Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
  • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
  • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
  • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
  • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
  • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D421/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms
  • C07D421/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having selenium, tellurium, or halogen atoms as ring hetero atoms containing three or more hetero rings
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/30—Devices controlled by radiation
  • H10K39/32—Organic image sensors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight

Definitions

• the present invention relates to a photoelectric conversion element, an imaging element, an optical sensor, and a compound.
• Non-Patent Document 1 discloses an ADA (acceptor-donor-acceptor) type dye that can be used as a p-type or n-type semiconductor.
• the photoelectric conversion element according to any one of [1] to [3], wherein the group represented by formula (A-1) described later is a group represented by formula (A-2) described later.
• R Z2 represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from the substituent group X described later, an acyl group having 2 to 3 carbon atoms, an aromatic ring group which may have a substituent selected from the substituent group S described later, an aliphatic heterocyclic group which may have a substituent selected from the substituent group S, or a group represented by *-Si(R Si2 ) 3 .
• the photoelectric conversion film further contains an n-type organic semiconductor, The photoelectric conversion element according to any one of [1] to [7], wherein the photoelectric conversion film has a bulk heterostructure formed by mixing the compound represented by formula (1) and the n-type organic semiconductor.
• R Z2 represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from substituent group X, an acyl group having 2 to 3 carbon atoms, an aromatic ring group which may have a substituent selected from substituent group S, an aliphatic heterocyclic group which may have a substituent selected from the above substituent group S, or a group represented by *-Si(R Si2 ) 3 .
• an imaging element, an optical sensor, and a compound can be provided.
• 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 hydrogen atom may be a protium atom (a normal hydrogen atom) or a deuterium atom (eg, a deuterium atom, etc.).
• 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.
• the bond direction of the divalent groups (e.g., -CO-O-, etc.) described in this specification is not limited unless otherwise specified.
• the compound may be either "X-O-CO-Z" or "X-CO-O-Z”.
• 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 heteroaryl group, or an aliphatic 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 alkoxycarbonyl
• alkyl group examples include an alkyloxy group, a primary, secondary or tertiary amino group (including anilino group), an alkylthio group, an arylthio group, a heterocyclic thio group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a carboxy group, a phosphate group, a sulfonic acid group, a hydroxy group, a thiol group, an acylamino group, a carbamoyl group, a ureido group, and a bor
• each of the above groups may further have a substituent (e.g., one or more of the above groups) if possible.
• a substituent e.g., one or more of the above groups
• an alkyl group which 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.
• 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 isopropyl 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 that the alkoxy group may have include the same as the substituent in the alkyl group which may have a substituent.
• examples of the substituent that the alkylthio group may have include the same as the substituent 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) aromatic ring is an aromatic ring having a plurality of (e.g., 2 to 6 rings) aromatic ring structures condensed as ring structures.
• the aromatic ring preferably has 4 to 15 member atoms.
• the aromatic ring may be 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, and a phenanthrene 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
• thienothiazole ring for example, thieno[2,3-d]thiazole ring, etc.
• benzothiadiazole ring benzodithiophene ring (for example, benzo[1,2-b:4,5-b']dithiophene ring, etc.), thienothiophene ring (for example, thieno[3,2-b]thiophene ring, etc.), thiazolothiazole ring (for example, thiazolo[5,4-d]thiazole ring, etc.), naphthodithiophene ring (for example, naphtho[2,3 [2,1-b:6,7-b']dithiophene ring, naphtho[2,1-b:6,5-b']dithiophene ring, naphtho[1,2-b:5,6-b']dithiophene ring, 1,8-dithiadicyclopenta[
• the type of the substituent which the aromatic ring may have may be, for example, the groups 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.).
• the aliphatic heterocyclic group preferably has 5 to 20 ring members, more preferably 5 to 12 ring members, and even more preferably 6 to 8 ring members.
• the heteroatom contained in the aliphatic 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, with a sulfur atom, an oxygen atom or a nitrogen atom being preferred.
• Examples of the aliphatic heterocycle constituting the aliphatic heterocyclic group 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 ⁇ -butyrolactone.
• the term "aliphatic heterocyclic group” includes, for example, a group obtained by removing one hydrogen atom from the above-mentioned aliphatic heterocycle.
• the photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, 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 later (hereinafter, also referred to as a "specific compound").
• the mechanism by which the photoelectric conversion element of the present invention having the above-mentioned configuration can solve the problems of the present invention is not necessarily clear, but the present inventors speculate as follows.
• the mechanism by which the effects are obtained is not limited by the following speculation, and therefore, even if the effects are obtained by a mechanism other than the following, it is included in the scope of the present invention.
• the specific compound contained in the photoelectric conversion element of the present invention is an A-D-A type dye in which two acceptor moieties (A) are bonded to a donor moiety (D).
• A acceptor moieties
• D donor moiety
• the specific compound absorbs light, it generates excitons, and then electric current can be extracted through charge separation and charge transport.
• One of the means for controlling the aggregation state of the dye is to introduce an appropriate aggregation inhibitor group into the donor site of the dye. If the donor site is unsubstituted, the dye aggregates in the photoelectric conversion film, and the charge separation efficiency decreases, resulting in a decrease in quantum efficiency.
• the aggregation inhibitor group introduced into the compound described in Patent Document 1 is a long-chain alkyl group, which is undesirable because it increases the intermolecular distance and reduces the charge transportability between molecules. In addition, it often makes deposition difficult when fabricating devices.
• alkoxy groups and groups containing an ester bond (--COO--) are also undesirable because they increase the intermolecular distance.
• the compound of the present invention has a specific substituent R Z2 as an aggregation inhibitor group, and thus the aggregation property can be appropriately controlled, and as a result, the compound exhibits high electrical properties (quantum efficiency and response speed).
• the acceptor site also affects the electrical properties.
• the dicyanomethylidene structure which is often found as an acceptor site, has a large dipole, which strengthens the interaction with the charge, and is thought to deteriorate the electrical properties (mainly the response speed and its electric field strength dependence).
• the cyclic acceptor in the specific compound of the present invention has a smaller dipole than dicyanomethylidene, and is therefore thought to be able to achieve a better response speed.
• the effect of the present invention is said to be superior when at least one of the effects of excellent quantum efficiency and excellent response speed is obtained when the photoelectric conversion element receives blue-green light (light with a wavelength in the range of 400 to 500 nm).
• the configuration of the photoelectric conversion element of the present invention will be described in detail below.
• 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 of the present invention has a photoelectric conversion film.
• the photoelectric conversion film contains a compound (specific compound) represented by formula (1).
• X1 and X2 each independently represent a sulfur atom or a selenium atom. It is preferable that both X1 and X2 are a sulfur atom.
• a plurality of R Z1 may be the same or different.
• Examples of the substituent represented by R 21 include the groups exemplified as the above-mentioned substituent W, and a halogen atom or a group represented by R 22 described below is preferable.
• R Z2 each independently represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms, an acyl group having 1 to 6 carbon atoms which may have a halogen atom, an aromatic ring group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, a group represented by *-Si(R Si1 ) 3 , or a group represented by *-C ⁇ C-Si(R Si1 ) 3.
• the aliphatic hydrocarbon group represented by R Z2 may have a halogen atom or a group represented by *-Si(R Si1 ) 3 described later.
• each group represented by R Z2 may have is not particularly limited, and examples thereof include the groups exemplified by the above-mentioned substituent W. Among them, the substituent that each group represented by R Z2 may have is preferably a substituent selected from the substituent group S described in detail later, and more preferably a substituent selected from the substituent group T described in detail later. In addition, each group represented by R Z2 may have two or more substituents.
• the definition of the aliphatic hydrocarbon group in this specification is as described above and is not particularly limited, but among them, an alkyl group is preferable.
• Examples of the aliphatic hydrocarbon group having 1 to 7 carbon atoms include linear aliphatic hydrocarbon groups, branched aliphatic hydrocarbon groups, and cyclic aliphatic hydrocarbon groups.
• the linear aliphatic hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.
• the branched aliphatic hydrocarbon group preferably has 3 to 5 carbon atoms, and more preferably has 3 to 4 carbon atoms.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 7, more preferably 3 to 6, and even more preferably 3 to 5.
• the number of carbon atoms in the cyclic aliphatic hydrocarbon group means the number of carbon atoms as ring atoms.
• the cyclic aliphatic hydrocarbon group may be either monocyclic or polycyclic.
• An example of the aliphatic hydrocarbon group having 1 to 7 carbon atoms includes a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from substituent group X.
• the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms has a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, or a cyclic aliphatic hydrocarbon group having 3 to 4 carbon atoms selected from substituent group X
• the total number of carbon atoms of the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms and the number of carbon atoms of the substituent selected from substituent group X is within the range of 3 to 7.
• Substituent group X linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 4 carbon atoms, halogen atoms, and groups represented by *-Si(R Si2 ) 3 described below.
• the aliphatic hydrocarbon group has a halogen atom, all of the hydrogen atoms in the aliphatic hydrocarbon group may be completely halogenated.
• the acyl group preferably has 2 to 5 carbon atoms, more preferably 2 to 3 carbon atoms, and even more preferably 2 carbon atoms (acetyl group).
• the acyl group may be either an aromatic acyl group or an aliphatic acyl group, but is preferably an aliphatic acyl group.
• the aromatic ring constituting the aromatic ring group is defined as above, and examples of the aromatic ring group include an aryl group and a heteroaryl group.
• the number of ring members of the aromatic ring group is not particularly limited, but is preferably 5 to 20, and more preferably 5 to 10.
• the aryl group is preferably a phenyl group which may have a substituent.
• the aromatic heterocycle constituting the heteroaryl group is preferably a thiophene ring which may have a substituent, a furan ring which may have a substituent, or a pyridine ring which may have a substituent.
• substituent that the aromatic ring group may have, a substituent selected from the substituent group S described in detail later is preferable, a substituent selected from the substituent group T described in detail later is more preferable, and an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is further preferable.
• the definition of the aliphatic heterocyclic group in this specification is as described above.
• the number of ring members of the aliphatic heterocyclic group is not particularly limited, and is preferably 5 to 20, more preferably 5 to 12, and even more preferably 5 to 8.
• the aliphatic heterocycle constituting the aliphatic heterocyclic group is preferably a tetrahydropyran ring, a pyrrolidine ring, a piperidine ring, or a morpholine ring.
• substituent that the aliphatic heterocyclic group may have, a substituent selected from the substituent group S described in detail later is preferable, a substituent selected from the substituent group T described in detail later is more preferable, and an alkyl group having 1 to 3 carbon atoms is further preferable.
• each R Si1 independently represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or an aromatic ring group which may have a substituent.
• the aliphatic hydrocarbon group represented by R 4 Si1 preferably has 1 to 3 carbon atoms, and more preferably has 1 or 2 carbon atoms.
• the definition of the aliphatic hydrocarbon group is as described above. Among them, the aliphatic hydrocarbon group is preferably an alkyl group.
• the aromatic ring group represented by R 4 Si1 preferably has 5 to 20 ring members, and more preferably has 5 to 10 ring members.
• the aromatic ring group includes an aryl group and a heteroaryl group, and a phenyl group is preferable.
• Examples of the substituent that the aliphatic hydrocarbon group or aromatic ring group represented by R 4 Si1 may have include the groups exemplified as the substituent W above.
• the group represented by *-Si(R Si1 ) 3 is preferably a group represented by *-Si(R Si2 ) 3 , and more preferably a group represented by *-Si(R Si3 ) 3.
• R Si2 each independently represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms, or an aromatic ring group which may have a substituent selected from the substituent group S described later in detail.
• substituent group S is a group consisting of the following substituents.
• Substituent group S linear aliphatic hydrocarbon groups having 1 to 3 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms, halogen atoms, and groups represented by *-Si(R Si2 ) 3 .
• substituent group T is a group consisting of the following substituents.
• Substituent group T linear aliphatic hydrocarbon groups having 1 to 2 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 4 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 5 carbon atoms, halogen atoms, and groups represented by *-Si(R Si3 ) 3 .
• the above-mentioned straight-chain aliphatic hydrocarbon group, the above-mentioned branched-chain aliphatic hydrocarbon group, and the above-mentioned cyclic aliphatic hydrocarbon group may have at least one of a halogen atom and an etheric oxygen atom.
• the above-mentioned aliphatic hydrocarbon group has an ethereal oxygen atom
• the ethereal oxygen atom may be located between carbon atoms in the aliphatic hydrocarbon group, or the ethereal oxygen atom may be located at the terminal of the aliphatic hydrocarbon group.
• the definition of the aliphatic hydrocarbon group is as described above. Among them, the aliphatic hydrocarbon group is preferably an alkyl group.
• the specific compound is preferably a compound represented by any one of formulas (2) to (7), more preferably a compound represented by any one of formulas (2) to (4), and even more preferably a compound represented by formula (2) or a compound represented by formula (3).
• X 1 , X 2 , R 1 , R 2 , A 1 , and A 2 are the same as X 1 , X 2 , R 1 , R 2 , A 1 , and A 2 in formula (1). 1 , R 2 , A 1 and A 2 will be described in detail below.
• R Z1 represents a hydrogen atom or a halogen atom.
• the halogen atom is preferably a fluorine atom or a chlorine atom. preferable.
• R Z2 has the same meaning as R Z2 in formula (1). Specific and preferred embodiments of each group represented by R Z2 are as described above.
• R 1 and R 2 each independently represent a hydrogen atom or a substituent.
• substituents represented by R1 and R2 include the groups exemplified as the above-mentioned substituent W. Among them, in terms of the superior effect of the present invention, it is preferable that R1 and R2 are hydrogen atoms.
• a 1 and A 2 each independently represent a group represented by formula (A-1) above.
• W 1 represents a sulfur atom, an oxygen atom, ⁇ NR W1 or ⁇ CR W2 R W3 .
• R W1 represents a hydrogen atom or a substituent.
• R W2 and R W3 each independently represent a cyano group, —SO 2 R W4 , —COOR W5 or —COR W6 .
• R W1 is preferably an oxygen atom or a sulfur atom in that the effects of the present invention are more excellent.
• substituent represented by R W1 include the substituents exemplified for the above-mentioned substituent W.
• R W4 to R W6 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 may be possessed by these groups represented by R W4 to R W6 include the substituents exemplified for the above-mentioned substituent W.
• the aliphatic hydrocarbon group is as defined above, and among them, an alkyl group is preferred, and a linear alkyl group is more preferred.
• the aliphatic hydrocarbon group preferably has 1 to 3 carbon atoms.
• the aromatic ring group is as defined above, and among them, an aryl group is preferable, and a phenyl group is more preferable.
• the aliphatic heterocyclic group is as defined above.
• C1 represents a ring containing 2 or more carbon atoms and which may have a substituent.
• the number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10.
• the number of carbon atoms includes the two carbon atoms specified in the formula.
• the ring may be either aromatic or non-aromatic.
• the ring may be either a monocyclic ring or a polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring.
• the number of rings forming the fused ring is preferably 1 to 4, and more preferably 1 to 3.
• the ring 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 is preferably a sulfur atom, a nitrogen atom, or an oxygen atom.
• the number of heteroatoms in the ring is preferably 0 to 10, and more preferably 0 to 5.
• substituents that the ring 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 ring represented by C1 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.
• (b) Pyrazolinone nucleus for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one, and the like.
• (c) Isoxazolinone nucleus for example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, and the like.
• (d) Oxindole nucleus for example, 1-alkyl-2,3-dihydro-2-oxindole, etc.
• (e) 2,4,6-trioxohexahydropyrimidine nucleus for example, barbituric acid, 2-thiobarbituric acid and derivatives thereof, etc.
• the derivatives 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, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl) and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheteroaryl compounds such as 1,3-di(2-pyridyl).
• 2-thio-2,4-thiazolidinedione nucleus for example, rhodanine and its derivatives, etc.
• the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3-heteroarylrhodanine such as 3-(2-pyridyl)rhodanine, etc.
• 2-thio-2,4-oxazolidinedione nucleus (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione.
• Thianaphthenone nucleus for example, 3(2H)-thianaphthenone-1,1-dioxide.
• 2-thio-2,5-thiazolidinedione nucleus for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.
• (j) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, and the like.
• 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus for example, 2-thio-2,4-imidazolidinedione and 3-ethyl-2-thio-2,4-imidazolidinedione.
• Imidazolin-5-one nucleus for example, 2-propylmercapto-2-imidazolin-5-one.
• 3,5-pyrazolidinedione nucleus for example, 1,2-diphenyl-3,5-pyrazolidinedione and 1,2-dimethyl-3,5-pyrazolidinedione.
• Benzothiophen-3(2H)-one nucleus for example, benzothiophen-3(2H)-one, oxobenzothiophen-3(2H)-one, dioxobenzothiophen-3(2H)-one, and the like.
• Indanone nucleus for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, and the like.
• Benzofuran-3-(2H)-one nucleus for example, benzofuran-3-(2H)-one, etc.
• the group represented by the above formula (A-1) is preferably a group represented by formula (A-2) in that the effects of the present invention are more excellent.
• * represents a bonding position.
• R Y1 represents a hydrogen atom or a substituent.
• R Y2 and R Y3 each independently represent a cyano group, -SO 2 R Y4 , -COOR Y5 or -COR Y6 .
• both Y2 and Y3 represent an oxygen atom.
• substituent represented by R Y1 include the substituents exemplified as the above-mentioned substituent W.
• R Y4 to R Y6 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 may be possessed by these groups represented by R Y4 to R Y6 include the substituents exemplified for the above-mentioned substituent W.
• the aliphatic hydrocarbon group is as defined above, and among them, an alkyl group is preferred, and a linear alkyl group is more preferred.
• the aliphatic hydrocarbon group preferably has 1 to 3 carbon atoms.
• the aromatic ring group is as defined above, and among them, an aryl group is preferable, and a phenyl group is more preferable.
• C2 represents a ring containing 3 or more carbon atoms and which may have a substituent.
• the three carbon atoms included in the above C2 are the three carbon atoms clearly shown in formula (A-2).
• the number of carbon atoms in the ring is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10.
• the number of carbon atoms in the ring is the number including the three carbon atoms specified in the formula.
• the ring may be either an aromatic ring or a non-aromatic ring.
• the ring may be either a monocyclic ring or a polycyclic ring, and is preferably a 5-membered ring, a 6-membered ring, or a fused ring containing at least one of a 5-membered ring and a 6-membered ring.
• the number of rings contained is preferably 2 to 6, and more preferably 2 or 3.
• the ring 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 is preferably a sulfur atom, a nitrogen atom, or an oxygen atom.
• the number of heteroatoms contained in the ring is preferably 0 to 10, and more preferably 0 to 5.
• Preferred embodiments of the substituent that the above ring may have are the same as the substituent that the above ring C1 may have.
• the group represented by the above formula (A-2) is preferably a group represented by the formula (C-1) or a group represented by the formula (C-2).
• R X1 represents a hydrogen atom or a substituent.
• R X2 and R X3 each independently represent a cyano group, —SO 2 R X4 , —COOR X5 or —COR X6 .
• R X4 , R X5 , and R X6 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.
• At least one of Xc1 and Xc2 is preferably an oxygen atom, and it is more preferable that both of Xc1 and Xc2 are oxygen atoms.
• C3 represents an aromatic ring which may have a substituent.
• the number of carbon atoms in the aromatic ring is preferably 4 to 30, more preferably 5 to 12, and even more preferably 6 to 8.
• the number of carbon atoms includes the two carbon atoms specified in the formula.
• the aromatic ring may be either a monocyclic ring or a polycyclic ring.
• the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, with an aromatic hydrocarbon ring being preferred.
• Examples of the aromatic ring represented by C3 include the rings exemplified in the above description of the aromatic ring.
• the aromatic ring represented by C3 is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring, and more preferably a benzene ring.
• the substituent that the aromatic ring may have include the groups exemplified as the substituent W above.
• X c3 to X c5 represent an oxygen atom, a sulfur atom, ⁇ NR X1 , or ⁇ CR X2 R X3 . It is preferable that Xc3 and Xc4 are all oxygen atoms, and it is more preferable that Xc3 , Xc4 and Xc5 are all oxygen atoms.
• Rc1 and Rc2 each independently represent a hydrogen atom or a substituent. Examples of the substituent represented by Rc1 and Rc2 include the groups exemplified by the above-mentioned substituent W. Among them, an alkyl group or a phenyl group is preferable, and an alkyl group is more preferable.
• the phenyl group may further have a substituent, and examples thereof include the groups exemplified as the substituent W above.
• the molecular weight of the specific compound is preferably from 400 to 1,200, more preferably from 400 to 1,000, and even more preferably from 500 to 800.
• the molecular weight is within the above range, it is presumed that the sublimation temperature of the specific compound is low, and the quantum efficiency is excellent even when the photoelectric conversion film is formed at high speed.
• the specific compound has an ionization potential of -5.0 to -6.5 eV in a single film.
• the maximum absorption wavelength of the specific compound is preferably in the range of 400 to 600 nm, and more preferably in the range of 400 to 500 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.
• A represents one of the following groups.
• each A specified in each specific compound may be the same or different.
• 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.,
• Examples of the compounds include 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 n-type organic semiconductor may be 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, quinone dyes, diphenylmethane dyes, polyene dyes, acridine dyes, a
• the molecular weight of the n-type organic semiconductor is preferably 200 to 1,200, and more preferably 200 to 900.
• 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 is preferably 15 to 75 vol%, and more preferably 30 to 75 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'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4'-bis[N-(naphthyl)-N-phenyl-amino]biphenyl ( ⁇ -NPD), compounds described in paragraphs [0128] to [0148] of JP-A No. 2011-228614, compounds described in paragraphs [0052] to [0063] of JP-A No. 2011-176259, compounds described in paragraphs [0052] to [0063] of JP-A No.
• TPD N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
• TPD 4,4'-bis[N-(naphthyl)-N-phen
• JP-A-2015-153910 compounds described in paragraphs [0119] to [0158] of JP-A-2015-153910, [0044] to [0051] of JP-A-2015-153910, and [0086] to [0090] of JP-A-2012-094660, etc.
• pyrazoline compounds e.g., thienothiophene derivatives, dibenzothiophene derivatives, benzodithiophene derivatives, dithienothiophene derivatives, [1]benzothieno[3,2-b][ 1] Benzothiophene (BTBT) derivatives, thieno[3,2-f:4,5-f']bis[1]benzothiophene (TBBT) derivatives, compounds described in paragraphs [0031] to [0036] of JP2018-014474A, compounds described in paragraphs [0043] to [0045] of
• 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 semiconductor material may be used alone or in combination of two or more kinds.
• 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 luminescent 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 maximum absorption wavelength of the dye is preferably in the visible light region, more preferably 400 to 650 nm, and even more preferably 450 to 650 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); metal thin 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, and nanocarbon materials such as carbon nanotubes and graphene. 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 made 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 granphenes.
• conductive metal oxides such as tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO),
• 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.
• 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.
• the present invention also includes the invention of a compound.
• the compound of the present invention is the above-mentioned specific compound.
• a photoelectric conversion element was produced using the above materials, and tests X and Y were carried out.
• the photoelectric conversion element (A) 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).
• n-type organic semiconductor fulllerene (C 60 )
• p-type organic semiconductor 1:1:1, calculated as thickness
• a compound (EB-2) was deposited 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) (thickness: 10 nm).
• an aluminum oxide (Al 2 O 3 ) layer was formed thereon by atomic layer chemical vapor deposition (ALCVD).
• ALD atomic layer chemical vapor deposition
• the dark current of each of the obtained photoelectric conversion elements (A) was measured by the following method. A voltage was applied to the lower electrode and the upper electrode 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 of each of the photoelectric conversion elements (A) was 50 nA/cm 2 or less, which is a sufficiently low dark current.
• the quantum efficiency of each of the obtained photoelectric conversion elements (A) was measured by the following method. After applying a voltage to each of the photoelectric conversion elements (A) so as to obtain an electric field strength of 2.0 ⁇ 10 5 V/cm, light was irradiated from the upper electrode (transparent conductive film) side to perform IPCE (incident photon-to-current conversion efficiency) measurement, and each photoelectric conversion efficiency (external quantum efficiency) at a wavelength of 460 nm was calculated. The photoelectric conversion efficiency was measured using a constant energy quantum efficiency measurement device manufactured by Optel. The amount of light irradiated was 50 ⁇ W/cm 2 .
• the response speed of each photoelectric conversion element (A) obtained was evaluated by the following method. A voltage was applied to the 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 460 nm at that time was measured with an oscilloscope to measure the rise time from 0% signal intensity to 97% signal intensity. Using the rise time at a wavelength of 460 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 0.5
• B Relative response speed is 0.5 or more and less than 0.75
• C Relative response speed is 0.75 or more and less than 1.0
• D Relative response speed is 1.0 or more and less than 1.25
• E Relative response speed is 1.25 or more
• ⁇ Evaluation of response speed dependence on electric field strength> For each of the obtained photoelectric conversion elements (A), the dependence of the response speed on the electric field strength was evaluated by the following method.
• ⁇ Evaluation of 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 460 nm at each applied voltage was used to calculate the relative ratio of the 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.
• the photoelectric conversion elements (A) in the numerator and denominator are the same.
• the rise time of the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm and a current density of 7.5 ⁇ 10 4 V/cm is compared with the rise time of the photoelectric conversion efficiency of Example 1-1 at a wavelength of 460 nm and a current density of 2.0 ⁇ 10 5 V/cm.
• Formula (S3): Relative ratio of rise time (rise time of each photoelectric conversion element (A) at an applied voltage of 7.5 ⁇ 10 4 V/cm)/(rise time of each photoelectric conversion element (A) at an applied voltage of 2.0 ⁇ 10 5 V/cm)
• Table 1 shows the evaluation results of the above test X.
• the symbols in Table 1 indicate the following: In the column “Formula (1)”, examples using a specific compound are labeled “A”, and comparative examples using a comparative compound are labeled “B".
• A-2 the case where the group represented by formula (A-1) in formula (1) is a group represented by formula (A-2) is marked as “A”, and the other cases are marked as "B”.
• C1 C2 the case where the group represented by formula (A-2) is a group represented by formula (C-1) or a group represented by formula (C-2) is indicated as "A", and the other cases are indicated as "B".
• R Z2 in formula (1) represents a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms which may have a substituent selected from substituent group X, an acyl group having 2 to 3 carbon atoms, an aromatic ring group which may have a substituent selected from substituent group S, an aliphatic heterocyclic group which may have a substituent selected from substituent group S, or a group represented by *-Si(R Si2 ) 3 , it is marked as "A”, and when it represents any other than the above, it is marked as "B".
• vapor deposition not possible indicates that, with respect to the evaluation results of Comparative Examples 1-2 or 1-5, when an attempt was made to form a photoelectric conversion film in producing a photoelectric conversion element, Compound C-2 or C-5 decomposed during vapor deposition and could not be evaluated.
• R Z2 in formula (1) is a linear aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a halogen atom, a branched aliphatic hydrocarbon group having 3 to 4 carbon atoms which may have a halogen atom, a cyclic aliphatic hydrocarbon group having 3 to 7 carbon atoms which may have a substituent selected from substituent group X, an acyl group having 2 to 3 carbon atoms, an aromatic ring group which may have a substituent selected from substituent group S, an aliphatic heterocyclic group which may have a substituent selected from substituent group S, or a group represented by *-Si(R Si2 ) 3 .
• Example 1-24 By comparing Example 1-24 with Example 1-25, it was confirmed that when the group represented by formula (A-1) in formula (1) is a group represented by formula (A-2), the response speed and the electric field strength dependence of the response speed are more excellent. By comparing Examples 1-1 to 1-15 with Example 1-19, it was confirmed that the quantum efficiency was superior when the group represented by formula (A-2) was a group represented by formula (C-2).
• the evaluation criteria for quantum efficiency at wavelengths of 460 nm and 600 nm are as follows.
• Relative response speed (rise time of photoelectric conversion element (C) of each Example or Comparative Example at a wavelength of 460 nm or 600 nm) / (rise time of photoelectric conversion element (C) of Comparative Example 2-3 at a wavelength of 460 nm or 600 nm)
• Relative response speed is less than 0.5
• B Relative response speed is 0.5 or more and less than 0.75
• C Relative response speed is 0.75 or more and less than 1.0
• D Relative response speed is 1.0 or more and less than 1.25
• E Relative response speed is 1.25 or more
• Table 2 shows the evaluation results of test Y.
• the notations in Table 2 are as described above for the notations in Table 1.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Electromagnetism (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Nanotechnology (AREA)
• Light Receiving Elements (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92674574

Family Applications (1)

Country Status (3)

Citations (5)

• 2024
  • 2024-02-14 WO PCT/JP2024/004947 patent/WO2024185418A1/ja not_active Ceased
  • 2024-02-14 JP JP2025505166A patent/JPWO2024185418A1/ja active Pending
  • 2024-02-29 TW TW113107288A patent/TW202440560A/zh unknown

Patent Citations (5)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events