WO2021221032A1 - 光電変換素子、撮像素子、光センサ、及び化合物 - Google Patents

光電変換素子、撮像素子、光センサ、及び化合物 Download PDF

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WO2021221032A1
WO2021221032A1 PCT/JP2021/016702 JP2021016702W WO2021221032A1 WO 2021221032 A1 WO2021221032 A1 WO 2021221032A1 JP 2021016702 W JP2021016702 W JP 2021016702W WO 2021221032 A1 WO2021221032 A1 WO 2021221032A1
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group
substituent
formula
photoelectric conversion
atom
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French (fr)
Japanese (ja)
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和平 金子
陽介 山本
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Fujifilm Corp
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Fujifilm Corp
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Priority to CN202180031340.9A priority Critical patent/CN115461884A/zh
Priority to JP2022518068A priority patent/JP7411073B2/ja
Publication of WO2021221032A1 publication Critical patent/WO2021221032A1/ja
Priority to US18/050,047 priority patent/US12484442B2/en
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    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a photoelectric conversion element, an image sensor, an optical sensor, and a compound.
  • a planar solid-state image sensor in which photodiodes (PDs) are arranged two-dimensionally and signal charges generated in each PD are read out by a circuit is widely used.
  • a structure in which a color filter that transmits light of a specific wavelength is arranged on the light incident surface side of the flat-type solid-state image sensor is common.
  • a single plate type in which color filters that transmit blue (B: blue) light, green (G: green) light, and red (R: red) light are regularly arranged on each PD arranged two-dimensionally.
  • Solid-state image sensors are well known.
  • Patent Document 1 discloses a photoelectric conversion element having a photoelectric conversion film containing the following compounds.
  • Patent Document 2 discloses a photoelectric conversion element having a photoelectric conversion film containing the following compounds.
  • Patent Document 3 discloses a photoelectric conversion element having a photoelectric conversion film containing the following compounds.
  • the photoelectric conversion film further contains an n-type semiconductor material, and has a bulk heterostructure formed in a state where the compound represented by the above formula (1) and the n-type semiconductor material are mixed [1].
  • An image pickup device including the photoelectric conversion element according to any one of [1] to [9].
  • [12] A compound represented by the formula (1) described later.
  • [13] The compound according to [12], which is represented by the formula (2) described later.
  • [14] The compound according to [12] or [13], which is represented by the formula (3) described later.
  • [15] The compound according to [14], wherein in the above formula (3), the above R c1 represents an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group which may have a substituent.
  • the present invention it is possible to provide a photoelectric conversion element exhibiting excellent external quantum efficiency and responsiveness to light having any wavelength in the red wavelength region, the green wavelength region, and the blue wavelength region.
  • the present invention can also provide an image pickup device, an optical sensor, and a compound related to the photoelectric conversion element.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the bonding direction of the divalent group described in the present specification is not particularly limited, and for example, in the case of -CO-O-, it may be either -CO-O- or -O-CO-.
  • the term (hetero) aryl means aryl and heteroaryl.
  • Photoelectric conversion element A feature of the present invention as compared with the prior art is that a compound represented by the formula (1) described later (hereinafter, also referred to as “specific compound”) is used for the photoelectric conversion film.
  • the photoelectric conversion element of the present invention exhibits excellent external quantum efficiency and responsiveness to light having any wavelength in the red wavelength region, the green wavelength region, and the blue wavelength region.
  • the specific compound has a structural site (formula (1)) capable of functioning as a donor as compared with the compounds disclosed in the prior documents 1 to 3.
  • the group represented by Y 11 of the specific compound is an oxygen atom
  • the overlap integral of HOMO and LUMO becomes larger because the flatness of the specific compound is further increased.
  • the effect of is more remarkably superior.
  • the external quantum efficiency for light of each wavelength in the red wavelength region, green wavelength region, and blue wavelength region, and / or the responsiveness to light of each wavelength in the red wavelength region, green wavelength region, and blue wavelength region will be improved. Superiority is also simply referred to as "the effect of the present invention is superior".
  • FIG. 1 shows a schematic cross-sectional view of an embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10a shown in FIG. 1 includes a conductive film (hereinafter, also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and an upper electrode. It has a structure in which functional transparent conductive films (hereinafter, also referred to as upper electrodes) 15 are laminated in this order.
  • FIG. 2 shows a schematic cross-sectional view of another embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10b shown in FIG. 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are laminated in this order on a lower electrode 11.
  • the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be appropriately changed depending on the application and characteristics.
  • the photoelectric conversion element 10a it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Further, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 ⁇ 10-5 to 1 ⁇ 10 7 V / cm is applied between the pair of electrodes. From the viewpoint of performance and power consumption, the applied voltage is more preferably 1 ⁇ 10 -4 to 1 ⁇ 10 7 V / cm, further preferably 1 ⁇ 10 -3 to 5 ⁇ 10 6 V / cm.
  • the voltage application method it is preferable to apply the voltage so that the electron blocking film 16A side serves as a cathode and the photoelectric conversion film 12 side serves as an anode in FIGS. 1 and 2.
  • a voltage can be applied by the same method.
  • the photoelectric conversion element 10a (or 10b) can be suitably applied to optical sensor applications and image sensor applications.
  • the carbon atom to which R b6 and R b7 are bonded and the carbon atom adjacent thereto (specified in the formula (2), A 41).
  • X 11 and X 12 independently represent an oxygen atom, a sulfur atom, a selenium atom, or -NR a4- .
  • R a4 represents a hydrogen atom or a substituent.
  • the type of the substituent represented by R a4 is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • Ra4 it is preferable to represent a substituent in that the effect of the present invention is more excellent, and among them, an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent, is more preferable.
  • an alkyl group or an aryl group which may have a substituent is more preferable, and an alkyl group or a phenyl group which may have a substituent and has 1 to 4 carbon atoms is further preferable.
  • substituents that the above-mentioned alkyl group, aryl group, and heteroaryl group may have include the groups exemplified by the substituent W described later.
  • the substituent is preferably an alkyl group having 1 to 6 carbon atoms.
  • oxygen atom, sulfur atom, or ⁇ NR a4-— is preferable because the effect of the present invention is more excellent.
  • R a5 represents a hydrogen atom or a substituent.
  • the type of the substituent represented by R a5 is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • Ra5 a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom is more preferable, in that the effect of the present invention is more excellent.
  • a nitrogen atom is preferable because the effect of the present invention is more excellent.
  • R a1 to R a3 independently represent a hydrogen atom or a substituent.
  • the type of the substituent represented by R a1 to R a3 is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • the molecular weight of the substituent is preferably 700 or less in terms of further improving the vapor deposition suitability of the specific compound.
  • the effect of the present invention is more excellent, and the above-mentioned substituents are other than the substituents represented by the formulas (DK-1) to (DK-4) described later. It is preferably a substituent.
  • Ra1 represents a substituent
  • the effect of the present invention is more excellent.
  • the substituent include an amino group, a substituted amino group, an indolin derivative group, a tetrahydroquinolin derivative group, and a 2-pyrazolin derivative group.
  • Ra1 it is preferable to represent a substituent because the effect of the present invention is more excellent, and among them, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group which may have a substituent is used. More preferably, it may have a substituent, an aryl group or an alkynyl group is more preferable, and it may have a substituent, a phenyl group or an alkynyl group having 1 to 4 carbon atoms (for example, an acetylynyl group, an ethynyl group).
  • a group, a propynyl group, a butynyl group, etc.) are more preferable, and a phenyl group or an alkynyl group having 1 to 2 carbon atoms, which may have a substituent, is particularly preferable.
  • substituents that the above-mentioned aryl group, heteroaryl group, alkenyl group, and alkynyl group may have include the groups exemplified by the substituent W described later.
  • the substituent is preferably a cyano group or the like.
  • the alkenyl group and the alkynyl group further have a substituent
  • the substituent is preferably an aryl group (for example, a phenyl group) or the like.
  • R a2 and R a3 a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group are preferable, and a hydrogen atom is more preferable, respectively, in that the effect of the present invention is more excellent.
  • a 11 represents a ring containing at least two carbon atoms.
  • the two carbon atoms are intended as a carbon atom to which Y 11 is bonded and a carbon atom adjacent to the carbon atom to which Y 11 is bonded in the formula (1), and both carbon atoms constitute A 11. It is an atom that does.
  • the number of carbon atoms of A 11 is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 15.
  • the carbon number is a number including two carbon atoms specified in the formula (1).
  • a 11 may have a hetero atom, and examples of the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Atoms, sulfur atoms, or oxygen atoms are preferred, with oxygen atoms being more preferred.
  • a 11 may have a substituent, and a halogen atom is preferable as the substituent.
  • the number of heteroatoms in A 11 0 preferably to 10, more preferably from 0 to 5, 0-2 is more preferable.
  • the number of the heteroatoms is a number that does not include the number of heteroatoms contained in the group represented by Y 11 in the formula (1) and the number of halogen atoms that A 11 can have as a substituent.
  • a 11 may indicate an aromatic, it may not illustrated.
  • a 11 may have a monocyclic structure or a condensed ring structure, but is preferably a condensed ring containing at least one of a 5-membered ring, a 6-membered ring, and a 5-membered ring and a 6-membered ring.
  • the number of rings forming the fused ring is preferably 2 to 4, more preferably 2 to 3.
  • the ring represented by A 11 preferably has a group represented by the following formula (A1). Note that * 1 represents the bond position with the carbon atom to which Y 11 specified in the formula (1) is bonded, and * 2 is the carbon atom to which Y 11 specified in the formula (1) is bonded. Represents the bond position with an adjacent carbon atom.
  • L represents a single bond or -NR L- .
  • RL represents a hydrogen atom or a substituent.
  • an alkyl group, an aryl group, or a heteroaryl group is preferable, and an alkyl group or an aryl group is more preferable.
  • L a single bond is preferable.
  • RY1 to RY5 independently represent a hydrogen atom or a substituent. As RY1 to RY5 , an alkyl group, an aryl group, or a heteroaryl group is preferable, and an alkyl group or an aryl group is more preferable, respectively.
  • R Z3 )- is more preferably represented, and -CO- is even more preferred.
  • R Z1 represents a hydrogen atom or a substituent.
  • the type of the substituent represented by R Z1 is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R Z1 a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom is more preferable, because the effect of the present invention is more excellent.
  • R Z2 and R Z3 each independently represent a cyano group or -COOR Z4.
  • R Z4 represents an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • the R Z2 and R Z3 are preferably cyano groups.
  • a ring formed by bonding -LYZ- and two carbon atoms specified in the formula (1) is 5-membered.
  • a ring or a combination of 6-membered rings is preferable.
  • the 5-membered ring or the 6-membered ring may be further fused with a different ring (preferably a benzene ring) to form a condensed ring structure.
  • the group represented by the formula (A1) the group represented by the following formula (A2) is more preferable.
  • a 1 and A 2 each independently represent a hydrogen atom or a substituent. It is preferred to form a ring with each other as A 1 and A 2, it is more preferable to form a benzene ring linked to each other to A 1 and A 2. It is also preferable that the benzene ring formed by A 1 and A 2 further has a substituent. As the substituent, a halogen atom is preferable, and a chlorine atom or a fluorine atom is more preferable. Further, the substituents of the benzene ring formed by A 1 and A 2 may be further linked to each other to form a ring.
  • the substituents of the benzene ring formed by A 1 and A 2 may be further linked to each other to form a benzene ring.
  • * 1 in formula (A2), * 2, and Z 1, * 1 in the above-mentioned formula (A1), have the same meanings as * 2, Z, preferred embodiments are also the same.
  • the group represented by the formula (A1) the group represented by the following formula (A3) is more preferable.
  • a 3 ⁇ A 6 each independently represent a hydrogen atom or a substituent.
  • a 3 and A 4 may be connected to each other to form a ring
  • a 4 and A 5 may be connected to each other to form a ring
  • a 5 and A 6 may be connected to each other. May form a ring.
  • a benzene ring is preferable as the ring formed by connecting A 3 and A 4 , A 4 and A 5 , and A 5 and A 6 to each other.
  • a 4 and A 5 are bonded to each other to form a ring, the ring and A 4 and A 5 are formed by connecting together a benzene ring is preferred.
  • the ring formed by connecting A 4 and A 5 to each other may be further substituted with a substituent.
  • * 1 in formula (A3), * 2, and Z 1, * 1 in the above-mentioned formula (A1), have the same meanings as * 2, Z, preferred embodiments are also the same.
  • a merocyanine dye usually used as an acidic nucleus is preferable, and specific examples thereof include the following.
  • Pyrazolinen nuclei for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, and 1- (2-benzothiazolyl) -3-methyl-2.
  • C Isooxazolinone nuclei: For example, 3-phenyl-2-isooxazoline-5-one, 3-methyl-2-isooxazoline-5-one and the like.
  • D Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxyindole and the like.
  • E 2,4,6-trioxohexahydropyrimidine nucleus: For example, barbituric acid or 2-thiobarbituric acid and its derivatives.
  • Examples of the derivative include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, and 1,3-.
  • 1,3-Diaryls such as diphenyl, 1,3-di (p-chlorophenyl), 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl such as 1-ethyl-3-phenyl
  • Examples include the body and 1,3-diheteroaryl compounds such as 1,3-di (2-pyridyl).
  • Examples of the derivative include 3-alkyl loadanine such as 3-methyl loadanine, 3-ethyl loadanine and 3-allyl loadanine, 3-aryl loadanine such as 3-phenyl loadanin, and 3- (2-). Examples thereof include 3-heteroaryl loadanine such as pyridyl) loadanine.
  • Examples of the derivative include 3-alkyl loadanine such as 3-methyl loadanine, 3-ethyl loadanine and 3-allyl loadanine, 3-aryl loadanine such as 3-phenyl loadanin, and 3- (2-).
  • Examples thereof include 3-heteroaryl loadanine such as pyridyl) loadanine.
  • (G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
  • Tianaftenone nucleus For example,
  • (I) 2-thio-2,5-thiazolidinedione nucleus For example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
  • (J) 2,4-Thiazolidinedione nucleus For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
  • (K) Thiazoline-4-one nuclei for example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.
  • (L) 2,4-Imidazolidinedione (hydantoin) nucleus For example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione and the like.
  • (M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nuclei for example, 2-thio-2,4-imidazolidinedione, and 3-ethyl-2-thio-2,4-imidazole. Lysine dione etc.
  • (N) Imidazoline-5-one nucleus For example, 2-propylmercapto-2-imidazolin-5-one and the like.
  • (O) 3,5-Pyrazolidinedione nuclei For example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione and the like.
  • Indanone nuclei For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone and the like.
  • R Benzofuran-3- (2H) -one nuclei: For example, benzofuran-3- (2H) -one and the like.
  • S 2,2-dihydrophenalene-1,3-dione nucleus and the like.
  • R a6 represents a hydrogen atom or a substituent.
  • the type of the substituent represented by R a6 is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • Ra6 a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group is preferable, and a hydrogen atom is more preferable, in that the effect of the present invention is more excellent.
  • R a7 and R a8 independently represent a cyano group or -COOR a9.
  • R a9 represents an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • a cyano group is preferable in that the effect of the present invention is more excellent.
  • Condition A In the formula (1), when X 11 represents ⁇ NR a4- , X 13 represents a nitrogen atom.
  • the above-mentioned substituent is not a substituent represented by the following formulas (DK-1) to (DK-4). Further, under the condition B, when Ra1 represents a substituent, the molecular weight of the substituent is 700 or less in that the vapor deposition suitability of the specific compound is further improved.
  • R x11 to R x14 each independently represent a hydrogen atom or a substituent.
  • R x11 and R x12 , R x12 and R x13 , R x13 and R x14 may be combined with each other to form a ring.
  • * X1 represents the coupling position.
  • R x21 and R x22 each independently represent a substituent.
  • Z x21 represents an oxygen atom or a sulfur atom.
  • * X2 represents the coupling position.
  • Ar x31 and Ar x32 each independently represent an aryl group or a heteroaryl group which may have a substituent.
  • Ar x33 represents an arylene group or a heteroarylene group which may have a substituent.
  • Ar x31 and Ar x32 may be attached to each other via a single bond or a divalent linking group.
  • m 1, Ar x31 and Ar x33 may be bonded to each other via a single bond or a divalent linking group.
  • Ar x32 and Ar x33 may be bonded to each other via a single bond or a divalent linking group.
  • m represents 0 or 1.
  • * X31 represents the coupling position.
  • R x41 represents a substituent. * X41 represents the coupling position.
  • the ring formed by combining R x11 and R x12 , R x12 and R x13 , and R x13 and R x14 with each other is aromatic but non-aromatic. It may be, for example, a benzene ring and the like.
  • the aryl group represented by Ar x31 and Ar x32 and the arylene group represented by Ar x33 are condensed rings in which two or more rings are fused even if they are monocyclic. It may have a structure (condensed ring structure). Examples of the fused ring structure in which two or more rings are fused include naphthalene and the like.
  • the heteroaryl group represented by Ar x31 and Ar x32 and the heteroarylene group represented by Ar x33 have two or more rings condensed even if they are monocyclic. It may have a fused ring structure (condensed ring structure). Examples of the condensed ring structure in which two or more rings are fused include benzothiophene and the like.
  • the specific compound may not have any of a carboxy group, a carboxy group salt, a phosphoric acid group, a phosphoric acid group salt, a sulfonic acid group, and a sulfonic acid group salt from the viewpoint of avoiding deterioration of vapor deposition suitability.
  • a carboxy group a carboxy group salt, a phosphoric acid group, a phosphoric acid group salt, a sulfonic acid group, and a sulfonic acid group salt from the viewpoint of avoiding deterioration of vapor deposition suitability.
  • monosulfate ester groups, monophosphate ester groups, phosphonic acid groups, phosphinic acid groups, boric acid groups, and salts of these groups are taken from the viewpoint of avoiding deterioration of vapor deposition suitability. It is preferable not to have any of the above.
  • the compound represented by the following formula (2) is preferable, and the compound represented by the following formula (3) is more preferable, in that the effect of the present invention is more excellent. ..
  • the compound represented by the formula (2) will be described in detail.
  • X 41 and X 42 independently represent an oxygen atom, a sulfur atom, a selenium atom, or -NR b4- .
  • R b4 has the same meaning as R a4 in the formula (1), and the preferred embodiment is also the same.
  • a sulfur atom or ⁇ NR b4 - is preferable, and ⁇ NR b4-— is more preferable, because the effect of the present invention is more excellent.
  • an oxygen atom, a sulfur atom, or ⁇ NR b4-— is preferable because the effect of the present invention is more excellent.
  • R b1 , R b2 , and R b3 have the same meanings as R a1 , R a2 , and R a3 in the formula (1), and the preferred embodiments are also the same.
  • a 41 represents a ring containing at least two carbon atoms.
  • the two carbon atoms are intended as a carbon atom to which Y 41 is bonded and a carbon atom adjacent to the carbon atom to which Y 41 is bonded in the formula (2), and both carbon atoms constitute A 41. It is an atom that does.
  • a 41 has the same meaning as A 11 in the formula (1), and the preferred embodiment is also the same.
  • R b5 has the same meaning as R a6 in the formula (1), and the preferred embodiment is also the same.
  • R b6 and R b7 each independently represent a cyano group or -COOR b8 , and the cyano group is particularly preferable in that the effect of the present invention is more excellent.
  • R b8 represents an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • X 51 represents an oxygen atom, a sulfur atom, a selenium atom, or -NR c5- .
  • R c5 is synonymous with Ra 4 in the formula (1), and the preferred embodiment is also the same.
  • X 51 is preferably an oxygen atom, a sulfur atom, or ⁇ NR c5 ⁇ in that the effect of the present invention is more excellent.
  • R c1 , R c2 , and R c3 have the same meanings as R a1 , R a2 , and R a3 in the formula (1), and the preferred embodiments are also the same.
  • R c4 represents a hydrogen atom or a substituent.
  • the type of the substituent represented by R c4 is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R c4 it is preferable to represent a substituent in that the effect of the present invention is more excellent, and among them, an alkyl group, an aryl group, or a heteroaryl group, which may have a substituent, is more preferable. It is more preferably an alkyl group or an aryl group which may have a substituent, and further preferably an alkyl group or a phenyl group having 1 to 4 carbon atoms which may have a substituent.
  • examples of the substituent that the above-mentioned alkyl group, aryl group, and heteroaryl group may have include the groups exemplified by the substituent W described later.
  • the substituent is preferably an alkyl group having 1 to 6 carbon atoms.
  • a 51 represents a ring containing at least two carbon atoms.
  • the two carbon atoms are intended as a carbon atom to which Y 51 is bonded and a carbon atom adjacent to the carbon atom to which Y 51 is bonded in the formula (3), and both carbon atoms constitute A 51. It is an atom that does.
  • a 51 has the same meaning as A 11 in the formula (1), and the preferred embodiment is also the same.
  • R c6 has the same meaning as R a6 in the formula (1), and the preferred embodiment is also the same.
  • R c7 and R c8 each independently represent a cyano group or -COOR c9 , and the cyano group is particularly preferable in that the effect of the present invention is more excellent.
  • R c9 represents an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • the compound is represented by the formula (3) and satisfies one or more of the following (X1) to (X3). It is more preferable that the compound is represented by the formula (3) and satisfies two or more of the following (X1) to (X3), and the compound is represented by the formula (3) and the following (X1). It is more preferable to satisfy all of (X3).
  • the group represented by (X1) R c1 is an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group which may have a substituent.
  • the group represented by (X2) Y 51 is an oxygen atom.
  • the group represented by R c4 is an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • substituent W in the present specification will be described.
  • substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, and an aryl.
  • heterocyclic group may be called heterocyclic group
  • cyano group hydroxy group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group
  • acyloxy group carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino Group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, ary
  • the substituent W may be further substituted with the substituent W.
  • the alkyl group may be substituted with a halogen atom.
  • the details of the substituent W are described in paragraph [0023] of JP-A-2007-234651.
  • the specific compound is any of a carboxy group, a salt of a carboxy group, a phosphoric acid group, a salt of a phosphoric acid group, a sulfonic acid group, and a salt of a sulfonic acid group. It is preferable not to have it.
  • Alkyl group, aryl group, heteroaryl group that the compound represented by any of the formulas (1) to (3) can have
  • the number of carbon atoms of the alkyl group contained in the specific compound (compound represented by any of the formulas (1) to (3)) is not particularly limited, but 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 4 is preferable. More preferred.
  • the alkyl group may be linear, branched or cyclic. Further, the alkyl group may be substituted with a substituent (for example, substituent W).
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group and the like.
  • the number of carbon atoms in the aryl group of the specific compound is not particularly limited, but 6 to 30 is preferable, 6 to 18 is more preferable, and 6 is further. preferable.
  • the aryl group may have a monocyclic structure or a condensed ring structure in which two or more rings are fused (condensed ring structure). Further, the aryl group may be substituted with a substituent (for example, substituent W).
  • aryl group examples include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, a biphenyl group, a fluorenyl group and the like, and a phenyl group, a naphthyl group or an anthryl group. Is preferable.
  • the number of carbon atoms in the heteroaryl group (monovalent aromatic heterocyclic group) of the specific compound (compound represented by any of the formulas (1) to (3)) is not particularly limited, but is preferably 3 to 30. 3 to 18 are more preferable.
  • the heteroaryl group may be substituted with a substituent (for example, substituent W).
  • the heteroaryl group has a hetero atom in addition to a carbon atom and a hydrogen atom.
  • hetero atom examples include a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a sulfur atom, an oxygen atom, or a nitrogen atom is preferable.
  • the number of heteroatoms contained in the heteroaryl group is not particularly limited, and is usually about 1 to 10, preferably 1 to 4, and more preferably 1 to 2.
  • the number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 8, more preferably 5 to 7, and even more preferably 5 to 6.
  • the heteroaryl group may have a monocyclic structure or a condensed ring structure in which two or more rings are fused.
  • an aromatic hydrocarbon ring having no heteroatom for example, a benzene ring
  • the heteroaryl group include pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, pteridinyl group, pyrazinyl group, quinoxalinyl group, pyrimidinyl group, quinazolyl group, pyridadinyl group, cinnolinyl group and phthalazinyl group.
  • the molecular weight of the specific compound is not particularly limited, but 300 to 900 is preferable. When the molecular weight is 900 or less, the vapor deposition temperature does not rise and the decomposition of the compound is unlikely to occur. When the molecular weight is 300 or more, the glass transition point of the vapor-deposited film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
  • the maximum absorption wavelength of the specific compound is preferably in the range of 500 to 650 nm, and more preferably in the range of 540 to 620 nm.
  • the maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance becomes 0.5 to 1.
  • Absorption coefficient at the maximum absorption wavelength of the specific compound is preferably 50000 cm -1 or more, more preferably 75000Cm -1 or more, 100000 -1 or more is more preferable.
  • the upper limit of the extinction coefficient is not particularly limited, and is, for example, 300,000 cm -1 or less.
  • the specific compound is preferably a compound having an ionization potential of 5.2 to 6.2 eV in a single film in terms of matching the energy level with the p-type semiconductor material described later, and is preferably 5.2 to 6. It is more preferably a compound having a value of 1 eV, and even more preferably a compound having a value of 5.4 to 6.0 eV.
  • one specific compound may be used alone, or two or more thereof may be used in combination.
  • the photoelectric conversion film preferably contains an n-type semiconductor material described later, or an n-type semiconductor material described later and a p-type semiconductor material described later, in addition to the specific compound described above.
  • Total film thickness in single layer conversion / total film thickness in single layer conversion of specific compound + film thickness in single layer conversion of n-type semiconductor material + film thickness in single layer conversion of p-type semiconductor material ⁇ 100) is preferably 15 to 75% by volume, more preferably 25 to 75% by volume.
  • the photoelectric conversion film is substantially composed of a specific compound and an n-type semiconductor material, or is substantially composed of a specific compound, an n-type semiconductor material, and a p-type semiconductor material. ..
  • “substantially” means that when the photoelectric conversion film is composed of a specific compound and an n-type semiconductor material, the total content of the specific compound and the n-type semiconductor material is 95 with respect to the total mass of the photoelectric conversion film.
  • the photoelectric conversion film is composed of a specific compound, an n-type semiconductor material, and a p-type semiconductor material with the intention of being mass% or more, the specific compound and the n-type semiconductor are relative to the total mass of the photoelectric conversion film. It is intended that the total content of the material and the p-type semiconductor material is 95% by mass or more.
  • the photoelectric conversion film preferably contains an n-type semiconductor material as a component other than the specific compound.
  • the n-type semiconductor material is an acceptor-type organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting electrons. More specifically, the n-type semiconductor material refers to an organic compound having better electron transportability than a specific compound. Further, the n-type semiconductor material preferably has a high electron affinity for a specific compound.
  • the electron mobility (electron carrier mobility) of a compound can be evaluated by using, for example, the Time-of-Flight method (range time method, TOF method) or a field effect transistor element.
  • the electron carrier mobility of the n-type semiconductor material is preferably 10 -4 cm 2 / V ⁇ s or more, more preferably 10 -3 cm 2 / V ⁇ s or more, and 10 ⁇ 2 cm 2 / s or more. It is more preferably V ⁇ s or more.
  • the upper limit of the electron carrier mobility is not particularly limited, but is preferably 10 cm 2 / V ⁇ s or less, for example, from the viewpoint of suppressing the flow of a small amount of current when not irradiated with light.
  • the value of the reciprocal of the LUMO value obtained by the calculation of B3LYP / 6-31G (d) using Gaussian '09 (software manufactured by Gaussian) as the electron affinity value (value multiplied by -1). ) Is used.
  • the electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.
  • the n-type semiconductor material includes, for example, fullerenes selected from the group consisting of fullerene and derivatives thereof, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and Fluorantene derivatives); 5- to 7-membered heterocyclic compounds having at least one nitrogen atom, oxygen atom, and sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline) , Isoquinolin, pteridine, acrydin, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.); polyarylene compound; fluoren
  • the n-type semiconductor material preferably contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
  • fullerenes include fullerenes C60, fullerenes C70, fullerenes C76, fullerenes C78, fullerenes C80, fullerenes C82, fullerenes C84, fullerenes C90, fullerenes C96, fullerenes C240, fullerenes C540, and mixed fullerenes.
  • the fullerene derivative include compounds in which a substituent is added to the fullerene.
  • the substituent is preferably an alkyl group, an aryl group, or a heterocyclic group.
  • the fullerene derivative the compound described in JP-A-2007-123707 is preferable.
  • the thickness) ⁇ 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 35 to 100% by volume.
  • An organic dye may be used as the n-type semiconductor material in place of the n-type semiconductor material described in the upper row or together with the n-type semiconductor material described in the upper row.
  • an organic dye By using an organic dye as the n-type semiconductor material, it is easy to control the absorption wavelength (maximum absorption wavelength) of the photoelectric conversion element in an arbitrary wavelength range.
  • the organic pigments include, for example, cyanine pigments, styryl pigments, hemicyanine pigments, merocyanine pigments (including zero methine merocyanin (simple merocyanin)), rodacianin pigments, allopolar pigments, oxonols pigments, hemioxonor pigments, squalium pigments, croconium pigments, and the like.
  • the n-type semiconductor material contains an organic dye
  • the thickness of the material in terms of a single layer) ⁇ 100) is preferably 15 to 100% by volume, more preferably 35 to 100% by volume.
  • the molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.
  • the photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type semiconductor material are mixed.
  • the bulk heterostructure is a layer in which a specific compound and an n-type semiconductor material are mixed and dispersed in a photoelectric conversion film.
  • the photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method. The bulk heterostructure is described in detail in paragraphs [0013] to [0014] of JP-A-2005-303266.
  • the n-type semiconductor material contained in the photoelectric conversion film may be used alone or in combination of two or more.
  • the photoelectric conversion film preferably contains a p-type semiconductor material in addition to the specific compound and the n-type semiconductor material as components other than the specific compound.
  • the p-type semiconductor material is intended to be a p-type semiconductor material other than the specific compound.
  • the p-type semiconductor material is a donor organic semiconductor material (compound) and refers to an organic compound having a property of easily donating electrons. More specifically, the p-type semiconductor material refers to an organic compound having better hole transport properties than a specific compound.
  • the hole transport property (hole carrier mobility) of a compound can be evaluated by using, for example, the Time-of-Flight method (range time method, TOF method) or a field effect transistor element.
  • the hole carrier mobility of the p-type semiconductor material is preferably 10 -4 cm 2 / V ⁇ s or more, more preferably 10 -3 cm 2 / V ⁇ s or more, and 10 ⁇ 2 cm 2 or more. It is more preferably / V ⁇ s or more.
  • the upper limit of the hole carrier mobility is not particularly limited, but is preferably 10 cm 2 / V ⁇ s or less, for example, from the viewpoint of suppressing the flow of a small amount of current when not irradiated with light. It is also preferable that the p-type semiconductor material has a small ionization potential with respect to a specific compound.
  • the photoelectric conversion film contains a p-type semiconductor material
  • it preferably has a bulk heterostructure formed in a state where a specific compound, a p-type semiconductor material, and the above-mentioned n-type semiconductor material are mixed.
  • Examples of the p-type semiconductor material include triarylamine compounds (for example, N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD), 4, 4'-Bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), the compound described in paragraphs [0128] to [0148] of JP2011-228614A, JP2011-176259.
  • TPD triarylamine compounds
  • Ring compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • porphyrin compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • porphyrin compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • porphyrin compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives,
  • the p-type semiconductor material is a compound represented by the formula (p1), a compound represented by the formula (p2), a compound represented by the formula (p3), a compound represented by the formula (p4), or a formula.
  • the compound represented by (p5) is also preferable.
  • the substituent represented by R include an alkyl group, an alkoxy group, a halogen atom, an alkylthio group, a (hetero) arylthio group, an alkylamino group, a (hetero) arylamino group, and a (hetero) aryl group. Be done. These groups may further have substituents where possible.
  • the (hetero) aryl group may be an arylaryl group which may further have a substituent (that is, a biaryl group; at least one of the aryl groups constituting this group may be a heteroaryl group).
  • R the group represented by R in the formula (IX) of WO2019 / 081416 is also preferable.
  • X and Y are each independently, -CR 2 2 -, sulfur atom, oxygen atom, -NR 2 -, or -SiR 2 2 - represents a.
  • R 2 is a hydrogen atom, an alkyl group which may have a substituent (preferably a methyl group or a trifluoromethyl group), an aryl group which may have a substituent, or a hetero which may have a substituent.
  • R 2 exist 2 or more aryl groups may each be the same or different.
  • the p-type semiconductor material contained in the photoelectric conversion film may be used alone or in combination of two or more.
  • the photoelectric conversion film in the present invention is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode).
  • the non-luminescent film is intended to be a film having an emission quantum efficiency of 1% or less, and the emission quantum efficiency is preferably 0.5% or less, more preferably 0.1% or less.
  • the photoelectric conversion film can be formed mainly by a coating film forming method and a dry film forming method.
  • the coating type film formation includes, for example, a drop casting method, a casting method, a dip coating method, a die coater method, a roll coater method, a bar coater method, and a coating method including a spin coating method, an inkjet method, a screen printing method, and a gravure printing method.
  • Various printing methods including a flexographic printing method, an offset printing method, and a microcontact printing method, and a Langmuir-Blodgett (LB) method and the like.
  • the dry film forming method includes, for example, a physical vapor deposition method such as a vapor deposition method (particularly a vacuum vapor deposition method), a sputtering method, an ion plating method, an MBE (Molecular Beam Epitaxy) method, and a CVD method such as plasma polymerization. Chemical Vapor Deposition) method can be mentioned. Of these, the dry film deposition method is preferable, and the vacuum vapor deposition method is more preferable. When the photoelectric conversion film is formed by the vacuum vapor deposition method, the manufacturing conditions such as the degree of vacuum and the vapor deposition temperature can be set according to a conventional method.
  • the thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and even more preferably 50 to 500 nm.
  • the electrodes are made of a conductive material.
  • the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected.
  • the material constituting the upper electrode 15 is, for example, antimony or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluid topped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO:: Conductive metal oxides such as Indium Tin Oxide) and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; mixtures of these metals with conductive metal oxides or Laminates; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and the like.
  • ATO Antimony Tin Oxide
  • FTO Fluid topped Tin Oxide
  • ITO Conductive metal oxides such as Indium Tin Oxide) and indium zinc oxide (IZO)
  • metal thin films such as gold, silver, chromium, and nickel
  • organic conductive materials such as polyaniline, polythiophene, and polypyr
  • the sheet resistance is preferably 100 to 10000 ⁇ / ⁇ .
  • the degree of freedom in the range of film thickness that can be thinned is large.
  • Increasing the light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
  • the film thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.
  • the lower electrode 11 may be transparent or may reflect light without being transparent, depending on the intended use.
  • Materials constituting the lower electrode 11 include, for example, antimony or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), and the like.
  • Conductive metal oxides metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides or nitrides of these metals (Titanium nitride (TiN) is taken as an example). Examples include mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.
  • the method for forming the electrode is not particularly limited and can be appropriately selected depending on the electrode material. Specifically, wet methods such as printing method and coating method; physical methods such as vacuum deposition method, sputtering method, and ion plating method; and chemical methods such as CVD and plasma CVD method, etc. Can be mentioned.
  • wet methods such as printing method and coating method; physical methods such as vacuum deposition method, sputtering method, and ion plating method; and chemical methods such as CVD and plasma CVD method, etc.
  • the electrode material is ITO
  • methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and application of a dispersion of indium tin oxide can be mentioned.
  • the photoelectric conversion element of the present invention has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
  • the intermediate layer include a charge blocking film.
  • the charge blocking film include an electron blocking film and a hole blocking film.
  • the photoelectric conversion element preferably has at least an electron blocking film as an intermediate layer. Each film will be described in detail below.
  • the electron blocking film is a donor organic semiconductor material (compound).
  • the electron blocking membrane preferably has an ionization potential of 4.8 to 5.8 eV.
  • the ionization potential Ip (B) of the electron blocking film, the ionization potential Ip (1) of the first compound, and the ionization potential Ip (2) of the second compound are Ip (B) ⁇ Ip (1).
  • a p-type semiconductor material can be used as the electron blocking film.
  • One type of p-type semiconductor material may be used alone, or two or more types may be used.
  • Examples of the p-type semiconductor material include p-type organic semiconductor materials, and specifically, a triarylamine compound (for example, N, N'-bis (3-methylphenyl)-(1,1'-biphenyl)). -4,4'-diamine (TPD), 4,4'-bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), paragraphs [0128] to JP-A-2011-228614
  • TPD triarylamine
  • TPD 4,4'-bis [N- (naphthyl) -N-phenyl-amino] biphenyl
  • paragraphs [0128] to JP-A-2011-228614 The compounds described in [0148], the compounds described in paragraphs [0052] to [0063] of JP-A-2011-176259, and the compounds described in paragraphs [0119]-[0158] of JP-A-2011-225544.
  • Examples thereof include compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted chalcone compounds, oxazole compounds, fluorenone compounds, silazane compounds, and metal complexes having a nitrogen-containing heterocyclic compound as a ligand.
  • Examples of the p-type semiconductor material include compounds having a smaller ionization potential than the n-type semiconductor material, and if this condition is satisfied, the organic dye exemplified as the n-type semiconductor material can also be used.
  • a polymer material can also be used as the electron blocking film.
  • the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrrole, pyrrole, picolin, thiophene, acetylene, and diacetylene, and derivatives thereof.
  • the electron blocking film may be composed of a plurality of films.
  • the electron blocking film may be made of an inorganic material.
  • Inorganic materials that can be electron blocking films include, for example, calcium oxide, chromium oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium oxide copper, niobium oxide, molybdenum oxide, and indium copper oxide. , Indium silver oxide, and iridium oxide.
  • the hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type semiconductor material can be used.
  • the method for producing the charge blocking film is not particularly limited, and examples thereof include a dry film forming method and a wet film forming method.
  • Examples of the dry film forming method include a vapor deposition method and a sputtering method.
  • the vapor deposition method may be any of a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable.
  • Examples of the wet film forming method include an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and a gravure coating method, and have high accuracy. From the viewpoint of patterning, the inkjet method is preferable.
  • the thickness of the charge blocking film is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.
  • the photoelectric conversion element may further have a substrate.
  • the type of substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate.
  • the position of the substrate is not particularly limited, and usually, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.
  • the photoelectric conversion element may further have a sealing layer.
  • the performance of the photoelectric conversion material may be significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is covered with a dense metal oxide, metal nitride, ceramics such as metal nitride, or a sealing layer such as diamond-like carbon (DLC: Diamond-like Carbon) that does not allow water molecules to permeate. By covering and sealing, the above deterioration can be prevented.
  • the material of the sealing layer may be selected and manufactured according to the paragraphs [0210] to [0215] of JP2011-082508.
  • the photoelectric conversion film may have a configuration of only one layer or a multilayer configuration of two or more layers.
  • the photoelectric conversion film in the photoelectric conversion element of the present invention has a multilayer structure of two or more layers, at least one layer may contain a specific compound.
  • the photoelectric conversion film in the photoelectric conversion element is, for example, a layer containing a specific compound and a layer having photosensitivity in the near-infrared to infrared region. It is also preferable to configure it as a laminated body with.
  • the configuration of such a photoelectric conversion element for example, the configurations of the photoelectric conversion elements disclosed in JP-A-2019-208026, JP-A-2018-125850, JP-A-2018-125884 and the like can be applied. ..
  • An image sensor is an element that converts optical information of an image into an electric signal. Normally, a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and each photoelectric conversion element (pixel) has an optical signal. Is converted into an electric signal, and the electric signal can be sequentially output to the outside of the image sensor for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
  • the image sensor is mounted on a digital camera, an image sensor such as a digital video camera, an electronic endoscope, an image sensor such as a mobile phone, and the like.
  • the photoelectric conversion element of the present invention is also preferably used for an optical sensor having the photoelectric conversion element of the present invention.
  • the optical sensor may be used by the photoelectric conversion element alone, or may be used as a line sensor in which the photoelectric conversion element is arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion element is arranged in a plane.
  • the present invention also relates to compounds.
  • the compound of the present invention is a compound (specific compound) represented by the above-mentioned formula (1), and the preferred embodiment is also the same.
  • the specific compound is particularly useful as a material for a photoelectric conversion film used in an optical sensor, an image sensor, or a photovoltaic cell. In general, the specific compound often functions as a p-type organic semiconductor in the photoelectric conversion film.
  • the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic agent material.
  • Compound (A-1) is derived from 2-bromothiazole-5-carboxyaldehyde, org. Lett. Synthesized according to the method described in 2019, 21, 3028-3033.
  • Compound (B-1) is derived from 2,4-thiazolidinedione, Bioorg. Med. Chem. Lett. , 2006, 16, 49-54, and synthesized by referring to the method.
  • Compound (D-15) was synthesized from compound (B-2) by referring to the method for synthesizing compound (D-1) (specifically, the method for synthesizing compound (A-3) and subsequent compounds).
  • the structures of the compounds (D-1) to (D-26) and the comparative compounds (R-1) to (R-3) are specifically shown below.
  • a C C double composed of a carbon atom to which R b2 is bonded and a carbon atom adjacent thereto. It is intended to include both cis and trans forms that can be distinguished based on the group corresponding to the bond.
  • a C C double composed of a carbon atom to which R c2 is bonded and a carbon atom adjacent thereto. It is intended to include both cis and trans forms that can be distinguished based on the group corresponding to the bond.
  • a photoelectric conversion element was manufactured by the following procedure.
  • the photoelectric conversion element includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, and an upper electrode 15.
  • an amorphous ITO is formed on a glass substrate by a sputtering method to form a lower electrode 11 (thickness: 30 nm), and a compound (EB-1) described later is vacuumed on the lower electrode 11.
  • An electron blocking film 16A was formed by forming a film by a heat vapor deposition method.
  • the compound described above (D-1) and n-type semiconductor material (fullerene (C 60)), p-type semiconductor as desired A material (a compound of any of the compounds (P-1) to (P-4) described later) and each of them were co-deposited by a vacuum vapor deposition method so as to have a single layer equivalent of 80 nm to form a film.
  • a photoelectric conversion film 12 having a bulk heterostructure of 160 nm (240 nm when a p-type semiconductor material was also used) was formed.
  • an amorphous ITO was formed on the photoelectric conversion film 12 by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
  • a SiO film is formed on the upper electrode 15 as a sealing layer by a vacuum deposition method, and then an aluminum oxide (Al 2 O 3 ) layer is formed on the SiO film by an ALCVD (Atomic Layer Chemical Vapor Deposition) method to form a photoelectric conversion element.
  • ALCVD Atomic Layer Chemical Vapor Deposition
  • the photoelectric conversion is carried out by the same method except that the compound (D-1) is changed to the compounds (D-2) to (D-26) or the comparative compounds (R-1) to (R-3).
  • the element was manufactured.
  • the compounds (D-2) to (D-26) and the comparative compounds (R-1) to (R-3) are as described above.
  • Electrode forming material As the electron blocking film forming material, the following compound (EB-1) was used.
  • n-type semiconductor material Fullerene (C 60 ) was used as the n-type semiconductor material.
  • ⁇ P-type semiconductor material> The following compounds (P-1) to (P-4) were used as the p-type semiconductor material.
  • the photoelectric conversion efficiency was 50% or more, and that the photoelectric conversion element had sufficient external quantum efficiency.
  • the external quantum efficiency was measured using an Optel constant energy quantum efficiency measuring device. The amount of light irradiated was 50 ⁇ W / cm 2 .
  • the photoelectric conversion efficiency of the photoelectric conversion element of Comparative Example 1 was standardized to 1, and the relative value of the photoelectric conversion efficiency of each photoelectric conversion element was obtained. Evaluated by criteria. From the viewpoint of practicality, an evaluation of "D” or higher is preferable, and an evaluation of "C” or higher is more preferable.
  • the rise time of the photoelectric conversion element of Comparative Example 1 was standardized to 1, and the relative value of the rise time of each photoelectric conversion element was obtained. evaluated. From the viewpoint of practicality, an evaluation of "D” or higher is preferable, and an evaluation of "C” or higher is more preferable.
  • Table 1 The results are shown in Table 1.
  • Table 1 The remarks column in Table 1 represents the main feature points of Examples 1 to 34.
  • the column “Formula (2)” indicates whether or not the dye corresponds to the compound represented by the formula (2).
  • the case where the dye corresponds to the compound represented by the formula (2) is referred to as "A”, and the case where the dye does not correspond to the compound represented by the formula (2) is referred to as "B”.
  • the column “Formula (3)” indicates whether or not the dye corresponds to the compound represented by the formula (3).
  • the case where the dye corresponds to the compound represented by the formula (3) is referred to as "A”
  • the case where the dye does not correspond to the compound represented by the formula (3) is referred to as "B".
  • R a1 / R b1 / R c1 when the dye is applied to the compound represented by the formula (1), the formula (2), or the formula (3), R a1 , R b1 , Or the group represented by R c1 is an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group which may have a substituent.
  • the case where the group represented by R a1 , R b1 or R c1 corresponds to the above-mentioned group is referred to as "A”, and the case where it does not correspond is referred to as "B".
  • R c4 is represented by R c4 when the dye corresponds to the compound represented by the formula (3) and the dye is applied to the compound represented by the formula (3). Indicates whether the group is an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • the case where the group represented by R c4 corresponds to the above-mentioned group is referred to as "A”, and the case where it does not correspond is referred to as "B”.
  • the compound which does not apply to the formula (3) was set as "-".
  • the columns "Y 11 / Y 41 / Y 51 " are Y 11 , Y 41 when the dye is applied to the compound represented by the formula (1), the formula (2), or the formula (3). , Or whether the group represented by Y 51 is an oxygen atom.
  • the case where the group represented by Y 11 , Y 41 , or Y 51 corresponds to an oxygen atom is referred to as “A”, and the case where it does not correspond is referred to as “B”.
  • the photoelectric conversion element of the example exhibited excellent external quantum efficiency and responsiveness to light of any wavelength in the red wavelength region, the green wavelength region, and the blue wavelength region. rice field. Further, it was confirmed that when the specific compound is a compound represented by the formula (2) (preferably, the compound represented by the formula (3)), the external quantum efficiency and / or the responsiveness is more excellent. (See, for example, the comparison between Examples 14 and 21-26, and the comparison between Examples 9 and 15-17 and Examples 18-20). Further, the specific compound is a compound represented by any of the formulas (1) to (3), and the group represented by R a1 , R b1 or R c1 may have a substituent.
  • an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group, and the group represented by Y 11 , Y 41 , or Y 51 is an oxygen atom
  • the external quantum efficiency and / or responsiveness is higher. It was confirmed to be excellent (for example, comparison between Examples 9 and 14, comparison between Examples 18 to 20 and Examples 24 to 26, and comparison between Examples 15 to 17 and Examples 21 to 23. See comparison).
  • the specific compound is a compound represented by the formula (3) and satisfies one or more of the following (X1) to (X3) (preferably two or more). More preferably, it was confirmed that the external quantum efficiency and / or responsiveness was more excellent (see comparison with Examples 1 to 14).
  • R c1 is an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group which may have a substituent.
  • the group represented by (X2) Y 51 is an oxygen atom.
  • the group represented by R c4 is an alkyl group, an aryl group, or a heteroaryl group which may have a substituent.
  • the photoelectric conversion element of the comparative example does not meet the desired requirements.
  • the comparative compound (R-1) does not satisfy the condition B. That is, it has a substituent represented by the formula (DK-3).
  • the comparative compound (R-2) does not satisfy the condition A.
  • the comparative compound (R-3) does not satisfy the condition B. That is, it has a substituent represented by the formula (DK-2).

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