductor material" in the ink composition is usually 0.01% by weight or more, more preferably 0.02% by weight or more, and still more preferably 0.15% by weight or more. The concentration of the "n-type semiconductor material" in the ink composition is usually 10 wt% or less, more preferably 5 wt% or less, and further preferably 4.50 wt% or less.
(8) Preparation of ink composition
The ink composition can be prepared by a known method. For example, a method in which a mixed solvent is prepared by mixing the 1 st solvent, or the 1 st solvent and the 2 nd solvent, and a p-type semiconductor material and an n-type semiconductor material are added to the obtained mixed solvent; a method in which a p-type semiconductor material is added to the 1 st solvent, an n-type semiconductor material is added to the 2 nd solvent, and then the 1 st solvent and the 2 nd solvent to which each material is added are mixed.
The 1 st and 2 nd solvents may be warmed and mixed with the p-type semiconductor material and the n-type semiconductor material to a temperature below the boiling point of the solvents.
After the 1 st solvent and the 2 nd solvent are mixed with the p-type semiconductor material and the n-type semiconductor material, the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as an ink composition. As the filter, for example, a filter formed of a fluororesin such as Polytetrafluoroethylene (PTFE) can be used.
The ink composition for forming an active layer is applied to an object to be coated selected according to the photoelectric conversion element and the method for producing the same. The ink composition for forming an active layer may be applied to a functional layer of a photoelectric conversion element, that is, a functional layer in which an active layer exists, in a process for producing a photoelectric conversion element. Therefore, the object to be coated with the ink composition for forming an active layer differs depending on the layer configuration and the order of layer formation of the photoelectric conversion element to be manufactured. For example, in the case where the photoelectric conversion element has a layer structure in which a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode are laminated, and a layer described further to the left is formed first, the ink composition for forming the active layer is applied to the hole transport layer. In addition, for example, in the case where the photoelectric conversion element has a layer structure in which a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode are stacked, and a layer described further to the left is formed first, the application target of the ink composition for forming an active layer is the electron transport layer.
Working procedure (ii)
As a method of removing the solvent from the coating film of the ink composition, that is, a method of removing the solvent from the coating film and curing, any suitable method may be used. Examples of the method for removing the solvent include a method of directly heating the solvent under an inert gas atmosphere such as nitrogen using a heating plate, a hot air drying method, an infrared heating drying method, a flash lamp annealing drying method, a vacuum drying method, and other drying methods.
The conditions for the step (ii), that is, the heating temperature, the heating time, and the like, may be any suitable conditions in consideration of the composition of the ink composition to be used, the boiling point of the solvent, and the like.
In the present embodiment, specifically, the step (ii) may be performed using a heating plate, for example, in a nitrogen atmosphere.
The process (ii) may include a plurality of heat treatment processes, such as a pre-bake process and a post-bake process. In this case, the heating temperature in the pre-baking step and/or the post-baking step may be about 100 ℃.
The total heat treatment time in the pre-baking step and the post-baking step may be, for example, 1 hour.
The heating temperature in the pre-baking process may be the same as or different from the heating temperature in the post-baking process.
The heating treatment time may be, for example, 10 minutes or longer. The upper limit of the heating treatment time is not particularly limited, and may be set to, for example, 4 hours in consideration of the takt time and the like.
The thickness of the active layer may be set to any desired thickness by appropriately adjusting the solid content concentration in the coating liquid and the conditions of the above-mentioned step (i) and/or step (ii).
The step of forming the active layer may include other steps in addition to the steps (i) and (ii) described above, provided that the objects and effects of the present invention are not impaired.
The method for manufacturing a photoelectric conversion element according to the present embodiment may be a method for manufacturing a photoelectric conversion element including a plurality of active layers, or may be a method in which the steps (i) and (ii) are repeated a plurality of times.
(step of Forming an Electron transporting layer)
The method for manufacturing a photoelectric conversion element according to the present embodiment includes a step of forming an electron transport layer (electron injection layer) provided on an active layer.
The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the process of forming the electron transport layer, it is preferable to form the electron transport layer by any conventionally known suitable vacuum deposition method.
(cathode Forming step)
The method for forming the cathode is not particularly limited. The cathode may be formed of the electrode material exemplified above on the electron transport layer by any conventionally known suitable method such as a coating method, a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like. The photoelectric conversion element of the present embodiment is manufactured through the above steps.
(step of forming seal)
In forming the sealing body, in the present embodiment, any conventionally known sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, after a sealing material such as a UV curable resin is applied to the support substrate so as to surround the periphery of the photoelectric conversion element to be manufactured, the sealing material is bonded without any gap, and then the photoelectric conversion element is sealed in the gap between the support substrate and the sealing substrate by a method suitable for the selected sealing material, such as irradiation of UV light, whereby a sealed body of the photoelectric conversion element can be obtained.
Examples
Hereinafter, examples are shown for the purpose of explaining the present invention in more detail. The present invention is not limited to the examples described below.
In this example, a polymer compound shown in table 1 below was used as a p-type semiconductor material (electron donating compound), and compounds shown in tables 2 and 3 below were used as n-type semiconductor materials (electron accepting compound).
TABLE 1
(Table 1)
[ Table 2] (Table 2)
TABLE 3
(Table 3)
The polymer compound P-1 as a P-type semiconductor material is synthesized and used by the method described in International publication No. 2011/052709.
The compounds N-1, N-2, N-3 and N-5 as N-type semiconductor materials were synthesized and used as in the synthesis examples described below.
The compound N-4 as an N-type semiconductor material is commercially available under the trade name Y6 (manufactured by 1-material Co.).
Synthesis example 1 (Synthesis of Compound 2)
Compound 2 was synthesized using compound 1 as described below.
[ chemical formula 82]
Specifically, in a 300mL three-necked flask in which the internal atmosphere was replaced with nitrogen gas, compound 1 (2.00 g,3.28 mmol), dehydrated chloroform (109 mL, 0.02M) and Vilsmeier reagent ((Chloromethylene) dimethyl ammonium chloride) dimethyliminium Chloride) (0.630 g,4.92 mmol) synthesized by the method described in paragraph [0335] of International publication No. 2011/052709 were charged, and the internal temperature of the three-necked flask was set to 60℃for 3 hours using an oil bath.
The three-necked flask was lifted from the oil bath, cooled to room temperature, quenched by injecting water into the reaction solution in the three-necked flask, and then stirred at room temperature by adding a saturated aqueous sodium bicarbonate solution.
After the organic layer was extracted from the obtained reaction liquid, the organic layer was washed with water 2 times, dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. The filtrate obtained by filtration was concentrated in the whole amount by a rotary evaporator, whereby a crude product was obtained.
The obtained crude product was purified by a silica gel column (eluent: hexane/ethyl acetate=100/0 to 98/2 (mass%)) to thereby obtain 2.00g of compound 2 as an orange-black viscous liquid (yield 96%).
NMR spectra were analyzed for the resulting compound 2. The results are described below.
1H-NMR (400 MHz, CHROFORM (chloroform) -D) δ9.76-9.72 (1H), 7.24 (1H), 6.70 (1H), 1.88-1.74 (4H), 1.22-1.41 (40H), 0.88-0.83 (6H),
synthesis example 2 (Synthesis of Compound 3)
Compound 3 was synthesized using compound 2 as described below.
[ chemical formula 83]
Into a 200mL three-necked flask, compound 2 (2.00 g,4.84 mmol) and 9- [4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl were charged]9H-carbazole (2.14 g,5.81 mmol) (Tokyo chemical industry Co., ltd.) and THF (48 mL, 0.1M) were added to Pd after replacing the internal atmosphere with nitrogen 2 (dba) 3 (0.13g，0.15mmol)、P(tBu) 3 HBF 4 (0.088 g,0.29 mmol), 3M K 3 PO 4 aq (48 mL), was warmed to 60 ℃.
After heating and stirring for 2 hours, the reaction solution was cooled to room temperature. The organic layer was extracted from the reaction solution, diluted with hexane, washed 2 times with water, dried over magnesium sulfate, and filtered to remove magnesium nitrate, and the filtrate thus obtained was concentrated in the entire amount by a rotary evaporator to obtain a crude product.
The obtained crude product was purified by a silica gel column (eluent: hexane/ethyl acetate=100/0 to 98/2 mass%) to thereby obtain 2.63g of compound 3 (yield 67.9%) as an orange viscous liquid.
Example 1 > (Synthesis of Compound 4)
Compound 4 (compound N-1) was synthesized using compound 3 and compound 12 as follows.
[ chemical formula 84]
Into a 50mL three-necked flask, compound 3 (0.310 g,0.387 mmol), dehydrated chloroform (19 g, 0.03M), compound 12 (0.153 g,0.581 mmol) synthesized by the method described in Adv. Mater.2017, 29, 1703080, and pyridine (0.306 g,3.87 mmol) were charged, and the three-necked flask was placed in an oil bath heated to 60℃and held.
After heating and stirring for 2 hours, the three-necked flask was lifted from the oil bath and cooled to room temperature. The reaction solution was washed with water 1 time, dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration through a tung mountain funnel. The resulting filtrate was concentrated in total amount by rotary evaporator to give a crude product.
The crude product obtained was purified by a silica gel column (eluent: chloroform) and then purified by a cyclic preparation GPC (eluent: chloroform), whereby 0.186g of Compound 4 was obtained as a black solid (yield 46%).
The obtained compound 4 was analyzed for NMR spectrum. The results are described below.
1H-NMR (400 MHz, CHLOFORM (chloroform) -D) delta 8.72 (1H), 8.71 (1H), 8.13 (2H), 7.84-7.87 (3H), 7.64-7.67 (2H), 7.38-7.46 (5H), 7.28-7.32 (2H), 7.10 (s, 1H), 1.89-2.00 (4H), 1.22-1.50 (40H), 0.84 (6H)
Example 2 > (Synthesis of Compound 5)
Compound 5 (compound N-2) was synthesized using compound 3 and compound 13 as described below.
[ chemical formula 85]
Into a 100mL three-necked flask, compound 3 (0.750 g,0.937 mmol), compound 13 (0.298 g,1.22 mmol), pTsOH (0.335 g,2.8 mmol), etOH (16 mL), toluene (31 mL), mgSO, synthesized according to the method described in International publication No. 2020/109823, and the like were charged 4 (0.38 g) the three-necked flask was placed in an oil bath heated to 60℃and held.
After heating and stirring for 2 hours, the three-necked flask was cooled to room temperature. The obtained reaction solution was concentrated by an evaporator, toluene was added to the reaction solution, the solution was washed 3 times with water, dried over magnesium sulfate, and after removing magnesium sulfate by filtration, the filtrate was concentrated in the whole amount by a rotary evaporator to obtain a crude product.
The crude product obtained was purified by a silica gel column (eluent: chloroform) and then purified by a cyclic preparation GPC (eluent: chloroform), whereby 0.495g of Compound 5 was obtained as a black solid (yield: 51%).
NMR spectra were analyzed for the resulting compound 5. The results are described below.
1HNMR(300MHz，CDCl3)δ8.94(s，1H)，8.73(s，1H)，8.10(2H)，8.06(1H)，7.88(2H)，7.68(2H)，7.42(5H)，7.31(3H)，7.14(1H)，1.97(m，4H)，1.49-1.18(m，40H)，0.84(6H，-CH3).
Synthesis example 4 (Synthesis of Compound 9)
Compound 9 was synthesized using compound 8 as described below.
[ chemical formula 86]
Compound 8 (1.1 g,2.2 mmol), TMEDA (0.25 g,2.2 mmol) and 16mL of dehydrated THF synthesized by the method described in paragraph [0271] of International publication No. 2011/052709 were charged into a 100mL four-necked flask in which the internal atmosphere was replaced with nitrogen, and the internal temperature was cooled to-70℃using a bath filled with dry ice and acetone. Next, nBuLi (3.5 mL,5 mmol) was further charged into the four-necked flask and the flask was kept for 2 hours.
DMF (0.47 g,0.6 mmol) was dissolved in 1.8mL of dehydrated THF, and the mixture was put into a four-necked flask, and after 1 hour of holding, the temperature was raised to room temperature.
Then, a saturated aqueous ammonium chloride solution was further introduced into the four-necked flask, and the mixture was separated into an organic layer by ethyl acetate. The obtained organic layer was dried with magnesium sulfate, and after removing magnesium sulfate by filtration, the obtained filtrate was concentrated with a rotary evaporator to obtain a crude product.
The obtained crude product was purified by a silica gel column (eluent: hexane/ethyl acetate=100/2 mass%) to thereby obtain 0.85g of compound 9 (yield 78%) as a yellow viscous liquid.
Synthesis example 5 (Synthesis of Compound 10)
Compound 10 (compound N-3) was synthesized using compound 9 as described below.
[ chemical formula 87]
Into a 100mL four-necked flask having an internal atmosphere replaced with nitrogen gas, compound 9 (0.85 g,1.44 mmol), dehydrated chloroform (17 g,20 WR), compound 12 (1.14 g,4.33 mmol) and pyridine (0.05 g,0.72 mmol) were charged, and the four-necked flask was placed in an oil bath heated to 65℃and held.
Heating and stirring for 4 hours, and cooling to normal temperature. Water was injected into the obtained reaction solution, and the solution was separated by using a separating funnel, and after the lower organic layer was collected, water was again added to separate the solution, and the organic layer was separated. The organic layer was dehydrated with magnesium sulfate, and the magnesium sulfate was removed by filtration. The resulting filtrate was concentrated in total amount by rotary evaporator to give a crude product.
The obtained crude product was purified by a silica gel column (eluent: chloroform), whereby 0.37g of compound 10 was obtained as a brown solid (yield 24%).
Example 3 > (Synthesis of Compound N-5)
Compound 21 was first synthesized as described below.
[ chemical formula 88]
Specifically, 4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b ] was charged into a 500mL three-necked flask in which the internal atmosphere was replaced with nitrogen gas: 3,4-b' ] dithiophene (8.46 g) (manufactured by Tokyo chemical industry Co., ltd.), dehydrated DMF (4.30 g) and dehydrated chloroform (212 mL) were cooled to 0℃in an ice bath.
Next, phosphorus oxychloride (3.87 g) was added thereto, and after heating to room temperature, the mixture was stirred for 14 hours. After quenching with 20% sodium acetate water, the organic layer was extracted, washed 2 times with water, dehydrated with magnesium sulfate, and removed by filtration. The filtrate obtained by filtration was concentrated in the whole amount by a rotary evaporator, whereby a crude product was obtained.
The obtained crude product was purified by a silica gel column (eluent was chloroform/hexane=70/30 (mass%)), whereby 6.32g of compound 21 was obtained (yield 70%).
Next, as described below, compound 22 was synthesized using compound 21.
[ chemical formula 89]
Specifically, in use N 2 Into a 1L four-necked flask in which the internal atmosphere was replaced with gas, compound 21 (6.31 g,14.7 mmol) and Tetrahydrofuran (THF) (316 mL) were charged, and the mixture was cooled to an internal temperature of 0℃in an ice bath. After N-bromosuccinimide (NBS) (2.66 g,14.9 mmol) was added, the mixture was stirred for 14 hours, and water was injected into the reaction solution. Hexane was added and the organic layer was extracted.
The obtained organic layer was washed with water 2 times, dehydrated with magnesium sulfate, and after removing magnesium sulfate by filtration, the filtrate was concentrated in the entire amount by a rotary evaporator to obtain a crude product.
The obtained crude product was purified by a silica gel column (eluent: hexane/chloroform=50/50 mass%) to thereby obtain 7.40g of compound 22.
Next, as described below, compound 23 was synthesized using compound 22.
[ chemical formula 90]
Specifically, compound 12 (2.57 g,5.04 mmol) 9- [4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] was put into a 200mL three-necked flask]-9H-carbazole (1.74 g,6.05 mmol) (manufactured by Tokyo chemical industry Co., ltd.) and THF (72 mL), the internal atmosphere was replaced with nitrogen, and then K was added in this order 2 CO 3 aq (25 mL) and Pd (PPh) 3 ) 4 (0.583 g,0.504 mmol) was heated to 60 ℃.
After heating and stirring for 2 hours, the reaction solution was cooled to room temperature, and 72mL of ethyl acetate was added thereto, followed by extraction of an organic layer from the reaction solution. The obtained organic layer was washed with water 2 times, dried over magnesium sulfate, and filtered to remove magnesium nitrate, and the filtrate thus obtained was concentrated in the entire amount by a rotary evaporator to obtain a crude product.
The crude product obtained was purified by a silica gel column (eluent hexane/toluene=20/80) to obtain 3.14g of compound 23 (yield 92.6%).
Next, as described below, compound N-5 was synthesized using compound 23.
[ chemical formula 91]
Specifically, a compound was put into a 100mL 3-necked flask23 (0.500 g,0.744 mmol), compound 13 (0.236 g,0.97 mmol), pTsOH.H 2 O (0.425 g,2.23 mmol), etOH (12 mL), toluene (25 mL), mgSO 4 (0.25 g) was placed in an oil bath heated to 60℃for heat preservation. After stirring for 2 hours, compound 13 (0.093 g,0.38 mmol) was added and further stirred for 4 hours.
Next, the 3-neck flask was lifted from the oil bath, cooled to room temperature, water was added, etOH was removed by an evaporator, methanol was added, and the precipitated solid was filtered and recovered by a tung mountain funnel (including No.5b filter paper), thereby obtaining a crude product.
The obtained crude product was recrystallized from chloroform, whereby 0.527g of Compound N-5 (0.587 mmol, yield 79%, LC area percentage value: 98.9%) was obtained as a brown solid.
NMR spectra were analyzed for the resulting compound N-5. The results are described below.
1H-NMR (400 MHz, tetrahydroOFURAN (tetrahydrofuran) -D8) delta 8.97 (1H), 8.95 (1H), 8.39 (1H), 8.12 (2H), 8.02-8.05 (2H), 7.99 (s, 1H), 7.77 (1H), 7.71 (2H), 7.45 (D, 2H), 7.37 (2H), 7.24 (2H), 2.05-2.22 (m, 4H), 0.98-1.08 (m, 16H), 0.72-0.77 (m, 6H), 0.63-0.69 (m, 6H)
(band gap (Eg) of Compound)
Solutions were obtained in which the compounds N-1 to N-5 prepared as described above were dissolved in o-xylene, respectively. Next, the obtained solutions were coated on glass substrates by spin coating to form coating films, and dried by a heating plate to prepare samples.
The band gap is calculated by the following formula using the absorption edge wavelength of the compound.
Eg=hc/absorption end wavelength
Where h represents the planck constant and c represents the speed of light.
Let h= 6.626 ×10 -34 Js, set to c=3×10 8 m/s.
The absorption edge wavelength was obtained by the following method.
For the thin film formed from the above sample, an absorption spectrum was measured with the absorbance on the vertical axis and the wavelength on the horizontal axis.
In the obtained absorption spectrum, the wavelength at the intersection of the baseline and the straight line fitted to the falling curve on the long wavelength side of the absorption peak curve is taken as the absorption edge wavelength.
The band gaps of the polymer compound P-1 and the compounds N-1 to N-5 used in this example are shown in Table 4 below.
TABLE 4
(Table 4)
Band gap (eV)
Polymer compound P-1 1.14
Compound 4 (Compound N-1) 1.59
Compound 5 (Compound N-2) 1.49
Compound 10 (Compound N-3) 1.35
Compound N-4 1.34
Compound N-5 1.55
(absorption Peak wavelength)
The polymer compound P-1 was subjected to an absorption spectrum by a conventional method. In the obtained absorption spectrum, a value corresponding to a wavelength corresponding to an absorption peak having the maximum absorbance is referred to as an "absorption peak wavelength". The absorption peak wavelength of the polymer compound P-1 was 921nm.
The values (eV) of the energy levels of LUMOs of the constituent units contained in the above-described compounds N-1 to N-5 as the N-type semiconductor material in the present embodiment are calculated by using a method of computational science on the compound corresponding to the constituent unit.
Specifically, a quantum chemical computation program Gaussian 03 was applied to each of the compounds (structures) corresponding to the respective structural units, which were obtained by cleaving bonds between structural units and adding hydrogen atoms to the bond bonds produced by cleavage, and the structure of the ground state was optimized by a density functional method at the level of B3LYP, and the optimized structure was calculated using 6-31g of a material as a basis function, and the obtained value was used as the value of the LUMO energy level of each structural unit.
The results are shown in tables 5 to 7 below. In the calculation, the alkyl group that may be contained in the compound (structure) is represented by a propyl group (-CH) 2 -CH 2 -CH 3 ) Calculations are made for example.
TABLE 5
(Table 5)
TABLE 6
(Table 6)
TABLE 7
(Table 7)
As described above, D in Compounds N-1 and N-2 1 Of the energy level of LUMO (E D-LUMO ) Constitution B 1 Of at least 1 structural unit of 1 or more structural units (E π-LUMO )、A 1 Of the energy level of LUMO (E A-LUMO ) Satisfy the requirement of "E D-LUMO ＞E B-LUMO ＞E A-LUMO ”。
Example 4 > (preparation of ink composition I-1)
In a mixed solution of o-xylene (oXAP) and Methyl Benzoate (MBZ) (95/5=vol%) as a solvent, a polymer compound P-1 as a P-type semiconductor material was mixed so as to be 1.3 mass% with respect to the total weight of the ink composition, and a compound N-1 (P-type semiconductor material/N-type semiconductor material=1/1) as an N-type semiconductor material was mixed so as to be 1.3 mass% with respect to the total weight of the ink composition, and the obtained mixed solution was stirred at 60 ℃ for 8 hours, and filtered using a filter, thereby obtaining an ink composition (I-1). The components and the like are also shown in table 8 below.
Example 5 > (preparation of ink composition I-2)
An ink composition (I-2) was prepared in the same manner as in example 4, except that an n-type semiconductor material was used as a combination shown in Table 8 below.
PREPARATION EXAMPLE 1 preparation of ink composition (I-3)
An ink composition (I-3) was prepared in the same manner as in example 4, except that an n-type semiconductor material was used as a combination shown in Table 8 below.
PREPARATION EXAMPLE 2 preparation of ink composition (I-4)
An ink composition (I-4) was prepared in the same manner as in example 4, except that the solvent was o-dichlorobenzene (ODCB) and the n-type semiconductor material was used in the combination shown in Table 8 below.
< example 6> (preparation of ink composition I-5)
An ink composition (I-5) was prepared in the same manner as in example 4, except that an n-type semiconductor material was used as a combination shown in Table 8 below.
TABLE 8
(Table 8)
Ink composition Solvent(s) P-type semiconductor material n-type semiconductor material
Example 4 I-1 oXAP/MBZ P-1 N-1
Example 5 I-2 oXAP/MBZ P-1 N-2
Preparation example 1 I-3 oXAP/MBZ P-1 N-3
Preparation example 2 I-4 ODCB P-1 N-4
Example 6 I-5 ODCB P-1 N-5
< example 7> (production and evaluation of photoelectric conversion element)
(1) Photoelectric conversion element and production of sealing body for same
A glass substrate on which an ITO thin film (anode) having a thickness of 50nm was formed by a sputtering method was prepared, and the glass substrate was subjected to an ozone UV treatment as a surface treatment.
Next, the ink composition (I-1) was coated on the ITO thin film by spin coating to form a coating film, and then, the coating film was dried by heat treatment using a heating plate heated to 100 ℃ for 10 minutes under a nitrogen atmosphere, thereby forming an active layer. The thickness of the formed active layer was about 300nm.
Next, znO was coated on the formed active layer by spin coating to form an electron transport layer having a thickness of about 50 nm.
Next, a silver (Ag) layer was formed on the formed electron transport layer at a thickness of about 60nm as a cathode.
The photoelectric conversion element was manufactured on the glass substrate through the above steps.
Next, a UV curable sealant as a sealing material was applied to a glass substrate as a supporting substrate so as to surround the periphery of the fabricated photoelectric conversion element, and after the glass substrate as a sealing substrate was bonded, UV light was irradiated, thereby sealing the photoelectric detection element in a gap between the supporting substrate and the sealing substrate, and a sealing body for the photoelectric conversion element was obtained. The planar shape of the photoelectric conversion element sealed in the gap between the support substrate and the sealing substrate was a square of 2mm×2mm when viewed in the thickness direction. The resulting sealed body was used as sample 1.
(2) Evaluation of photoelectric conversion element (evaluation of dark Current)
In the produced sample 1, a voltage of-10V to 2V was applied in a dark state without light irradiation, and a current value at the time of applying a reverse bias voltage of-2V measured by a known method was obtained as a value of a dark current. The results are shown in Table 9 below.
< examples 8 and 9 and comparative examples 1 and 2> (production and evaluation of photoelectric conversion element)
A sealing body for a photoelectric conversion element was produced in the same manner as that of example 7 described above, except that the ink compositions (I-2) to (I-5) were used in place of the ink composition (I-1), and evaluation was made. The results are shown in Table 9 below.
TABLE 9
(Table 9)
Ink composition P-type semiconductor material n-type semiconductor material Dark current value (nA/cm) 2 )
Example 7 I-1 P-1 N-1 1
Example 8 I-2 P-1 N-2 111
Comparative example 1 I-3 P-1 N-3 281
Comparative example 2 1-4 P-1 N-4 33241
Example 9 I-5 P-1 N-5 137
Description of the reference numerals
1: image detection unit
2: display device
10: photoelectric conversion element
11. 210: support substrate
12: anode
13: hole transport layer
14: active layer
15: electron transport layer
16: cathode electrode
17: sealing member
20: CMOS transistor substrate
30: interlayer insulating film
32: interlayer wiring part
40: sealing layer
42: scintillator
44: reflective layer
46: protective layer
50: color filter
100: fingerprint detection unit
200: display panel part
200a: display area
220: organic EL element
230: touch sensor panel
240: sealing substrate
300: vein detection unit
302: glass substrate
304: light source unit
306: cover part
310: insertion part
400: image detection unit for TOF type distance measuring device
401: insulating layer
402: floating diffusion layer
404: photoelectric door
406: light shielding part

Claims (13)

1. A composition comprising a p-type semiconductor material and an n-type semiconductor material,
the n-type semiconductor material comprises a compound represented by the following formula (I),
D 1 -B 1 -A 1 (I)
in the formula (I) of the present invention,
D 1 represents an electron donating group, and is represented by,
A 1 represents an electron-withdrawing group and is represented by,
B 1 represents a 2-valent group which comprises 1 or more structural units and constitutes a pi-conjugated system.
2. The composition of claim 1, wherein the n-type semiconductor material has a band gap greater than that of the p-type semiconductor material.
3. The composition according to claim 1 or 2, wherein D 1 Energy level of LUMO of (E) D-LUMO Constitution B 1 Energy level of LUMO of at least 1 structural unit of 1 or more structural units, i.e., E π-LUMO And A 1 Energy level of LUMO of (E) A-LUMO The conditions shown in the following formula are satisfied:
E D-LUMO ＞E B-LUMO ＞E A-LUMO 。
4. the composition of claim 1 or 2, wherein the p-type semiconductor material is a high molecular compound.
5. The composition of claim 4, wherein the p-type semiconductor material is a high molecular compound having an absorption peak wavelength of greater than 700 nm.
6. An ink composition comprising the composition of claim 1 or 2 and a solvent.
7. A film having a bulk heterojunction structure comprising the composition of claim 1 or 2.
8. A photoelectric conversion element comprising the film according to claim 7 as an active layer.
9. The photoelectric conversion element according to claim 8, which is a light detection element.
10. A compound represented by the following formula (I),
D 1 -B 1 -A 1 (I)
in the formula (I) of the present invention,
D 1 represents an electron donating group, and is represented by,
A 1 is an electron-withdrawing group and represents an electron-withdrawing group having a ring structure,
B 1 represents a 2-valent group which comprises 1 or more structural units and constitutes a pi-conjugated system,
the 1 st structural unit which is at least 1 of the 1 st structural units is a structural unit represented by the following formula (II), and the remaining 2 nd structural units other than the 1 st structural unit are a 2-valent group comprising an unsaturated bond, a 2-valent aromatic carbocyclic group or a 2-valent aromatic heterocyclic group,
in the case where there are 2 or more of the 1 st structural units, the 2 or more of the 1 st structural units present are optionally the same or different from each other, in the case where there are 2 or more of the 2 nd structural units, the 2 or more of the 2 nd structural units present are optionally the same or different from each other,
in the formula (II) of the present invention,
Ar 1 and Ar is a group 2 Each independently represents an optionally substituted aromatic carbocyclic ring or an optionally substituted aromatic heterocyclic ring,
y represents a group represented by a direct bond, -C (=O) -, or an oxygen atom,
R each independently represents:
a hydrogen atom,
Halogen atom,
An optionally substituted alkyl group,
Cycloalkyl optionally having substituents,
Aryl optionally having substituents,
Alkoxy optionally having substituent(s),
Optionally substituted cycloalkoxy,
Aryloxy group optionally having a substituent,
Alkylthio optionally having a substituent,
A cycloalkylthio group optionally having a substituent,
Arylthio optionally having a substituent,
A 1-valent heterocyclic group optionally having a substituent,
Substituted amino optionally having substituent(s),
Acyl optionally having substituent(s),
An optionally substituted imine residue,
An amide group optionally having a substituent,
An imide group optionally having a substituent,
Substituted oxycarbonyl optionally having a substituent,
Alkenyl optionally having substituent(s),
Optionally substituted cycloalkenyl,
Alkynyl optionally having substituents,
Optionally substituted cycloalkynyl,
Cyano group,
Nitro group,
-C(＝O)-R a A group of the formula
-SO 2 -R b The radicals are shown in the figures,
R a and R is b Each independently represents:
a hydrogen atom,
An optionally substituted alkyl group,
Aryl optionally having substituents,
Alkoxy optionally having substituent(s),
Aryloxy group optionally having substituent(s), or
A 1-valent heterocyclic group optionally having a substituent,
the plurality of R's present are optionally the same or different from each other.
11. The compound according to claim 10, wherein the 1 st structural unit is a structural unit represented by the following formula (III),
in the formula (III) of the present invention,
y and R are as defined above,
X 1 and X 2 Each independently represents a sulfur atom or an oxygen atom,
Z 1 and Z 2 Each independently represents a group represented by =c (R) -or a nitrogen atom.
12. The compound according to claim 11, wherein the 1 st structural unit is a structural unit represented by the following formula (IV-1),
in the formula (IV-1),
y represents a group represented by-C (=O) -or an oxygen atom,
r each independently represents:
a hydrogen atom,
Halogen atom,
An optionally substituted alkyl group,
Cycloalkyl optionally having substituents,
Aryl optionally having substituents,
Alkoxy optionally having substituent(s),
Optionally substituted cycloalkoxy,
Aryloxy group optionally having a substituent,
Alkylthio optionally having a substituent,
A cycloalkylthio group optionally having a substituent,
Arylthio optionally having a substituent,
A 1-valent heterocyclic group optionally having a substituent,
Substituted amino optionally having substituent(s),
Acyl optionally having substituent(s),
An optionally substituted imine residue,
An amide group optionally having a substituent,
An imide group optionally having a substituent,
Substituted oxycarbonyl optionally having a substituent,
Alkenyl optionally having substituent(s),
Optionally substituted cycloalkenyl,
Alkynyl optionally having substituents,
Optionally substituted cycloalkynyl,
Cyano group,
Nitro group,
-C(＝O)-R a A group of the formula
-SO 2 -R b The radicals are shown in the figures,
R a and R is b Each independently represents:
a hydrogen atom,
An optionally substituted alkyl group,
Aryl optionally having substituents,
Alkoxy optionally having substituent(s),
Aryloxy group optionally having substituent(s), or
A 1-valent heterocyclic group optionally having a substituent,
the plurality of R's present are optionally the same or different from each other.
13. The compound of any one of claims 10-12, wherein B 1 A 2-valent group having any 1 structure selected from the structures represented by the following formulas (VI-1) to (VI-16),
-CU1-(VI-1)
-CU1-CU1-(VI-2)
-CU1-CU2-(VI-3)
-CU1-CU1-CU1-(VI-4)
-CU1-CU2-CU1-(VI-5)
-CU1-CU1-CU2-(VI-6)
-CU1-CU2-CU2-(VI-7)
-CU2-CU1-CU2-(VI-8)
-CU1-CU1-CU1-CU1-(VI-9)
-CU1-CU1-CU1-CU2-(VI-10)
-CU1-CU1-CU2-CU1-(VI-11)
-CU1-CU1-CU2-CU2-(VI-12)
-CU1-CU2-CU1-CU2-(VI-13)
-CU1-CU2-CU2-CU1-(VI-14)
-CU1-CU2-CU2-CU2-(VI-15)
-CU2-CU1-CU2-CU2-(VI-16)
in the formulas (V-1) to (V-16),
CU1 represents the 1 st structural unit,
CU2 represents the 2 nd building block,
in the case where CU1 exists in 2 or more numbers, the 2 or more numbers of CU1 that exist are optionally the same or different from each other, and in the case where CU2 exists in 2 or more numbers, the 2 or more numbers of CU2 that exist are optionally the same or different from each other, wherein in formula (VI-8), the case where 2 numbers of CU2 that exist are the same is not included.
CN202280051331.0A 2021-07-28 2022-07-25 Compound, composition, and photoelectric conversion element Pending CN117769897A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-123353 2021-07-28
JP2022101134A JP2023020911A (en) 2021-07-28 2022-06-23 Compound, composition and photoelectric conversion element
JP2022-101134 2022-06-23
PCT/JP2022/028636 WO2023008376A1 (en) 2021-07-28 2022-07-25 Compound, composition, and photoelectric conversion element

Publications (1)

Publication Number Publication Date
CN117769897A true CN117769897A (en) 2024-03-26

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Country Link
CN (1) CN117769897A (en)

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