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Definitions

• the present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound.
• Patent Document 1 discloses a compound having a specific structure as a material for use in photoactive organic electronic components.
• a photoelectric conversion element is required to have high quantum efficiency when it receives red and green light, where the red and green light has a wavelength in the range of 500 to 700 nm.
• the present inventors have studied a photoelectric conversion element using the compound disclosed in Patent Document 1 and have found that there is room for improvement in quantum efficiency when red and green light is received.
• an object of the present invention is to provide a photoelectric conversion element that has excellent quantum efficiency when receiving red and green light.
• Another object of the present invention is to provide an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound related to the above-mentioned photoelectric conversion element.
• a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film contains a compound represented by formula (1) described below.
• X3 represents -C ( Rc1Rc2 )-.
• R c1 and R c2 may be bonded to each other to form a ring which may have a substituent.
• the above-mentioned substituents may be bonded to each other to form a ring which may have a substituent.
• Each R a2 independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, a cyano group, a nitro group, an amino group, or -Si(R Si1 R Si2 R Si3 ).
• Each R Si1 , R Si2 , and R Si3 independently represent an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent.
• the photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of [1] to [8], wherein the photoelectric conversion film has a bulk heterostructure formed in a state in which the compound represented by the formula (1) and the n-type organic semiconductor are mixed.
• the photoelectric conversion element according to [9] wherein the n-type organic semiconductor contains a fullerene selected from the group consisting of fullerenes and derivatives thereof.
• An imaging element having the photoelectric conversion element according to any one of [1] to [13].
• An optical sensor comprising the photoelectric conversion element according to any one of [1] to [13].
• [16] A method for producing an imaging element, comprising the step of producing the photoelectric conversion element according to any one of [1] to [13].
• [17] A compound represented by the formula (1) described below.
• [18] The compound according to [17], wherein X3 represents -C ( Rc1Rc2 )-.
• R c1 and R c2 may be bonded to each other to form a ring which may have a substituent.
• the above-mentioned substituents may be bonded to each other to form a ring which may have a substituent.
• Each R a2 independently represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, a cyano group, a nitro group, an amino group, or -Si(R Si1 R Si2 R Si3 ).
• Each R Si1 , R Si2 , and R Si3 independently represent an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent.
• the present invention it is possible to provide a photoelectric conversion element that has excellent quantum efficiency when receiving red and green light. Furthermore, according to the present invention, there can be provided an imaging element, an optical sensor, a method for manufacturing an imaging element, and a compound related to the above-mentioned photoelectric conversion element.
• FIG. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element.
• FIG. 2 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits.
• the hydrogen atom may be either a protium atom (normal hydrogen atom) or a deuterium atom (for example, a deuterium atom, etc.).
• substituents, linking groups, etc. hereinafter also referred to as "substituents, etc." represented by specific symbols, or when a plurality of substituents, etc. are simultaneously specified, it means that the respective substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.
• the substituent W in this specification will be described.
• the substituent W can be, for example, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), 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, an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a secondary
• each of the above groups may further have a substituent (for example, one or more groups among the above groups, etc.) if possible.
• a substituent for example, one or more groups among the above groups, etc.
• an alkyl group that may have a substituent is also included as one form of the substituent W.
• the substituent W has a carbon atom
• the number of carbon atoms contained in the substituent W is, for example, 1 to 20.
• the number of atoms other than hydrogen atoms contained in the substituent W is, for example, 1 to 30.
• the specific compound described later does not have a carboxy group, a salt of a carboxy group, a salt of a phosphate group, a sulfonic acid group, a salt of a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, a boronic acid group (-B(OH) 2 ), and/or a primary amino group as a substituent.
• halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.
• the aliphatic hydrocarbon group may be any of linear, branched, and cyclic.
• the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• the alkyl group may be linear, branched, or cyclic.
• 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, and a cyclopentyl group.
• the alkyl group may be any one of a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may have these ring structures as partial structures.
• examples of the substituent which the alkyl group may have examples of the substituent which the alkyl group may have include the groups exemplified as the substituent W.
• an aryl group preferably having 6 to 18 carbon atoms, more preferably having 6 carbon atoms
• a heteroaryl group preferably having 5 to 18 carbon atoms, more preferably having 5 to 6 carbon atoms
• a halogen atom preferably a fluorine atom or a chlorine atom
• the alkyl group moiety in the alkoxy group is preferably the above-mentioned alkyl group
• the alkyl group moiety in the alkylthio group is preferably the above-mentioned alkyl group.
• examples of the substituent which the alkoxy group may have include the same substituents as those in the alkyl group which may have a substituent.
• examples of the substituent which the alkylthio group may have include the same substituents as those in the alkyl group which may have a substituent.
• the alkenyl group may be any of linear, branched, and cyclic.
• the number of carbon atoms in the alkenyl group is preferably 2 to 20.
• examples of the substituent which the alkenyl group may have include the same as those of the substituent in the alkyl group which may have a substituent.
• the alkynyl group may be any of linear, branched, and cyclic.
• the number of carbon atoms in the alkynyl group is preferably 2 to 20.
• an aromatic ring or an aromatic ring constituting an aromatic ring group may be either a monocyclic ring or a polycyclic ring (e.g., 2 to 6 rings).
• a monocyclic aromatic ring is an aromatic ring having only one aromatic ring structure as a ring structure.
• a polycyclic (e.g., 2 to 6 rings, etc.) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6, etc.) aromatic ring structures condensed as ring structures.
• the aromatic ring preferably has 5 to 15 ring members.
• the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle.
• the number of heteroatoms contained as ring member atoms is, for example, 1 to 10.
• the heteroatom 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.
• the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring.
• Examples of the aromatic heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring (e.g., a 1,2,3-triazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring), a tetrazine ring (e.g., a 1,2,4,5-tetrazine ring), a quinoxaline ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a
• the type of substituent that the aromatic ring may have is, for example, the group exemplified as the substituent W.
• the number of the substituents may be 1 or more (for example, 1 to 4, etc.).
• aromatic ring group includes, for example, groups obtained by removing one or more (eg, 1 to 5, etc.) hydrogen atoms from the above-mentioned aromatic ring.
• aryl group includes, for example, a group obtained by removing one hydrogen atom from a ring that corresponds to an aromatic hydrocarbon ring among the above aromatic rings.
• heteroaryl group includes, for example, a group in which one hydrogen atom has been removed from a ring corresponding to an aromatic heterocycle among the above aromatic rings.
• arylene group includes, for example, a group formed by removing two hydrogen atoms from a ring corresponding to an aromatic hydrocarbon ring among the above aromatic rings.
• heteroarylene group includes, for example, a group formed by removing two hydrogen atoms from a ring corresponding to an aromatic heterocycle among the above aromatic rings.
• the types of the substituents which these groups may have include, for example, the groups exemplified for the substituent W.
• the number of the substituents may be 1 or more (for example, 1 to 4, etc.).
• non-aromatic ring refers to a ring structure that is not aromatic.
• non-aromatic rings include aliphatic hydrocarbon rings and aliphatic heterocycles.
• examples of the aliphatic hydrocarbon ring include cycloalkanes, cycloalkenes, and cycloalkynes.
• Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, and a ⁇ -butyrolactone ring.
• aliphatic hydrocarbon ring group includes, for example, a group in which one or more hydrogen atoms (for example, 1 to 5, etc.) have been removed from a ring corresponding to an aliphatic hydrocarbon ring.
• aliphatic heterocyclic group includes, for example, a group in which one or more hydrogen atoms (for example, 1 to 5, etc.) have been removed from a ring corresponding to an aliphatic heterocycle.
• rings e.g., aromatic rings and non-aromatic rings
• rings may be either monocyclic or polycyclic (e.g., 2 to 6 rings).
• a monocyclic ring is a ring structure having only one ring
• a polycyclic ring is a ring structure having multiple (e.g., 2 to 6, etc.) condensed rings.
• a formula showing a chemical structure contains a plurality of identical symbols showing the type or number of groups, unless otherwise specified, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different.
• a formula showing a chemical structure contains a plurality of groups of the same type (for example, alkyl groups, etc.), unless otherwise specified, the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the groups of the same type may be the same or different.
• the bond direction of the divalent group is not limited unless otherwise specified.
• the compound may be either "X-O-CO-Z" or "X-CO-O-Z”.
• the general formula or structural formula representing the compound may be described in only one of the cis and trans forms for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to either the cis or trans form, and the compound may be in either the cis or trans form, or a mixture of these.
• the general formula or structural formula representing the compound may be described without distinguishing between stereoisomers for convenience. Even in such cases, unless otherwise specified, the form of the compound is not limited to any one, and may be any one form or a mixture.
• a compound having an asymmetric carbon atom may be either the S-form or the R-form, or a mixture of these.
• the photoelectric conversion element of the present invention is a photoelectric conversion element having a photoelectric conversion film and a transparent conductive film in this order, and the photoelectric conversion film contains a compound represented by formula (1) described below (hereinafter also referred to as a "specific compound").
• the specific compound is a so-called ADA type compound having a donor site (D) in the center of the molecule and an acceptor site (A) at both ends.
• D donor site
• A acceptor site
• the absorptivity tends to decrease, but by making at least one of the acceptor sites of the specific compound a specific monocyclic structure, the internal quantum efficiency when red and green light is received is surprisingly improved, resulting in excellent quantum efficiency of the photoelectric conversion element when red and green light is received.
• the quantum efficiency of the photoelectric conversion element when red and green light is received is excellent.
• superior quantum efficiency when the photoelectric conversion element receives red and green light is also referred to as "superior effect of the present invention.”
• FIG. 1 is a schematic cross-sectional view of one embodiment of a photoelectric conversion element of the present invention.
• the photoelectric conversion element 10a shown in Figure 1 has a configuration in which a conductive film (hereinafter also referred to as the "lower electrode") 11 functioning as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound, and a transparent conductive film (hereinafter also referred to as the "upper electrode”) 15 functioning as an upper electrode are stacked in this order.
• Fig. 2 shows a configuration example of another photoelectric conversion element.
• 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 laminated 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 changed as appropriate depending on the application and characteristics.
• the photoelectric conversion element 10 a it is preferable that light is incident on the photoelectric conversion film 12 through the upper electrode 15 . Furthermore, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and it is preferable to apply a voltage of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 7 V/cm between the pair of electrodes. In terms of performance and power consumption, the applied voltage is more preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 7 V/cm, and even more preferably 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 6 V/cm.
• the voltage is preferably applied so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode.
• the photoelectric conversion element 10a (or 10b) is used as an optical sensor or incorporated in an imaging element, a voltage can be applied in a similar manner.
• the photoelectric conversion element 10a (or 10b) can be suitably used as an imaging element. The configuration of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.
• the photoelectric conversion element has a photoelectric conversion film.
• the photoelectric conversion film contains a specific compound, which is a compound represented by formula (1).
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• X 3 represents -C(R c1 R c2 )-, -O-C(R c3 R c4 )-, -NR N1 -C(R c5 R c6 )-, or -NR N11 -.
• R c1 , R c2 , R c3 , R c4 , R c5 , R c6 , R N1 , and R N11 each independently represent a hydrogen atom or a substituent.
• R c1 and R c2 , R c3 and R c4 , and R c5 and R c6 may be bonded to each other to form a ring that may have a substituent.
• the substituents may be bonded to each other to form a ring that may have a substituent.
• A1 and A2 each independently represent formula (A-1).
• B1 represents a monocyclic or polycyclic ring containing at least 3 carbon atoms and optionally having a substituent, provided that when B1 represents the monocyclic ring and the monocyclic ring has two or more of the substituents, the number of aromatic ring groups among the substituents possessed by the monocyclic ring is 1 or less.
• R Y1 represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent.
• R Y4 , R Y5 , R Y6 , and R Y7 each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent. * indicates the bond position.
• at least one of A 1 and A 2 represents a group represented by the above formula (A-1) in which B 1 is represented by the above monocycle.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• substituents represented by R 1 and R 2 include the substituents exemplified as the substituent W described above.
• R 1 and R 2 are preferably hydrogen atoms.
• R a1 represents a hydrogen atom or a substituent. Examples of the substituent represented by R a1 include the substituents exemplified as the substituent W described above, and the substituent represented by R a2 described below is preferable. When a plurality of R a1 are present, the groups represented by the plurality of R a1 may be the same or different.
• the specific compound is a compound represented by formula (1-1).
• a 1 , A 2 , R 1 , R 2 and X 3 have the same meanings as the respective groups in formula (1).
• the definition and preferred embodiments of R a1 are as described above, and a plurality of R a1's may be the same or different.
• R a2 represents an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, a cyano group, a nitro group, an amino group, or -Si(R Si1 R Si2 R Si3 ).
• the groups represented by the plurality of R a2's may be the same or different.
• the group represented by R a2 is preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an acyl group which may have a substituent, an aliphatic hetero group which may have a substituent, or -Si(R Si1 R Si2 R Si3 ), and more preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, a halogen atom, an alkoxy group which may have a substituent, an acyl group which may have a substituent, or -Si(R Si1 R Si2 R Si3 ).
• the aliphatic hydrocarbon group represented by R a2 includes a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
• the number of carbon atoms in the linear aliphatic hydrocarbon group is, for example, 1 to 20, and from the viewpoint of superior production suitability, is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
• Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group, and a methyl group, an ethyl group, or an n-propyl group is preferred.
• the branched aliphatic hydrocarbon group may have 3 to 20 carbon atoms, and from the viewpoint of superior manufacturability, it is preferably 3 to 10, more preferably 3 to 6, and even more preferably 3 or 4.
• Specific examples include an isopropyl group, a sec-butyl group, an iso-butyl group, a tert-butyl group, a neopentyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-butyloctyl group, a 2-hexyloctyl group, a 2-hexyldodecyl group, and a 2-octyldodecyl group, with an isopropyl group or a tert-butyl group being preferred.
• the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.
• Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a dicyclobutanyl group, a bicyclo[1.1.1]pentyl group, and a bicyclo[2.2.2]pentyl group, of which a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group is preferable, and a cyclopropyl group is more preferable.
• the aromatic ring group represented by R a2 which may have a substituent may be either a monocyclic or polycyclic ring, preferably a monocyclic ring.
• the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic ring group, preferably an aromatic hydrocarbon ring group.
• the aromatic ring group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, and even more preferably 5 to 8 ring members.
• the number of carbon atoms in the aromatic ring group which may have a substituent is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
• the lower limit is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more.
• heteroatom contained in the aromatic heterocyclic group 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.
• aromatic ring group examples include aromatic hydrocarbon ring groups such as a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, and a fluorenyl group; and aromatic heterocyclic groups such as a pyridine ring group, a pyrimidine ring group, a pyridazine ring group, a pyrazine ring group, a triazine ring group, a tetrazine ring group, a quinoxaline ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a benzimidazole ring group, a
• Examples of the substituent that the aromatic ring group may have include the substituents exemplified as the substituent W described above, and the substituent selected from the substituent group S described below is preferable.
• the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.
• halogen atom represented by R a2 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
• the alkyl group which may have a substituent may be any one of linear, branched, and cyclic.
• Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups, isopropyl, sec-butyl, iso-butyl, tert-butyl, neopentyl, 1-ethylpentyl, 2,6-dimethylheptyl, 1-butylheptyl, 1-hexylheptyl, and 1-hexyl.
• alkyl groups include branched alkyl groups such as an undecyl group and a 1-octylundecyl group, and cyclic alkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a dicyclobutanyl group, a bicyclo[1.1.1]pentyl group, and a bicyclo[2.2.2]pentyl group.
• branched alkyl groups such as an undecyl group and a 1-octylundecyl group
• cyclic alkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohepty
• a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
• the alkoxy group may have 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms, in terms of superior manufacturability.
• Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, and a cyclopropoxy group, with a methoxy group or an ethoxy group being preferred.
• Examples of the substituent that the alkoxy group may have include the substituents exemplified as the substituent W described above, and a substituent selected from the substituent group S described below is preferable.
• the optionally substituted hydrocarbon group in the optionally substituted acyl group represented by R a2 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon ring group, and is preferably an aliphatic hydrocarbon group.
• the aliphatic hydrocarbon group contained in the acyl group may be linear, branched, or cyclic.
• the number of carbon atoms in the aliphatic hydrocarbon group of the acyl group can be 1 to 20, and from the viewpoint of superior production suitability, it is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
• the carbon atom in the aliphatic hydrocarbon group include linear aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group, isopropyl group, sec-butyl group, iso-butyl group, tert-butyl group, neopentyl group, 1-ethylpentyl group, 2,6-dimethylheptyl, 1-butylheptyl group, 1-hexylheptyl group, 1-hexylundecyl group, and and 1-octylundecyl group; and cyclic aliphatic hydrocarbon groups such as
• a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a tert-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
• the number of carbon atoms in the aromatic hydrocarbon ring group of the acyl group is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6.
• Specific examples include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, and a fluorenyl group, with a phenyl group being preferred.
• the acyl group may have 2 to 21 carbon atoms, preferably 2 to 11 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2 or 3 carbon atoms, in terms of superior production suitability.
• Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, and a benzoyl group, and an acetyl group or a propionyl group is preferable.
• the substituent that the acyl group may have include the substituents exemplified as the substituent W described above, and a substituent selected from the substituent group S described below is preferable.
• the aliphatic heterocyclic group represented by R a2 which may have a substituent may be either a monocyclic or polycyclic ring.
• the aliphatic heterocyclic group preferably has 6 to 20 ring members, more preferably 6 to 12 ring members, and even more preferably 6 to 8 ring members.
• the aliphatic heterocyclic group which may have a substituent preferably has 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 4 to 10 carbon atoms.
• heteroatom contained in the aliphatic heterocyclic group 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.
• Examples of the aliphatic heterocyclic group include a pyrrolidine ring group, an oxolane ring group, a thiolane ring group, a piperidine ring group, a tetrahydrofuran ring group, a tetrahydropyran ring group, a thiane ring group, a piperazine ring group, a morpholine ring group, a quinuclidine ring group, a pyrrolidine ring group, an azetidine ring group, an oxetane ring group, an aziridine ring group, a dioxane ring group, a pentamethylene sulfide ring group, and a ⁇ -butyrolactone ring group, and a piperidine ring group is preferable.
• Examples of the substituent that the aliphatic heterocyclic group may have include the substituents exemplified as the substituent W described above, and a substituent selected from the substituent group S described below is preferable.
• the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.
• the amino group represented by R a2 may be any one of a primary amino group, a secondary amino group, and a tertiary amino group, with a tertiary amino group being preferred.
• the hydrocarbon group substituting the amino group is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group.
• R.sub.Si1 , R.sub.Si2 and R.sub.Si3 each independently represent an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent.
• the definitions and preferred embodiments of the optionally substituted aliphatic hydrocarbon group and optionally substituted aromatic ring group represented by R Si1 , R Si2 , and R Si3 are the same as those of the optionally substituted aliphatic hydrocarbon group and optionally substituted aromatic ring group represented by R a2 , respectively.
• R Si1 , R Si2 , and R Si3 are preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms or an aromatic ring group which may have a substituent selected from the substituent group S described below, and more preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a phenyl group.
• —Si(R Si1 R Si2 R Si3 ) include a trimethylsilyl group, a triethylsilyl group, a dimethylisopropylsilyl group, a diethylisopropylsilyl group, a cyclohexyldimethylsilyl group, a dimethylphenylsilyl group, and a tert-butyldimethylsilyl group, with a trimethylsilyl group or a triethylsilyl group being preferred, and a trimethylsilyl group being more preferred.
• Substituent group S linear aliphatic hydrocarbon groups having 1 to 4 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 5 carbon atoms , cyclic aliphatic hydrocarbon groups having 3 to 8 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, halogen atoms, and -Si( RSi1RSi2RSi3 ).
• the linear aliphatic hydrocarbon group having 1 to 4 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms, and the cyclic aliphatic hydrocarbon group having 3 to 8 carbon atoms in the above-mentioned Substituent Group S may have a halogen atom.
• Examples of the linear aliphatic hydrocarbon group having 1 to 4 carbon atoms in the above-mentioned substituent group S include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, with a methyl group, an ethyl group, or an n-propyl group being preferred, and a methyl group being more preferred.
• Examples of the branched aliphatic hydrocarbon group having 3 to 5 carbon atoms in the above-mentioned substituent group S include an isopropyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, and a neopentyl group, with an isopropyl group or a tert-butyl group being preferred, and an isopropyl group being more preferred.
• Examples of the cyclic aliphatic hydrocarbon having 3 to 8 carbon atoms in the above-mentioned substituent group S include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
• a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group is preferable, and a cyclopropyl group is more preferable.
• halogen atom which the aliphatic hydrocarbon group in the above-mentioned substituent group S may have include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom or a chlorine atom being preferred.
• Examples of the alkoxy group having 1 to 5 carbon atoms in the above substituent group S include a methoxy group, an ethoxy group, an isopropoxy group, and a cyclopropoxy group, with a methoxy group being preferred.
• Halogen atoms in the above-mentioned substituent group S include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, with fluorine atoms and chlorine atoms being preferred.
• the group selected from the above-mentioned substituent group S is preferably a group selected from a linear aliphatic hydrocarbon group having 1 or 2 carbon atoms, a branched aliphatic hydrocarbon group having 3 or 4 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a halogen atom.
• X3 represents -C( Rc1Rc2 ) -, -O- C ( Rc3Rc4 )-, -NRN1 -C( Rc5Rc6 )-, or -NRN11- .
• the bonding direction of the group represented by X 3 is not particularly limited.
• the specific compound is a compound represented by formula (1-X1) when X 3 is -C(R c1 R c2 )- in formula (1), a compound represented by formula (1-X2) or a compound represented by formula (1-X3) when X 3 is -O-C(R c3 R c4 )-, a compound represented by formula (1-X4) or a compound represented by formula (1-X5) when X 3 is -NR N1 -C(R c5 R c6 )-, and a compound represented by formula (1-X6) when X 3 is -NR N11 -.
• X3 is preferably -C( Rc1Rc2 )-. That is, the specific compound is preferably a compound represented by formula (1-X1).
• a 1 , A 2 , R 1 , R 2 , X 1 , X 2 , R c1 , R c2 , R c3 , R c4 , R c5 , R c6 , R N1 , and R N11 have the same meanings as the respective groups in formula (1).
• R c1 , R c2 , R c3 , R c4 , R c5 , R c6 , R N1 and R N11 each independently represent a hydrogen atom or a substituent.
• R c1 and R c2 , R c3 and R c4 , and R c5 and R c6 may be bonded to each other to form a ring that may have a substituent.
• the above-mentioned substituents of the ring that may have the above-mentioned substituent may be bonded to each other to form a ring that may have a substituent.
• Examples of the substituents represented by Rc1 , Rc2 , Rc3 , Rc4 , Rc5 , Rc6 , RN1 , and RN11 include the substituents exemplified for the substituent W described above.
• the molecular weight of the substituents represented by Rc1 , Rc2 , Rc3 , Rc4 , Rc5 , Rc6 , RN1 , and RN11 is preferably 150 or less, more preferably 90 or less, and even more preferably 50 or less. There is no particular lower limit, but a molecular weight of 15 or more is preferable.
• the number of carbon atoms in the substituents represented by R c1 , R c2 , R c3 , R c4 , R c5 , R c6 , R N1 , and R N11 is preferably 7 or less, more preferably 5 or less, and even more preferably 3 or less. There is no particular lower limit, but 1 or more is preferable.
• the above-mentioned substituent is preferably an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.
• the aliphatic hydrocarbon groups represented by Rc1 , Rc2 , Rc3 , Rc4 , Rc5 , Rc6 , RN1 , and RN11 include linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups.
• the number of carbon atoms in the linear aliphatic hydrocarbon group can be 1 to 20, preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.
• Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group, with a methyl group, an ethyl group, or an n-propyl group being preferred, and a methyl group or an ethyl group being more preferred.
• the branched aliphatic hydrocarbon group may have 3 to 20 carbon atoms, preferably 3 to 10, more preferably 3 to 6, and even more preferably 3 or 4.
• Specific examples include an isopropyl group, a sec-butyl group, an iso-butyl group, a tert-butyl group, a neopentyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-butyloctyl group, a 2-hexyloctyl group, a 2-hexyldodecyl group, and a 2-octyldodecyl group, with an isopropyl group, a sec-butyl group, an iso-butyl group, or a tert-butyl group being preferred.
• the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.
• Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a dicyclobutanyl group, a bicyclo[1.1.1]pentyl group, and a bicyclo[2.2.2]pentyl group, of which a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group is preferable, and a cyclopropyl group is more preferable.
• the aromatic ring groups which may have the above-mentioned substituents represented by Rcl , Rc2 , Rc3, Rc4 , Rc5 , Rc6 , RN1 and RNIl may be either monocyclic or polycyclic .
• the aromatic ring group may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, with an aromatic hydrocarbon ring group being preferred.
• the aromatic ring group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, and even more preferably 5 to 8 ring members.
• the number of carbon atoms in the aromatic ring group which may have a substituent is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
• the lower limit is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more.
• the heteroatom contained in the aromatic heterocyclic group 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.
• aromatic ring group examples include aromatic hydrocarbon ring groups such as a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, and a fluorenyl group; and aromatic heterocyclic groups such as a pyridine ring group, a pyrimidine ring group, a pyridazine ring group, a pyrazine ring group, a triazine ring group, a tetrazine ring group, a quinoxaline ring group, a pyrrole ring group, a furan ring group, a thiophene ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a benzimidazole ring group, a
• Examples of the substituent that the aliphatic hydrocarbon group may have include the substituents exemplified as the substituent W described above, and groups selected from the substituent group S described above are preferred.
• the number of the substituents is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 3.
• the aliphatic heterocyclic groups which may have the above-mentioned substituents represented by Rc1 , Rc2 , Rc3, Rc4 , Rc5 , Rc6 , RN1 , and RN11 may be either monocyclic or polycyclic .
• the aliphatic heterocyclic group preferably has 6 to 20 ring members, more preferably 6 to 12 ring members, and even more preferably 6 to 8 ring members.
• the aliphatic heterocyclic group preferably has 1 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 4 to 10 carbon atoms.
• heteroatom contained in the aliphatic heterocyclic group 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.
• Examples of the aliphatic heterocyclic group include a pyrrolidine ring group, an oxolane ring group, a thiolane ring group, a piperidine ring group, a tetrahydrofuran ring group, a tetrahydropyran ring group, a thiane ring group, a piperazine ring group, a morpholine ring group, a quinuclidine ring group, a pyrrolidine ring group, an azetidine ring group, an oxetane ring group, an aziridine ring group, a dioxane ring group, a pentamethylene sulfide ring group, and a ⁇ -butyrolactone ring group, and a piperidine ring group is preferable.
• Examples of the substituent that the aliphatic heterocyclic group may have include the substituents exemplified as the substituent W described above, and the substituents selected from the substituent group S described above are preferred.
• the number of the substituents is not particularly limited, but is preferably 1 to 4, and more preferably 1 to 3.
• R c1 , R c2 , R c3 , R c4 , R c5 , R c6 , R N1 , and R N11 are preferably substituted, more preferably an aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent, and even more preferably an aliphatic hydrocarbon group which may have a substituent.
• R c1 and R c2 , R c3 and R c4 , and R c5 and R c6 may be bonded to each other to form a ring which may have a substituent.
• the ring is preferably a monocyclic ring.
• the ring may be any one of an aliphatic hydrocarbon ring, an aliphatic hetero ring, and an aromatic ring, with an aliphatic hydrocarbon ring being preferred.
• the ring preferably has 3 to 10 ring members, more preferably 3 to 8 ring members, and even more preferably 4 to 7 ring members.
• aliphatic hydrocarbon ring examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopentadiene ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a cyclodecane ring.
• a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring is preferable, and a cyclohexane ring is more preferable.
• heteroatom contained in the aliphatic heterocycle 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.
• Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydrofuran ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, a pyrrolidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, a pentamethylene sulfide ring, and a ⁇ -butyrolactone ring, and a piperidine ring is preferable.
• the ring may have a substituent, and preferably has a substituent in that the effects of the present invention are more excellent.
• substituents include the substituents exemplified as the substituent W described above, and an alkyl group, an aromatic ring group, or a halogen atom is preferable, and an alkyl group or a halogen atom is more preferable.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom.
• the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.
• the substituents may be bonded to each other to form a further ring.
• the ring formed by bonding the substituents to each other may be any of an aliphatic hydrocarbon ring, an aliphatic heterocycle, and an aromatic ring, but is preferably an aliphatic hydrocarbon ring.
• Such an embodiment may be, for example, an embodiment in which the alkyl groups substituted on the cyclohexane ring are bonded to each other to form a norbornene ring as a whole.
• Examples of structures formed by further forming a ring by bonding the substituents of the ring to each other include a norbornene ring structure, a bicyclo[3.1.1]heptane ring structure, a bicyclo[1.1.1]pentane ring structure, a bicyclo[2.2.2]pentane ring structure, and a fluorene ring structure.
• the structure formed by further forming a ring by bonding the substituents of the ring preferably has 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms.
• R N11 is preferably a group represented by formula (C-1) or a group represented by formula (C-2) in that the quantum efficiency has a smaller electric field strength dependency.
• R d1 to R d5 each independently represent a hydrogen atom or a substituent, provided that at least one of the following requirements C1 and C2 is satisfied.
• Requirement C1: R d1 and R d5 are different groups.
• Requirement C2: R d2 and R d4 are different groups.
• Examples of the substituents represented by R d1 to R d5 include the substituents exemplified as the substituent W described above, and the substituents selected from the substituent group S described above are preferred.
• R d6 to R d8 each independently represent a hydrogen atom or a substituent, provided that R d6 to R d8 are different groups.
• substituents represented by R d6 to R d8 include the substituents exemplified for the substituent W described above.
• An optionally substituted aliphatic hydrocarbon group, an optionally substituted aromatic ring group, or an optionally substituted aliphatic heterocyclic group is preferable, an optionally substituted aliphatic hydrocarbon group or an optionally substituted aromatic ring group is more preferable, and an optionally substituted aliphatic hydrocarbon group is even more preferable.
• R d6 to R d8 are the same as those of the groups described above as the substituents represented by R c1 , R c2 , R c3 , R c4 , R c5 , R c6 , R N1 , and R N11 .
• the specific compound satisfies any one of the following requirements 1 to 4 with respect to X3 . In terms of superior manufacturability, it is also preferable that the specific compound satisfies any one of requirements 1 to 3.
• Requirement 3 X3 represents -NR N1 -C(R c5 R c6 )-, and R c5 and R c6 are different groups, or R c5 and R c6 form a monocycle having a substituent.
• the substituted monocyclic ring in requirements 1 to 3 has a plurality of substituents, the substituents may be bonded to each other to form a ring which may have a substituent.
• the specific compound satisfies any one of the following requirements 5 to 7 and the above requirement 4 with respect to X3 . In terms of superior manufacturability, it is also preferable that the specific compound satisfies any one of requirements 5 to 7.
• a 1 and A 2 each independently represent formula (A-1). However, at least one of A 1 and A 2 represents a group represented by formula (A-1) in which B 1 is a monocyclic ring. In terms of better effects of the present invention, it is preferable that both A 1 and A 2 represent a group represented by formula (A-1) in which B 1 is a monocyclic ring.
• B 1 represents a monocyclic or polycyclic ring containing at least three carbon atoms and optionally having a substituent, and is preferably a monocyclic ring optionally having a substituent.
• the at least three carbon atoms contained in B 1 are the three carbon atoms specified in formula (A-1).
• the number of ring members is preferably 3 to 20, more preferably 3 to 10, and still more preferably 4 to 8.
• the ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring.
• the monocyclic ring preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms.
• the number of ring members is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10.
• it is preferably a condensed ring containing at least one of a 5-membered ring and a 6-membered ring.
• the numbers of ring members and carbon atoms in the above monocyclic and polycyclic rings include the three carbon atoms specified in the formula.
• the monocyclic and polycyclic rings may be either aromatic or non-aromatic rings.
• the monocyclic and polycyclic rings may have a heteroatom, such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, or a boron atom, and preferably a sulfur atom, a nitrogen atom, or an oxygen atom.
• the number of heteroatoms contained in the monocyclic ring is preferably 0 to 10, more preferably 0 to 5, and even more preferably 1 to 4.
• the monocyclic ring and polycyclic ring may have a substituent as described above. However, when the monocyclic ring has two or more substituents, the number of aromatic ring groups among the substituents of the monocyclic ring is 1 or less, and preferably 0. Examples of the substituent that the monocyclic and polycyclic rings may have include the groups exemplified as the substituent W above.
• a halogen atom, an alkyl group, an aromatic ring group, or a silyl group is preferable, and a halogen atom or an alkyl group is more preferable.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear.
• the alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 3 carbon atoms.
• the alkyl group may have a substituent.
• the substituent that the alkyl group may have is preferably a halogen atom, an aromatic ring group, or a silyl group.
• the aromatic ring group may have a substituent, and the substituent that the aromatic ring group may have is preferably a halogen atom, an alkyl group, or a silyl group.
• substituteduent on the ring refers to a monovalent group other than a hydrogen atom bonded to a ring member atom, and also includes a group bonded to a heteroatom that constitutes the ring.
• the number of aromatic ring groups in the substituents of the ring refers to the number of aromatic ring groups as monovalent groups bonded to ring atoms, and does not include aromatic ring groups as substituents substituting monovalent groups bonded to ring atoms, for example, aromatic ring groups in alkyl groups substituted with aromatic ring groups, such as the phenyl group contained in a phenylmethyl group (Ph-CH 2 -, where Ph is a phenyl group).
• R Y1 represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic ring group which may have a substituent. Examples of the substituent that the group represented by R Y1 may have include the groups exemplified as the substituent W above.
• the aliphatic hydrocarbon group represented by R Y1 may be any one of linear, branched, and cyclic, and preferably has 1 to 3 carbon atoms.
• the aromatic ring group represented by R Y1 may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and is preferably a phenyl group.
• R Y4 , R Y5 , R Y6 , and R Y7 each independently represent an aliphatic hydrocarbon group which may have a substituent, an aromatic ring group which may have a substituent, or an aliphatic heterocyclic group which may have a substituent.
• Examples of the substituent that the groups represented by R Y4 , R Y5 , R Y6 , and R Y7 may have include the groups exemplified for the substituent W above.
• the aliphatic hydrocarbon groups represented by R Y4 , R Y5 , R Y6 and R Y7 may be linear, branched or cyclic, and preferably have 1 to 3 carbon atoms.
• the aromatic ring group represented by R Y4 , R Y5 , R Y6 , and R Y7 may be either an aromatic hydrocarbon ring group or an aromatic heterocyclic group, and is preferably a phenyl group.
• the aliphatic heterocyclic groups represented by R Y4 , R Y5 , R Y6 and R Y7 each preferably have 5-20 ring members, more preferably 5-12 ring members, and even more preferably 6-8 ring members.
• heteroatoms contained in the aliphatic heterocyclic groups represented by R Y4 , R Y5 , R Y6 , and R Y7 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.
• Examples of the aliphatic heterocycle constituting the aliphatic heterocyclic group include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydrofuran ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, a pyrrolidine ring, an azetidine ring, an oxetane ring, an aziridine ring, a dioxane ring, a pentamethylene sulfide ring, and ⁇ -butyrolactone.
• the group (monocyclic or polycyclic) represented by the above formula (A-1) is preferably a ring used as an acidic nucleus (for example, an acidic nucleus in a merocyanine dye), and examples thereof include the following nuclei: (a) 1,3-dicarbonyl nucleus: for example, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione, and the like. (b) 2,4,6-trioxohexahydropyrimidine nucleus: for example, barbituric acid, 2-thiobarbituric acid, and derivatives thereof.
• an acidic nucleus for example, an acidic nucleus in a merocyanine dye
• derivatives examples 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-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl.
• 3,5-pyrazolidinedione nucleus for example, 1,2-dimethyl-3,5-pyrazolidinedione.
• 1,3-dicarbonyl nucleus for example, a 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, and 1,3-dioxane-4,6-dione.
• a group represented by formula (A-1) in which B 1 is a monocycle is represented by formula (A-11)
• a group represented by formula (A-1) in which B 1 is a polycycle is represented by formula (A-12). That is, in the compound represented by formula (1), at least one of A 1 and A 2 represents a group represented by formula (A-11), and the other represents a group selected from formula (A-11) and formula (A-12). In terms of better effects of the present invention, it is preferable that both A 1 and A 2 are groups represented by formula (A-11).
• Y 1 and Y 2 are the same as Y 1 and Y 2 in formula (A-1).
• B2 represents a monocycle containing at least 3 carbon atoms and which may have a substituent, provided that when the monocycle represented by B2 has two or more substituents, the number of aromatic ring groups among the substituents is 1 or less, and preferably 0. * indicates the bond position.
• B3 represents a monocyclic ring which contains at least 3 carbon atoms and may have a substituent.
• B4 represents a ring which may have a substituent. B4 is condensed with the monocyclic ring represented by B3 .
• B4 may be either a monocyclic ring or a polycyclic ring. * indicates the bond position.
• the group represented by formula (A-1) is preferably a group represented by formula (A-2), and it is more preferable that A1 and A2 are each independently a group represented by formula (A-2).
• R 1 N2 and R 1 N3 each independently represent a hydrogen atom or a substituent, provided that one of R 1 N2 and R 1 N3 represents a hydrogen atom or a substituent other than an aromatic ring group.
• substituents include the groups exemplified as the substituent W above.
• An aliphatic hydrocarbon group which may have a substituent or an aromatic ring group which may have a substituent is preferable, an alkyl group or an aryl group is more preferable, and an alkyl group is even more preferable.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear.
• the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
• the aryl group may be either a monocyclic or polycyclic ring, and is preferably a phenyl group.
• the phenyl group may further have a substituent, and examples of the substituent include the groups exemplified by the substituent W.
• the aliphatic hydrocarbon group includes an alkyl group, an alkenyl group, and an alkynyl group, and is preferably an alkyl group. The preferred embodiments of the alkyl group are as described above.
• Examples of the substituent that the aliphatic hydrocarbon group may have include the groups exemplified as the substituent W above, and a halogen atom, an aryl group, or a silyl group is preferable, and a halogen atom or a silyl group is more preferable. It is also preferable that one of R N2 and R N3 represents a hydrogen atom or an optionally substituted aliphatic hydrocarbon group, and the other of R N2 and R N3 represents a hydrogen atom or a substituent.
• R N2 and R N3 are different groups from each other, since the symmetry of the group represented by formula (A-2) is reduced, aggregation of the specific compound is further suppressed, and the electric field strength dependency of the quantum efficiency is more excellent.
• Y3 represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.
• the specific compound is preferably a compound represented by formula (1-A2).
• formula (1-A1) and formula (1-A2) a plurality of groups represented by the same symbol may be the same or different.
• TMS trimethylsilyl
• each A independently represents one of the following groups. However, at least one A is a monocyclic group.
• the molecular weight of the specific compound is preferably 450 to 900, more preferably 500 to 800, and even more preferably 550 to 700.
• the molecular weight is within the above range, the sublimation temperature of the specific compound is lowered, and it is presumed that the compound has excellent suitability for production.
• the specific compound has an ionization potential of -5.0 to -6.0 eV in a single film.
• the maximum absorption wavelength of the specific compound is preferably in the range of 500 to 700 nm, and more preferably in the range of 500 to 650 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 is 0.5 to 1.0.
• solvent chloroform
• the specific compound is evaporated and the value measured using the specific compound in a film state is regarded as the maximum absorption wavelength of the specific compound.
• the specific compounds are particularly useful as materials for photoelectric conversion films used in imaging devices, photosensors, or photovoltaic cells.
• the specific compounds often function as dyes within the photoelectric conversion films.
• the specific compounds can also be used as coloring materials, liquid crystal materials, organic semiconductor materials, charge transport materials, medicinal materials, and fluorescent diagnostic materials.
• the particular compound may be purified if necessary.
• methods for purifying the specific compound include sublimation purification, purification using silica gel column chromatography, purification using gel permeation chromatography, reslurry washing, reprecipitation purification, purification using an adsorbent such as activated carbon, and recrystallization purification.
• the specific compound may be used alone or in combination of two or more. When two or more types are used, the total amount thereof is preferably within the above range.
• the photoelectric conversion film preferably contains an n-type organic semiconductor in addition to the specific compound.
• the n-type organic semiconductor is a compound different from the above specific compound.
• An n-type organic semiconductor is an acceptor organic semiconductor material (compound) that is an organic compound that has the property of easily accepting electrons.
• an n-type organic semiconductor is an organic compound that has a larger electron affinity when two organic compounds are used in contact with each other. In other words, any organic compound that has electron accepting properties can be used as an acceptor organic semiconductor.
• n-type organic semiconductors include fullerenes selected from the group consisting of fullerenes and derivatives thereof; condensed aromatic carbon ring compounds (e.g., naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives); 5- to 7-membered heterocyclic compounds having at least one selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms (e.g., pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyridine ...
• condensed aromatic carbon ring compounds e.g.,
• Suitable aryl groups include arylazoles, imidazoles, thiazoles, etc.; polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic anhydride; 1,4,5,8-naphthalenetetracarboxylic anhydride imide derivatives and oxadiazole derivatives; anthraquinodimethane derivatives; diphenylquinone derivatives; bathocuproine, bathophenanthroline, and derivatives thereof; triazole compounds; distyrylarylene derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silole compounds; and the compounds described in paragraphs [0056] to [0057] of JP2006-100767A.
• fullerenes selected from the group consisting of fullerene and derivatives thereof are preferred.
• fullerenes include fullerene C60 , fullerene C70 , fullerene C76 , fullerene C78, fullerene C80 , fullerene C82 , fullerene C84 , fullerene C90 , fullerene C96 , fullerene C240 , fullerene C540 , and mixed fullerenes.
• the fullerene derivative may be, for example, a compound 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 is preferably a compound described in JP-A-2007-123707.
• the molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.
• the maximum absorption wavelength of the n-type organic semiconductor is preferably 400 nm or less or in the range of 500 to 600 nm.
• the photoelectric conversion film preferably has a bulk heterostructure formed by mixing a specific compound with an n-type organic semiconductor.
• the bulk heterostructure is a layer in the photoelectric conversion film in which a specific compound and an n-type organic semiconductor are mixed and dispersed.
• a 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 2005-303266 A.
• the difference in electron affinity between the specific compound and the n-type organic semiconductor is preferably 0.1 eV or more.
• the n-type organic semiconductor may be used alone or in combination of two or more.
• the content of the n-type organic semiconductor in the photoelectric conversion film is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and even more preferably 20 to 50 vol%.
• the content of fullerenes relative to the total content of n-type organic semiconductors is preferably 50 to 100 volume %, more preferably 80 to 100 volume %.
• Fullerenes may be used alone or in combination of two or more types.
• the content of the specific compound relative to the total content of the specific compound and the n-type organic semiconductor is preferably 20 to 80 vol%, and more preferably 40 to 80 vol%.
• the content of the specific compound is preferably 10 to 75 vol%, and more preferably 15 to 50 vol%. It is preferable that the photoelectric conversion film is substantially composed of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor contained as desired.
• the total content of the specific compound, the n-type organic semiconductor, and the p-type organic semiconductor relative to the total mass of the photoelectric conversion film is 90 to 100 volume %, preferably 95 to 100 volume %, and more preferably 99 to 100 volume %.
• the photoelectric conversion film preferably contains a p-type organic semiconductor in addition to the specific compound.
• the p-type organic semiconductor is a compound different from the above specific compound.
• a p-type organic semiconductor is a donor organic semiconductor material (compound) that has the property of easily donating electrons.
• a p-type organic semiconductor is an organic compound that has a smaller ionization potential when two organic compounds are used in contact with each other.
• the p-type organic semiconductor may be used alone or in combination of two or more.
• Examples of p-type organic semiconductors include triarylamine compounds (e.g., N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl ( ⁇ -NPD), the compounds described in paragraphs [0128] to [0148] of JP-A No. 2011-228614, the compounds described in paragraphs [0052] to [0063] of JP-A No. 2011-176259, the compounds described in paragraphs [0052] to [0063] of JP-A No.
• TPD N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
• ⁇ -NPD 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl
• the p-type organic semiconductor includes compounds described in JP-A-2022-123944, compounds described in JP-A-2022-122839, compounds described in JP-A-2022-120323, compounds described in JP-A-2022-120273, compounds described in JP-A-2022-115832, compounds described in JP-A-2022-108268, compounds described in JP-A-2023-005703, compounds described in JP-A-2022-100258, compounds described in JP-A-2022-181226, compounds described in JP-A-2022-27575, and compounds described in JP-A-2021-163968.
• Examples of p-type organic semiconductors include compounds having a smaller ionization potential than n-type organic semiconductors. If this condition is satisfied, the organic dyes exemplified as n-type organic semiconductors can be used. Examples of compounds that can be used as the p-type organic semiconductor compound are given below.
• the difference in ionization potential between the specific compound and the p-type organic semiconductor is preferably 0.1 eV or more.
• the p-type organic semiconductor material may be used alone or in combination of two or more.
• the content of the p-type organic semiconductor in the photoelectric conversion film is preferably 15 to 75 vol%, more preferably 20 to 60 vol%, and even more preferably 25 to 50 vol%.
• the photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode).
• a non-luminescent film means a film with a luminescence quantum efficiency of 1% or less, preferably 0.5% or less, and more preferably 0.1% or less. The lower limit is often 0% or more.
• the photoelectric conversion film preferably contains a dye in addition to the specific compound.
• the dye is a compound different from the above specific compound.
• the dye is preferably an organic dye.
• organic dyes include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes (including zeromethine merocyanine (simple merocyanine)), rhodacyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarylium dyes, croconium dyes, azamethine dyes, coumarin dyes, arylidene dyes, anthraquinone dyes, triphenylmethane dyes, azo dyes, azomethine dyes, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes,
• acridinone dyes diphenylamine dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, dioxane dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, subphthalocyanine dyes, metal complexes, WO2020/013246, WO2022/168856, JP2023-10305A, and JP2023-10299A described imidazoquinoxaline dyes, acceptor-donor-acceptor type dyes in which two acidic nuclei are bonded to a donor, and donor-acceptor-donor type dyes in which two donors are bonded to an acceptor, etc. Among them, in terms of maximum absorption wavelength, cyanine dyes, imidazoquinoxaline dyes, or acceptor-donor-acceptor type dyes are preferred.
• the maximum absorption wavelength of the dye is preferably in the visible light region, more preferably in the wavelength range of 400 to 650 nm, and even more preferably in the wavelength range of 400 to 550 nm.
• the dyes may be used alone or in combination of two or more.
• the photoelectric conversion film may be formed, for example, by a dry film formation method.
• the dry film formation method include physical vapor deposition methods such as vapor deposition (particularly vacuum deposition), sputtering, ion plating, and MBE (Molecular Beam Epitaxy), and CVD (Chemical Vapor Deposition) methods such as plasma polymerization, and the vacuum deposition method is preferred.
• the manufacturing conditions such as the degree of vacuum and the 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 photoelectric conversion element preferably has an electrode.
• the electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected.
• Examples of materials constituting the upper electrode 15 include conductive metal oxides such as antimony- or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine doped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Indium Tin Oxide), and indium zinc oxide (IZO: Indium Zinc Oxide); thin metal films such as gold, silver, chromium, and nickel; mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, nanocarbon materials such as carbon nanotubes and graphene, and the like. In terms of high conductivity and transparency, conductive metal oxides are preferred.
• the sheet resistance may be 100 to 10,000 ⁇ / ⁇ , and there is a large degree of freedom in the range of the film thickness that can be thinned.
• An increase in light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
• the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.
• the lower electrode 11 may be made transparent or may be non-transparent and reflect light.
• Materials constituting the lower electrode 11 include, for example, conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum; conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN)); mixtures or laminates of these metals and conductive metal oxides; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and carbon materials such as carbon nanotubes and graphene.
• conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium
• the method for forming the electrodes can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing and coating, physical methods such as vacuum deposition, sputtering, and ion plating, and chemical methods such as CVD and plasma CVD.
• wet methods such as printing and coating
• physical methods such as vacuum deposition, sputtering, and ion plating
• chemical methods such as CVD and plasma CVD.
• the electrode material is ITO
• methods such as an electron beam method, a sputtering method, a resistance heating deposition method, a chemical reaction method (such as a sol-gel method), and coating of a dispersion of indium tin oxide can be used.
• the photoelectric conversion element preferably has one or more intermediate layers between the conductive film and the transparent conductive film in addition to the photoelectric conversion film.
• the intermediate layer may be, for example, a charge blocking film.
• the charge blocking film may be, for example, an electron blocking film or a hole blocking film.
• the electron blocking film is a donor organic semiconductor material (compound), and the above-mentioned p-type organic semiconductor can be used. Furthermore, polymeric materials can also be used as the electron blocking film. Examples of the polymeric material include polymers of phenylenevinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, and derivatives thereof.
• the electron blocking film may be made up of multiple films.
• the electron blocking film may be made of an inorganic material.
• inorganic materials have a higher dielectric constant than organic materials, so when an inorganic material is used for the electron blocking film, a higher voltage is applied to the photoelectric conversion film, and the quantum efficiency is increased.
• examples of inorganic materials that can be used for the electron blocking film include calcium oxide, chromium oxide, copper chromium oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, copper gallium oxide, copper strontium oxide, niobium oxide, molybdenum oxide, copper indium oxide, silver indium oxide, and iridium oxide.
• the hole blocking film is an acceptor organic semiconductor material (compound), and the above-mentioned n-type organic semiconductor can be used.
• the hole blocking film may be made up of multiple films.
• Methods for manufacturing the charge blocking film include, for example, a dry film formation method and a wet film formation method.
• dry film formation methods include a vapor deposition method and a sputtering method.
• the vapor deposition method may be either a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method, with physical vapor deposition methods such as vacuum vapor deposition being preferred.
• wet film formation methods include an inkjet method, a spray method, a nozzle print method, a spin coat method, a dip coat method, a cast method, a die coat method, a roll coat method, a bar coat method, and a gravure coat method, with the inkjet method being preferred in terms of high-precision patterning.
• each of the charge blocking films is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm.
• the photoelectric conversion element may further include a substrate.
• the substrate include a semiconductor substrate, a glass substrate, and a plastic substrate.
• the conductive film, the photoelectric conversion film, and the transparent conductive film are usually laminated in this order on the substrate.
• the photoelectric conversion element may further include a sealing layer.
• the performance of photoelectric conversion materials may be significantly deteriorated in the presence of deterioration factors such as water molecules, etc. Therefore, the deterioration can be prevented by covering and sealing the entire photoelectric conversion film with a sealing layer such as ceramics such as dense metal oxide, metal nitride, or metal nitride oxide that does not allow water molecules to penetrate, or diamond-like carbon (DLC).
• a sealing layer such as ceramics such as dense metal oxide, metal nitride, or metal nitride oxide that does not allow water molecules to penetrate, or diamond-like carbon (DLC).
• the sealing layer is described, for example, in paragraphs [0210] to [0215] of JP-A-2011-082508, the contents of which are incorporated herein by reference.
• the photoelectric conversion element can be produced by a known production method. Specifically, for example, there is mentioned a method for producing a photoelectric conversion element, which includes a step of forming a conductive film on a substrate, a step of forming a photoelectric conversion film, and a step of forming a transparent conductive film.
• the method for producing a photoelectric conversion element may include other steps in addition to those described above (for example, a step of forming a charge blocking film and a step of forming a sealing layer). The method for forming each layer is as described above.
• Photoelectric conversion elements are used, for example, as imaging elements.
• An imaging element is an element that converts the optical information of an image into an electrical signal, and is usually composed of multiple photoelectric conversion elements arranged in a matrix on the same plane, with each photoelectric conversion element (pixel) converting the optical signal into an electrical signal, and outputting the electrical signal pixel by pixel from the imaging element. For this reason, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
• the photoelectric conversion element include, for example, a photocell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor.
• the photoelectric conversion element may be used alone, or the photoelectric conversion element may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line, or as a two-dimensional sensor in which the photoelectric conversion elements are arranged on a plane.
• reaction solution was diluted with ethyl acetate and hexane, washed with water and saturated saline, and the resulting organic layer was dried over magnesium sulfate, filtered, and concentrated under reduced pressure.
• the obtained compound was used to prepare a photoelectric conversion element (A) having the configuration shown in Fig. 2.
• the photoelectric conversion element comprises a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.
• amorphous ITO was formed on a glass substrate by sputtering to form a lower electrode 11 (thickness: 30 nm), and a compound (EB-1) was further formed on the lower electrode 11 by vacuum heating deposition to form an electron blocking film 16A (thickness: 30 nm).
• the film formation speed of the photoelectric conversion film 12 was set to 1.0 ⁇ /sec.
• a compound (EB-2) was evaporated on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm).
• Amorphous ITO was deposited on the hole blocking film 16B by sputtering to form an upper electrode 15 (transparent conductive film) (film thickness: 10 nm).
• an aluminum oxide (Al 2 O 3 ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD) to produce each photoelectric conversion element (A).
• the dark current was measured by the following method. A voltage was applied to the lower and upper electrodes of each photoelectric conversion element (A) so as to obtain an electric field strength of 2.5 ⁇ 10 5 V/cm, and the current value (dark current) in a dark place was measured. As a result, it was confirmed that the dark current in each photoelectric conversion element (A) was 50 nA/cm 2 or less, which is a sufficiently low dark current.
• the quantum efficiency was evaluated by the following method. A voltage was applied to each photoelectric conversion element (A) so as to achieve an electric field strength of 2.0 ⁇ 10 5 V/cm. Thereafter, light was irradiated from the upper electrode (transparent conductive film) side, and the quantum efficiency (photoelectric conversion efficiency) at a wavelength of 600 nm was measured. Using the quantum efficiency at a wavelength of 600 nm of each of the obtained photoelectric conversion elements (A), the relative ratio of the quantum efficiency at each wavelength was calculated according to formula (S1). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria.
• each photoelectric conversion element (A) was evaluated by the following method. A voltage was applied to each photoelectric conversion element (A) so that the intensity was 2.0 ⁇ 10 5 V/cm. Then, the LED (light emitting diode) was turned on instantaneously to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 600 nm was measured with an oscilloscope, and the rise time from 0% signal intensity to 97% signal intensity was measured. Using the rise time at a wavelength of 600 nm of each obtained photoelectric conversion element (A), the relative response speed was calculated according to formula (S2). From the obtained value, the response speed was evaluated according to the following evaluation criteria.
• Relative response speed is less than 1.1
• B Relative response speed is 1.1 or more and less than 1.5
• C Relative response speed is 1.5 or more and less than 2.0
• D Relative response speed is 2.0 or more
• ⁇ Response speed vs. electric field strength> For each photoelectric conversion element (A), the dependence of the response speed on the electric field strength was evaluated by the following method.
• ⁇ Response speed> the rise time at an applied voltage of 7.5 ⁇ 10 4 V/cm was measured in the same manner as above, except that the voltage applied to each photoelectric conversion element (A) was changed to 7.5 ⁇ 10 4 V/cm.
• the rise time of each photoelectric conversion element (A) at a wavelength of 600 nm at each applied voltage was used to calculate the relative rise time according to formula (S3). From the obtained values, the electric field strength dependency of the response speed was evaluated according to the following evaluation criteria.
• Photoelectric conversion elements having the configurations of the respective Examples and Comparative Examples were evaluated for manufacturability by the following method.
• Photoelectric conversion elements (B) of each Example or Comparative Example were produced in the same manner as for the photoelectric conversion element (A), except that the deposition rate of the photoelectric conversion film 12 was set to 3.0 ⁇ /sec.
• the photoelectric conversion efficiency at 600 nm of the obtained photoelectric conversion element (B) was measured in the same manner as in ⁇ Evaluation of quantum efficiency (external quantum efficiency)>.
• the relative ratio B/A of the photoelectric conversion efficiencies at 600 nm of the photoelectric conversion element (A) and the photoelectric conversion element (B) having the same configuration as the example or comparative example was calculated according to the formula (S4).
• the manufacturability was evaluated from the obtained value according to the following evaluation criteria. The closer the value of the relative ratio B/A is to 1, the less the characteristics of the photoelectric conversion element are likely to deteriorate when the film formation rate is increased, that is, the more excellent the manufacturability is.
• the numerator and denominator are values measured for the photoelectric conversion element of the same Example or Comparative Example.
• the numerator and denominator are both quantum efficiencies measured at 600 nm.
• the electric field strength dependency of the quantum efficiency is preferably rated C or higher.
• results The evaluation results are shown in the table below.
• the "X 3 " column indicates that the specific compound is a compound in which X 3 in formula (1) is --C(R c1 R c2 )--, and indicates that the specific compound is otherwise indicated as “A,” and “B.”
• the "A 1 , A 2 " column indicates that the specific compound is a compound in which A 1 and A 2 in formula (1) are groups represented by formula (A-2), and is indicated as “A” otherwise.
• R N2 ⁇ R N3 when R N2 and R N3 are different groups, it is marked “A", and in other cases it is marked "B".
• the column “Requirements 1 to 4” if the specific compound is a compound that satisfies any one of requirements 1 to 4, it is marked “A,” and if not, it is marked “B.”
• the column “Requirements 4 to 7” if the specific compound is a compound that satisfies any one of requirements 4 to 7, it is marked “A,” and if not, it is marked “B.”
• Example 1-24 From a comparison of Example 1-24 with Examples 1-3 to 1-14, it was confirmed that when X 3 in formula (1) is -C(R c1 R c2 )-, the response speed when red and green light is received, the electric field strength dependence of the response speed, and the manufacturability are superior.
• Comparison of Example 1-21 with Examples 1-3 to 1-14, and comparison of Example 1-20 with Examples 1-17 to 1-19 confirmed that when A 1 and A 2 in formula (1) are groups represented by formula (A-2), the quantum efficiency when red and green light is received is superior.
• the dark current of the obtained photoelectric conversion element (C) was measured in the same manner as in ⁇ Measurement of Dark Current> in [Test X]. As a result, it was confirmed that all the photoelectric conversion elements (C) had a dark current of 50 nA/cm 2 or less, which was a sufficiently low dark current.
• the quantum efficiency was evaluated by the following method. A voltage was applied to each photoelectric conversion element (C) so as to achieve an electric field strength of 2.0 ⁇ 10 5 V/cm. Thereafter, light was irradiated from the upper electrode (transparent conductive film) side, and the quantum efficiency (external quantum efficiency) at a wavelength of 460 nm or 600 nm was measured. Using the quantum efficiency at a wavelength of 460 nm or 600 nm of each of the obtained photoelectric conversion elements (C), the relative ratio of the quantum efficiency at each wavelength was calculated according to formula (S5). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria. Using the photoelectric conversion efficiency of each photoelectric conversion element (C), the relative ratio of quantum efficiency was calculated at each wavelength according to formula (S5). From the obtained values, the quantum efficiency was evaluated according to the following evaluation criteria.
• the photoelectric conversion efficiency at the same wavelength was used as the numerator and denominator.
• each photoelectric conversion element (C) was evaluated by the following method. A voltage was applied to each photoelectric conversion element (C) so that the intensity was 2.0 ⁇ 10 5 V/cm. Then, the LED was turned on momentarily to irradiate light from the upper electrode (transparent conductive film) side, and the photocurrent at a wavelength of 460 nm or 600 nm was measured with an oscilloscope, and the rise time from 0% signal intensity to 97% signal intensity was measured. Using the rise time at each wavelength of each photoelectric conversion element (C) obtained, the relative response speed was calculated at each wavelength according to formula (S6). From the obtained value, the response speed was evaluated according to the following evaluation criteria.
• Equation (S6): Relative response speed (rise time of each photoelectric conversion element (C)) / (rise time of photoelectric conversion element (C) in Example 2-1)
• Relative response speed (rise time of each photoelectric conversion element (C)) / (rise time of photoelectric conversion element (C) in Example 2-1)
• Relative response speed is less than 1.1
• B Relative response speed is 1.1 or more and less than 1.5
• C Relative response speed is 1.5 or more and less than 2.0
• D Relative response speed is 2.0 or more
• the rise times at the same wavelength were used as the numerator and denominator.
• each photoelectric conversion element For each photoelectric conversion element, the dependence of quantum efficiency on electric field strength was evaluated by the following method.
• the quantum efficiency (external quantum efficiency) of each photoelectric conversion element (C) was measured at an electric field strength of 7.0 ⁇ 10 4 V/cm in the same manner as in the evaluation of the above-mentioned ⁇ quantum efficiency>.
• the quantum efficiency of each photoelectric conversion element (C) at each applied voltage at a wavelength of 460 nm or 600 nm was used to calculate the electric field strength dependency of the quantum efficiency according to the following formula (SX2), and the electric field strength dependency of the quantum efficiency was evaluated according to the following evaluation criteria.
• the numerator and denominator are values measured for the photoelectric conversion element of the same example or comparative example.
• the numerator and denominator are both quantum efficiencies for light of the same wavelength measured at 460 nm or 600 nm.
• the electric field strength dependency of the quantum efficiency is preferably rated C or higher.
• Example 2-30 From a comparison of Example 2-30 with Examples 2-9 to 2-20, it was confirmed that when X 3 in formula (1) is -C(R c1 R c2 )-, the response speed and the electric field strength dependence of the response speed when receiving either red/green light or blue light are more excellent.
• Comparison of Examples 2-21 to 2-22 and Examples 2-32 to 2-38 with Examples 2-9 to 2-20, and comparison of Examples 2-39 to 2-44 with Examples 2-23 to 2-25 confirmed that when a specific compound satisfies any one of Requirements 1 to 3, the quantum efficiency when red and green light is received is superior. Comparison of Examples 2-23 to 2-25 with Examples 2-9 to 2-20, and comparison of Examples 2-39 to 2-44 with Examples 2-32 to 2-38 confirmed that when at least one of X1 and X2 in formula (1) is -CR a2 , the response speed and the electric field strength dependence of the response speed when either red/green light or blue light is received are more excellent.

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