WO2020203355A1 - Élément de conversion photoélectrique, élément d'imagerie, capteur optique, matériau pour élément de conversion photoélectrique, matériau pour élément d'imagerie, et matériau pour capteur optique - Google Patents

Élément de conversion photoélectrique, élément d'imagerie, capteur optique, matériau pour élément de conversion photoélectrique, matériau pour élément d'imagerie, et matériau pour capteur optique Download PDF

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WO2020203355A1
WO2020203355A1 PCT/JP2020/012327 JP2020012327W WO2020203355A1 WO 2020203355 A1 WO2020203355 A1 WO 2020203355A1 JP 2020012327 W JP2020012327 W JP 2020012327W WO 2020203355 A1 WO2020203355 A1 WO 2020203355A1
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substituent
group
photoelectric conversion
atom
carbon atoms
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PCT/JP2020/012327
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Japanese (ja)
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知昭 吉岡
孝一 岩▲崎▼
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富士フイルム株式会社
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Priority to JP2021511449A priority Critical patent/JP7133707B2/ja
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    • 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

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  • the present invention relates to a photoelectric conversion element, an image sensor, an optical sensor, a material for a photoelectric conversion element, a material for an image sensor, and a material for an optical sensor.
  • Patent Document 1 discloses an organic photoelectric conversion element having a layer containing a predetermined compound.
  • the photoelectric conversion element is required to further improve the photoelectric conversion efficiency.
  • the photoelectric conversion element is required to have stable performance even when the photoelectric conversion film is vapor-deposited using a vapor deposition material which is continuously subjected to vapor deposition for a long time (for example, 5 hours). Has been done.
  • the present invention is a photoelectric conversion element having excellent photoelectric conversion efficiency and having stable performance even when a photoelectric conversion film is vapor-deposited using a vapor deposition material that is continuously subjected to vapor deposition for a long time.
  • the challenge is to provide.
  • Another object of the present invention is to provide an image sensor, an optical sensor, a material for a photoelectric conversion element, a material for an image sensor, and a material for an optical sensor.
  • the A 1 has the formula (1-B) and represents any one of structures represented by formula (1-C), the photoelectric conversion element according to [1] or [2].
  • X b1 represents a sulfur atom, an oxygen atom, or NR b11
  • R b11 has an alkyl group or a substituent which may have a substituent.
  • X C1 represents a sulfur atom, an oxygen atom, or NR c11
  • R c11 is an alkyl group which may have a substituent or an aryl which may have a substituent.
  • the photoelectric conversion element according to any one of [1] to [3], which represents a heteroaryl group which may have a group or a substituent.
  • both Ar 1 and Ar 4 are independently selected from the group consisting of an aryl group which may have a substituent and a heteroaryl group which may have a substituent.
  • the photoelectric conversion element according to any one of [1] to [4], which has one or more substituents.
  • both Ar 2 and Ar 3 may independently have an alkyl group having 6 or less carbon atoms and may have a substituent, respectively. It has the following alkoxy group, an alkylthio group having 6 or less carbon atoms which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and a substituent.
  • the photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the formula (1) and the n-type semiconductor material are mixed.
  • the photoelectric conversion element according to any one of [1] to [7] which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. ..
  • the present invention it is possible to provide a photoelectric conversion element having excellent photoelectric conversion efficiency and having stable performance even when a photoelectric conversion film is vapor-deposited using a vapor deposition material which is continuously subjected to vapor deposition for a long time. Further, according to the present invention, it is possible to provide an image pickup element, an optical sensor, a material for a photoelectric conversion element, a material for an image pickup element, and a material for an optical sensor.
  • the substituent W in the present specification will be described.
  • the substituent W is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (cyclo). (Including alkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heteroaryl group (may be called heterocyclic group), cyano group, hydroxy group, carboxy group, nitro group, alkoxy group, aryloxy group.
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • an alkyl group including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group
  • each of the above-mentioned groups may further have a substituent (for example, one or more groups of each of the above-mentioned groups) if possible.
  • a substituent for example, one or more groups of each of the above-mentioned groups
  • an alkyl group which may have a substituent is also included as a form of the substituent W.
  • the substituent W has a carbon atom
  • the number of carbon atoms of the substituent W is, for example, 1 to 20.
  • the number of atoms other than the hydrogen atom of the substituent W is, for example, 1 to 30.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
  • the alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclopentyl group and the like.
  • the alkyl group may be, for example, a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group, and may have a cyclic structure thereof as a partial structure.
  • the alkyl group which may have a substituent is not particularly limited, and examples thereof include a substituent W, and an aryl group (preferably 6 to 18 carbon atoms, more preferably). Has 6 carbon atoms), a heteroaryl group (preferably 5 to 18 carbon atoms, more preferably 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom).
  • the above-mentioned alkyl group is preferable as the alkyl group moiety in the alkoxy group.
  • the above-mentioned alkyl group is preferable as the alkyl group moiety in the alkylthio group.
  • the substituent that the alkoxy group may have includes the same examples as the substituent in the alkyl group that may have a substituent.
  • the alkylthio groups which may have a substituent the substituent which the alkylthio group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
  • the carbon number is preferably 1 to 6 and more preferably 1 to 4.
  • the alkyl group having 6 or less carbon atoms may be linear, branched, or cyclic. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclopentyl group and the like. ..
  • the substituent which the alkyl group having 6 or less carbon atoms may have is not particularly limited, and examples thereof include the substituent W, and an aryl group (preferably 6 to 18 carbon atoms, more preferably 6 carbon atoms). ), A heteroaryl group (preferably 5 to 18, more preferably 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom).
  • the alkyl group portion of the alkoxy group having 6 or less carbon atoms includes the same embodiment as the above-mentioned alkyl group having 6 or less carbon atoms.
  • examples of the substituent which the alkoxy group may have include the same substituents which the above-mentioned alkyl group having 6 or less carbon atoms may have. ..
  • the alkyl group portion of the alkylthio group having 6 or less carbon atoms includes the same embodiment as the above-mentioned alkyl group having 6 or less carbon atoms.
  • examples of the substituent which the alkylthio group may have include the same substituents which the above-mentioned alkyl group having 6 or less carbon atoms may have. ..
  • the aryl group is preferably an aryl group having 6 to 18 ring members.
  • the aryl group may be monocyclic or polycyclic.
  • a phenyl group, a naphthyl group, an anthryl group, or a phenanthrenyl group is preferable, and a phenyl group is more preferable.
  • the substituent which the aryl group may have is not particularly limited, and examples thereof include a substituent W and an alkyl group which may have a substituent (preferably).
  • the number of carbon atoms is preferably 1 to 10), and a methyl group is more preferable.
  • the heteroaryl group includes heteroatoms such as nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and / or boron atom.
  • a heteroaryl group having a monocyclic or polycyclic ring structure is preferable.
  • the number of carbon atoms in the ring member atom of the heteroaryl group is not particularly limited, but is preferably 3 to 18 and more preferably 3 to 5.
  • the number of heteroatoms in the ring member atom of the heteroaryl group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 2.
  • the number of ring members of the heteroaryl group is not particularly limited, but is preferably 5 to 8, more preferably 5 to 7, and even more preferably 5 to 6.
  • the heteroaryl group includes a fryl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a pteridinyl group, a pyrazinyl group, a quinoxalinyl group, a pyrimidinyl group, a quinazolyl group, a pyridadinyl group, a synnolinyl group and a phthalazinyl group.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the hydrogen atom may be a light hydrogen atom (ordinary hydrogen atom) or a deuterium atom (double hydrogen atom or the like).
  • a feature of the photoelectric conversion element of the present invention is that the photoelectric conversion film contains a compound represented by the formula (1) described later (hereinafter, also referred to as “specific compound”) and an n-type semiconductor material.
  • the specific compound has a predetermined structure on both sides of the condensed ring which is the central ring (any structure represented by the formulas (1-A) to (1-C) in the formula (1)). It has a structure in which aromatic rings are bonded.
  • the photoelectric conversion film containing the specific compound can efficiently separate charges and is excellent in photoelectric conversion efficiency.
  • the photoelectric conversion film containing the specific compound is also excellent in manufacturability (particularly, continuous vapor deposition suitability) due to the above-mentioned structure of the specific compound (hereinafter, "excellent in continuous vapor deposition suitability of the photoelectric conversion film”). It is presumed. As a result, the performance of the photoelectric conversion element has high stability even when the photoelectric conversion film is vapor-deposited by continuous vapor deposition for a long time.
  • excellent photoelectric conversion efficiency and / or excellent continuous vapor deposition suitability of the photoelectric conversion film is also simply referred to as "excellent effect of the present invention”.
  • FIG. 1 shows a schematic cross-sectional view of an embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10a shown in FIG. 1 includes a conductive film (hereinafter, also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and an upper electrode. It has a structure in which functional transparent conductive films (hereinafter, also referred to as upper electrodes) 15 are laminated in this order.
  • FIG. 2 shows a configuration example of another photoelectric conversion element.
  • FIGS. 1 and 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are laminated in this order on a lower electrode 11.
  • the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be appropriately changed depending on the application and characteristics.
  • the photoelectric conversion element 10a it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Further, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 ⁇ 10 -5 to 1 ⁇ 10 7 V / cm is applied between the pair of electrodes. From the viewpoint of performance and power consumption, the applied voltage is more preferably 1 ⁇ 10 -4 to 1 ⁇ 10 7 V / cm, further preferably 1 ⁇ 10 -3 to 5 ⁇ 10 6 V / cm.
  • the voltage application method it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2.
  • a voltage can be applied by the same method.
  • the photoelectric conversion element 10a (or 10b) can be suitably applied to an image sensor application.
  • the photoelectric conversion film is a film containing a specific compound.
  • the specific compound will be described in detail.
  • Ar 1 and Ar 4 are independently an alkyl group having 6 or less carbon atoms which may have a substituent, an alkoxy group having 6 or less carbon atoms which may have a substituent, and a substituent.
  • One or more kinds selected from the group consisting of halogen atoms include fluorine atom, chlorine atom, bromine atom, iodine atom and the like. The same applies to the halogen atom described below).
  • the aromatic ring may be a monocyclic ring or a polycyclic ring.
  • the polycyclic aromatic ring is preferably a condensed 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 2 to 4, more preferably 2 to 3.
  • the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of the heteroatom of the aromatic heterocycle 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 number of heteroatoms in the ring member atoms of the aromatic heterocycle is preferably 1 to 5, and more preferably 1 to 2.
  • the number of ring members of the aromatic ring is preferably 5 to 20, more preferably 6 to 10.
  • Examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, quinoxaline ring, pyridine ring, pyrazine ring, pyrrole ring, furan ring, thiazole ring, benzothiazole ring, thiophene ring, benzothiophene ring, and imidazole ring. Examples include a ring and an oxazole ring.
  • the substituents represented by the aromatic rings represented by Ar 1 and Ar 4 may have an alkyl group having 6 or less carbon atoms which may have a substituent and 6 or less carbon atoms which may have a substituent.
  • Examples of the silyl group which may have the above-mentioned substituent include a group represented by ⁇ Si ( RS1 ) ( RS2 ) ( RS3 ).
  • R S1 , R S2 , and R S3 independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent.
  • both Ar 1 and Ar 4 are independently composed of an aryl group which may have a substituent and a heteroaryl group which may have a substituent. It is preferable to have one or more substituents selected from the group. Specific examples of the aryl group which may have a substituent and the heteroaryl group which may have a substituent are as described above.
  • the aromatic ring represented by Ar 1 and / or Ar 4 has two or more of the above-mentioned substituents
  • the substituents may be bonded to each other to form a ring.
  • the aromatic ring represented by Ar 1 has an alkyl group having 6 or less carbon atoms which may have a substituent and an aryl group which may have a substituent
  • the aromatic ring may have the above substituent.
  • a good alkyl group having 6 or less carbon atoms and an aryl group which may have the above-mentioned substituent may be bonded to form a ring.
  • the effect of the present invention is more excellent, when the monocyclic aromatic ring represented by Ar 1 and / or Ar 4 has two or more of the above-mentioned substituents, the substituents are bonded to each other to form a ring. It is preferable not to do so.
  • n1 represents 1 and Ar 1 has an aryl group as a substituent
  • n2 represents 1 and Ar 4 has an aryl group as a substituent
  • Ar 2 and Ar 3 may independently have an alkyl group having 6 or less carbon atoms which may have a substituent, an alkoxy group having 6 or less carbon atoms which may have a substituent, and a substituent. From a group consisting of a good alkylthio group having 6 or less carbon atoms, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a silyl group which may have a substituent, and a halogen atom. Represents a monocyclic aromatic ring which may have one or more substituents of choice.
  • the monocyclic aromatic ring represented by Ar 2 and Ar 3 is not particularly limited, and may be an aromatic hydrocarbon ring or an aromatic heterocycle.
  • the heteroatom of the aromatic heterocycle 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 number of heteroatoms in the ring member atoms of the aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.
  • the number of ring members of the monocyclic aromatic ring represented by Ar 2 and Ar 3 is preferably 5 to 10, more preferably 5 or 6, and even more preferably 6.
  • Examples of the monocyclic aromatic ring represented by Ar 2 and Ar 3 include a benzene ring, a pyridine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiazole ring, a thiophene ring, an imidazole ring, and an oxazole ring. ..
  • a benzene ring or a thiophene ring is preferable. Among them, it is preferable that the monocyclic aromatic rings represented by Ar 2 and Ar 3 are all thiophene rings in that the effect of the present invention is more excellent.
  • an alkyl group having 6 or less carbon atoms which may have a substituent and a carbon which may have a substituent may be used. It has an alkoxy group having a number of 6 or less, an alkylthio group having 6 or less carbon atoms which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, and a substituent. It is a substituent selected from the group consisting of a optionally silyl group and a halogen atom.
  • the silyl group which may have the above-mentioned substituents includes the above-mentioned silyl group which may have a substituents as the substituents which the aromatic rings represented by Ar 1 and Ar 4 may have. Similar things can be mentioned.
  • the substituents may be bonded to each other to form a ring.
  • the monocyclic aromatic ring represented by Ar 2 has an alkyl group having 6 or less carbon atoms which may have a substituent and an aryl group which may have a substituent, it has the above substituent.
  • An alkyl group having 6 or less carbon atoms and an aryl group which may have the above-mentioned substituent may be bonded to form a ring.
  • the effect of the present invention is more excellent, when the monocyclic aromatic ring represented by Ar 2 and / or Ar 3 has two or more of the above-mentioned substituents, the substituents are bonded to each other to form a ring. It is preferable not to do so.
  • L 1 and L 2 independently represent a sulfur atom, an oxygen atom, a selenium atom, CR 1 R 2 , SiR 3 R 4 , or NR 5 .
  • R 1 to R 5 independently represent a hydrogen atom or a substituent.
  • the substituent represented by R 1 to R 5 is not particularly limited, but for example, an alkyl group is preferable.
  • n1 and n2 independently represent 0 or 1, respectively. However, when n1 represents 0, L 1 does not exist, and Ar 1 and Ar 2 are connected only by the single bond specified in the equation (1). Further, when n2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (1). That is, when both n1 and n2 represent 0, the compound represented by the formula (1) is intended to be the compound represented by the following formula (1X). When n1 represents 1 and n2 represents 0, the compound represented by the formula (1) is intended to be a compound represented by the following formula (1Y). When n1 represents 0 and n2 represents 1, the compound represented by the formula (1) is intended to be a compound represented by the following formula (1Z).
  • Ar 1 to Ar 4 , L 1 , L 2 , and A 1 are Ar 1 to Ar 4 , L 1 , L 2 , L 2 , respectively, in the formula (1).
  • a 1 are synonymous with, and the preferred embodiment is also the same.
  • a 1 represents any structure represented by the following formulas (1-A) to (1-C). Hereinafter, each structure of the formulas (1-A) to (1-C) will be described.
  • R a1 to R a6 each independently represent a hydrogen atom or a substituent.
  • R a1 to R a6 (preferably R a3 and R a4 , or R a1 and R a6 ) may be bonded to each other to form a ring structure.
  • hydrogen atoms are preferable as R a1 to R a6 .
  • * 1 represents the bonding position with Ar 2 in the formula (1)
  • * 2 represents the bonding position with Ar 3 in the formula (1).
  • R b1 to R b13 independently represent a hydrogen atom or a substituent.
  • R b1 to R b13 (preferably R b2 and R b3 , R b3 and R b4 , or R b4 and R b5 ) may be bonded to each other to form a ring structure.
  • R b1 to R b8 hydrogen atoms are preferable as R b1 to R b8 .
  • the substituents represented by R b9 to R b13 may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Heteroaryl groups are preferred.
  • X b1 is represented by CR b12 R b13
  • the carbon atom to which R b12 and R b13 are linked may be a spiro atom.
  • * 1 represents the bonding position with Ar 2 in the formula (1)
  • * 2 represents the bonding position with Ar 3 in the formula (1).
  • R c1 to R c13 independently represent a hydrogen atom or a substituent.
  • R c1 to R c13 (preferably R c1 and R c2 , R c3 and R c4 , or R c5 and R c6 ) may be bonded to each other to form a ring structure.
  • R c1 to R c8 hydrogen atoms are preferable as R c1 to R c8 .
  • the substituents represented by R c9 to R c13 may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Heteroaryl groups are preferred.
  • X c1 is represented by CR c12 R c13
  • the carbon atom to which R c12 and R c13 are linked may be a spiro atom.
  • * 1 represents the bonding position with Ar 2 in the formula (1)
  • * 2 represents the bonding position with Ar 3 in the formula (1).
  • a 1 preferably represents any of the structures represented by the formulas (1-B) and (1-C) in that the effect of the present invention is more excellent.
  • Condition 1 In the equation (1), A 1 represents any of the structures represented by the equations (1-B) and (1-C), and both Ar 2 and Ar 3 are independent of each other.
  • an alkyl group having 6 or less carbon atoms which may have a substituent an alkoxy group having 6 or less carbon atoms which may have a substituent, and an alkylthio group having 6 or less carbon atoms which may have a substituent
  • a 1 represents one of the structures represented by the formulas (1-B) and (1-C), and both Ar 2 and Ar 3 are independent of each other.
  • Ar 1 and Ar 4 may independently have an aryl group and a substituent which may have a substituent. It has one or more substituents selected from the group consisting of heteroaryl groups which may have.
  • the molecular weight of the specific compound is not particularly limited, but is preferably 450 to 1000. When the molecular weight is 1000 or less, the vapor deposition temperature does not rise and the decomposition of the compound is unlikely to occur. When the molecular weight is 450 or more, the glass transition point of the vapor-deposited film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
  • the specific compound may be used alone or in combination of two or more.
  • the specific compound is particularly useful as a material for a photoelectric conversion film used in an image sensor or an optical sensor.
  • the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescence diagnostic agent material.
  • a compound having an ionization potential of -5.0 to -6.0 eV in a single membrane is preferable in terms of matching the energy level with the n-type semiconductor material described later.
  • the maximum absorption wavelength of the specific compound is not particularly limited, but is preferably in the range of, for example, 300 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 becomes 0.5 to 1.
  • the maximum absorption wavelength of the photoelectric conversion film is not particularly limited, but is preferably in the range of 300 to 700 nm, for example.
  • the photoelectric conversion film contains an n-type semiconductor material as a component other than the above-mentioned specific compound.
  • the n-type semiconductor material is an acceptor-type organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting electrons. More specifically, the n-type semiconductor material refers to an organic compound having a higher electron affinity than the specific compound when used in contact with the above-mentioned specific compound.
  • the electron affinity value is the reciprocal value of the LUMO (Lowest Unellad Molecular Orbital) value obtained by the calculation of B3LYP / 6-31G (d) using Gaussian '09 (software manufactured by Gaussian).
  • the LUMO of the n-type semiconductor material is preferably ⁇ 2.5 to ⁇ 5.0 eV.
  • Examples of the n-type semiconductor material include fullerene selected from the group consisting of fullerene and derivatives thereof, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, etc.
  • 5- to 7-membered heterocyclic compounds having at least one nitrogen atom, oxygen atom, and sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxalin, quinazoline, phthalazine, Synnoline, isoquinolin, pteridine, aclysine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, etc.); polyarylene compounds; fluorene compounds; cyclopentadiene compounds; silyl compounds; 1,4,5,8-naphthalenetetracarboxylic acid anhydrides Substances; 1,4,5,8-naphthalenetetracarboxylic acid anhydride imide derivative, oxadiazole derivative; anthracinodimethane derivative; diphenylquinone derivative; vasocpro
  • the n-type semiconductor material preferably contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
  • fullerenes include fullerenes C60, fullerenes C70, fullerenes C76, fullerenes C78, fullerenes C80, fullerenes C82, fullerenes C84, fullerenes C90, fullerenes C96, fullerenes C240, fullerenes C540, and mixed fullerenes.
  • fullerene derivative include compounds in which a substituent is added to the above fullerene.
  • an alkyl group, an aryl group, or a heterocyclic group is preferable.
  • the fullerene derivative the compound described in JP-A-2007-123707 is preferable.
  • the n-type semiconductor material contains fullerenes
  • the thickness) ⁇ 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 20 to 60% by volume.
  • An organic dye may be used as the n-type semiconductor material in place of the n-type semiconductor material described in the upper row or together with the n-type semiconductor material described in the upper row.
  • an organic dye as the n-type semiconductor material, it is easy to control the absorption wavelength (maximum absorption wavelength) of the photoelectric conversion element in an arbitrary wavelength range.
  • the organic pigments include cyanine pigments, styryl pigments, hemicyanine pigments, merocyanine pigments (including zero methimerocyanine (simple merocyanine)), rodacyanine pigments, allopolar pigments, oxonor pigments, hemioxonor pigments, squalium pigments, and croconium pigments.
  • the n-type semiconductor material contains an organic dye
  • the film thickness) ⁇ 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 35 to 80% by volume.
  • the molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.
  • the photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type semiconductor material are mixed.
  • the bulk heterostructure is a layer in which a specific compound and an n-type semiconductor material are mixed and dispersed in a photoelectric conversion film.
  • the bulk heterostructure is described in detail in paragraphs [0013] to [0014] of JP-A-2005-303266.
  • the film thickness of the n-type semiconductor material (thickness in terms of a single layer) ⁇ 100) is preferably 15 to 75% by volume, more preferably 30 to 75% by volume.
  • the photoelectric conversion film is substantially composed of a specific compound and an n-type semiconductor material. Substantially means that the total content of the specific compound and the n-type semiconductor material is 95% by mass or more with respect to the total mass of the photoelectric conversion film.
  • the n-type semiconductor material contained in the photoelectric conversion film may be used alone or in combination of two or more.
  • the photoelectric conversion film 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).
  • the non-luminescent film is intended to be a film having an emission quantum efficiency of 1% or less, and the emission quantum efficiency is preferably 0.5% or less, more preferably 0.1% or less.
  • the photoelectric conversion film can be formed mainly by a dry film forming method.
  • the dry film forming method include a physical vapor deposition method such as a vapor deposition method (particularly a vacuum vapor deposition method), a sputtering method, an ion plating method, and an MBE (Molecular Beam Epitaxy) method, and CVD such as plasma polymerization. (Chemical Vapor Deposition) method can be mentioned. Of these, the vacuum deposition method is preferable.
  • the manufacturing conditions such as the degree of vacuum and the vapor deposition temperature can be set according to a conventional method.
  • the thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, further preferably 50 to 500 nm, and particularly preferably 50 to 300 nm.
  • the electrodes are made of a conductive material.
  • the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected.
  • the material constituting the upper electrode 15 include antimony or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine topped Tin Oxide), tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO).
  • Conductive metal oxides such as Indium Tin Oxide), and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; mixtures of these metals with conductive metal oxides.
  • conductive metal oxides are preferable from the viewpoints of high conductivity and transparency.
  • the sheet resistance is preferably 100 to 10000 ⁇ / ⁇ .
  • the degree of freedom in the range of film thickness that can be thinned is large.
  • Increasing the light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
  • the film thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.
  • the lower electrode 11 may be transparent or may reflect light without being transparent, depending on the intended use.
  • the material constituting the lower electrode 11 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium tin oxide (IZO).
  • Conductive metal oxides such as; metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides or nitrides of these metals (example: titanium nitride (TiN)). ); Mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.
  • the method for forming the electrode is not particularly limited, and can be appropriately selected depending on the electrode material. Specific examples include wet methods such as printing methods and coating methods; physical methods such as vacuum deposition, sputtering, and ion plating; and chemical methods such as CVD and plasma CVD. Be done.
  • wet methods such as printing methods and coating methods
  • physical methods such as vacuum deposition, sputtering, and ion plating
  • chemical methods such as CVD and plasma CVD. Be done.
  • the electrode material is ITO, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and a dispersion of indium tin oxide can be mentioned.
  • the photoelectric conversion element of the present invention preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
  • the intermediate layer include a charge blocking film.
  • the charge blocking film include an electron blocking film and a hole blocking film. Each film will be described in detail below.
  • the electron blocking film is a donor organic semiconductor material (compound), and for example, the following p-type organic semiconductors can be used.
  • One type of p-type organic semiconductor may be used alone, or two or more types may be used.
  • Examples of the p-type organic semiconductor include triarylamine compounds (for example, N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD), 4, 4'-Bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), the compound described in paragraphs [0128] to [0148] of JP2011-228614A, JP2011-176259.
  • TPD triarylamine compounds
  • TPD 4, 4'-Bis [N- (naphthyl) -N-phenyl-amino] biphenyl
  • ⁇ -NPD [N- (naphthyl) -N-phenyl-amino] biphenyl
  • cyanine compounds Oxonol compounds, polyamine compounds, indol compounds, pyrrol compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and Fluolanthene derivatives), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted calcon compounds, oxazole compounds, fluorenone compounds, silazane compounds, and nitrogen-containing heterocyclic compounds.
  • aromatic carbocyclic compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives,
  • Examples thereof include metal compounds having the above as a ligand.
  • Examples of the p-type organic semiconductor include compounds having a smaller ionization potential than the n-type semiconductor material, and if this condition is satisfied, the organic dye exemplified as the n-type semiconductor material can be used.
  • a polymer material can also be used as the electron blocking film.
  • the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrrole, pyrrole, picolin, thiophene, acetylene, and diacetylene, and derivatives thereof.
  • the electron blocking film may be composed of a plurality of films.
  • the electron blocking film may be made of an inorganic material.
  • the inorganic material has a higher dielectric constant than the organic material, when the inorganic material is used for the electron blocking film, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency becomes high.
  • the inorganic material that can be an electron blocking film include calcium oxide, chromium oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium oxide copper, niobium oxide, molybdenum oxide, and indium oxide. Examples include copper, indium silver oxide, and iridium oxide.
  • the hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type semiconductor material can be used.
  • the method for producing the charge blocking film is not particularly limited, and examples thereof include a dry film forming method and a wet film forming method.
  • the dry film forming method include a vapor deposition method and a sputtering method.
  • the vapor deposition method may be any of a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable.
  • Examples of the wet film forming method include an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and a gravure coating method. From the viewpoint of precision patterning, the inkjet method is preferable.
  • the thickness of the charge blocking film is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.
  • the photoelectric conversion element may further have a substrate.
  • the type of substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate.
  • the position of the substrate is not particularly limited, but usually, the conductive film, the photoelectric conversion film, and the transparent conductive film are laminated in this order on the substrate.
  • the photoelectric conversion element may further have a sealing layer.
  • the performance of the photoelectric conversion material may be significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is covered with a ceramic such as a dense metal oxide, metal nitride, or metal nitride that does not allow water molecules to permeate, or a sealing layer such as diamond-like carbon (DLC: Diamond-like Carbon).
  • DLC Diamond-like Carbon
  • FIG. 3 is a schematic cross-sectional view showing a schematic configuration of an image pickup device for explaining an embodiment of the present invention.
  • This image pickup element is mounted on an image pickup element such as a digital camera and a digital video camera, an electronic endoscope, and an image pickup module such as a mobile phone.
  • the imaging element 20a shown in FIG. 3 includes a photoelectric conversion element 10a (green photoelectric conversion element 10a) of the present invention, a blue photoelectric conversion element 22, and a red photoelectric conversion element 24, and these include a direction in which light is incident. Are laminated.
  • the photoelectric conversion element 10a is the photoelectric conversion element of the present invention, and is mainly used as a green photoelectric conversion element by controlling the absorption wavelength so that green light can be received. Examples of the method of controlling the absorption wavelength of the photoelectric conversion element of the present invention include a method of using an organic dye suitable as an n-type semiconductor material.
  • the image sensor 20a is a so-called laminated body type color-separated image sensor.
  • the photoelectric conversion element 10a, the blue photoelectric conversion element 22, and the red photoelectric conversion element 24 have different wavelength spectra to be detected. That is, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 correspond to photoelectric conversion elements that receive light having a wavelength different from the light received (absorbed) by the photoelectric conversion element 10a.
  • the photoelectric conversion element 10a can mainly receive green light
  • the blue photoelectric conversion element 22 can mainly receive blue light
  • the red photoelectric conversion element can mainly receive red light.
  • the green light is intended to be light having a wavelength in the range of 500 to 600 nm
  • the blue light is intended to be light in the wavelength range of 400 to 500 nm
  • the red light is intended to be light in the wavelength range of 600 to 700 nm.
  • the photoelectric conversion element 10a mainly absorbs green light, but blue light and red light pass through the photoelectric conversion element 10a.
  • the blue light is mainly absorbed, but the red light is transmitted through the blue photoelectric conversion element 22.
  • the red photoelectric conversion element 24 is absorbed by the red photoelectric conversion element 24.
  • the image sensor 20a which is a laminated color-separated image sensor, one pixel can be composed of three light receiving units of green, blue, and red, and a large area of the light receiving unit can be obtained.
  • the configurations of the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 are not particularly limited.
  • a photoelectric conversion element having a configuration in which silicon is used to separate colors according to the difference in light absorption length may be used.
  • the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 may both be made of silicon.
  • the photoelectric conversion element 10a mainly receives the green light having the middle wavelength, and the remaining blue light. And red light can be easily separated.
  • blue light is easily absorbed near the surface of silicon, and red light reaches a relatively deep position in silicon. Can invade.
  • blue light is mainly received by the blue photoelectric conversion element 22 existing at a shallower position
  • red light is mainly received by the red photoelectric conversion element 24 existing at a deeper position.
  • the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 have a conductive film, an organic photoelectric conversion film having a maximum absorption of blue light or red light, and a transparent conductive film formation in this order.
  • the element (blue photoelectric conversion element 22 or red photoelectric conversion element 24) may be used.
  • the blue photoelectric conversion element 22 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so that the blue light has an absorption maximum.
  • the red photoelectric conversion element 24 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so that the red light has an absorption maximum.
  • the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention are arranged in this order from the incident side of the light, but the present invention is not limited to this, and the arrangement is not limited to this. May be good.
  • the blue photoelectric conversion element, the photoelectric conversion element of the present invention, and the red photoelectric conversion element may be arranged in this order from the side where the light is incident.
  • the green photoelectric conversion element may be used as a photoelectric conversion element other than the photoelectric conversion element of the present invention, and the blue photoelectric conversion element and / or the red photoelectric conversion element may be used as the photoelectric conversion element of the present invention.
  • the configuration in which the photoelectric conversion elements of the three primary colors of blue, green, and red are stacked has been described, but two layers (two colors) or four layers (4 colors) or more may be used. Absent.
  • the photoelectric conversion element 10a of the present invention may be arranged on the arranged blue photoelectric conversion element 22 and the red photoelectric conversion element 24. If necessary, a color filter that further absorbs light having a predetermined wavelength may be arranged on the incident side of the light.
  • the form of the image sensor is not limited to that shown in FIG. 3 and the above-mentioned form, and may be another form.
  • the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention may be arranged at the same in-plane position.
  • the photoelectric conversion element may be used in a single layer.
  • a blue, red, and green color filters may be arranged on the photoelectric conversion element 10a of the present invention to separate colors.
  • the photoelectric conversion element of the present invention is preferably used as an optical sensor.
  • the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion element is arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion element is arranged on a plane.
  • the present invention also relates to an invention of a material for a photoelectric conversion element, an invention of a material for an image sensor, and an invention of a material for an optical sensor.
  • the material for a photoelectric conversion element of the present invention is a material used for manufacturing a photoelectric conversion element, which contains a compound (specific compound) represented by the formula (1).
  • the material for an image sensor of the present invention is a material used for manufacturing a photoelectric conversion element for an image sensor, which contains a compound (specific compound) represented by the formula (1).
  • the material for an optical sensor of the present invention is a material used for manufacturing a photoelectric conversion element for an optical sensor, which contains a compound (specific compound) represented by the formula (1).
  • the compound represented by the formula (1) in the material for the photoelectric conversion element, the material for the image pickup device, and the material for the optical sensor is the same as the compound represented by the above formula (1).
  • the specific compound contained in the material for the image sensor and the material for the optical sensor is used for producing the photoelectric conversion film provided for the image sensor and the optical sensor, respectively.
  • the contents of the specific compound contained in the material for the photoelectric conversion element, the material for the image sensor, and the material for the optical sensor are the total mass of the material for the photoelectric conversion element, the total mass of the material for the image sensor, and the optical sensor, respectively. It is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 99 to 100% by mass, based on the total mass of the material.
  • the specific compound contained in the material for the photoelectric conversion element, the material for the image pickup element, and the material for the optical sensor may be one kind alone or two or more kinds.
  • the above compound is suitable for producing a photoelectric conversion element, and is preferably used for forming a photoelectric conversion film.
  • N-Phenyl-3,6-dibromocarbazole (2.00 g, 5.0 mmol) and 4-p-biphenylphenylboronic acid (2.67 g, 13.5 mmol) were added to tetrahydrofuran (100 mL) in the flask.
  • a 2M aqueous sodium carbonate solution (60 mL) was added thereto.
  • a series of operations of evacuation and nitrogen substitution in the flask was repeated three times in this order, and tetrakis (triphenylphosphine) palladium (0) (115 mg, 0.10 mmol) was added to the obtained reaction solution to obtain the obtained reaction solution.
  • the reaction solution was refluxed and reacted for 6 hours.
  • HOMO Highest Occupied Molecular Orbital
  • LUMO value of each compound are shown below.
  • the HOMO value and the LUMO value were obtained by calculation of B3LYP / 6-31G (d) using Gaussian '09 (software manufactured by Gaussian), respectively.
  • the value of the reciprocal of the obtained LUMO value was adopted as the value of the electron affinity of the compound.
  • the photoelectric conversion element includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.
  • an amorphous ITO is formed on a glass substrate by a sputtering method to form a lower electrode 11 (thickness: 30 nm), and the following compound (B-1) is further vacuumed on the lower electrode 11.
  • An electron blocking film 16A was formed by forming a film by a heat vapor deposition method.
  • a photoelectric conversion film 12 having a bulk heterostructure of 200 nm was formed by co-depositing and forming a film by a vacuum vapor deposition method so as to have a temperature of 100 nm and 100 nm (photoelectric conversion film forming step). Further, the following compound (B-2) was formed on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm).
  • an amorphous ITO was formed on the hole blocking film 16B by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
  • a SiO film is formed on the upper electrode 15 as a sealing layer by a vacuum vapor deposition method, and then an aluminum oxide (Al 2 O 3 ) layer is formed on the SiO film by an ALCVD (Atomic Layer Chemical Vapor Deposition) method to form a photoelectric conversion element.
  • ALCVD Atomic Layer Chemical Vapor Deposition
  • a photoelectric conversion element having a film was produced.
  • the relative value is (the value of the dark current of the photoelectric conversion film formed by performing the photoelectric conversion film forming step after 5 hours / the dark current of the photoelectric conversion element manufactured by performing the photoelectric conversion film forming step at the start of vapor deposition. The value) was calculated, and the suitability for continuous vapor deposition of the photoelectric conversion film was evaluated. Photoelectric conversion containing each compound by the same method except that compounds (D-2) to (D-9) and (R-1) to (R-2) were used instead of compound (D-1). The suitability for continuous vapor deposition of the film was evaluated.
  • the suitability for continuous vapor deposition of the photoelectric conversion film using each compound is A if the relative value is 1.5 or less, B if it is larger than 1.5 and 3 or less, B if it is larger than 3 and 10 or less, C or 10 If it was large, it was evaluated as D. In practice, B or higher is preferable, and A is more preferable.
  • Table 1 The photoelectric conversion element used in [evaluation of quantum efficiency (photoelectric conversion efficiency)] and [evaluation of drive confirmation (dark current))] was produced by carrying out a photoelectric conversion film forming step at the start of vapor deposition. It is a conversion element.
  • the photoelectric conversion element of the present invention is excellent in photoelectric conversion efficiency. Further, the photoelectric conversion element of the present invention has a small increase in dark current value and stable performance (in other words, continuous photoelectric conversion film) even when the photoelectric conversion element is manufactured by thin film deposition for a long time. Excellent vapor deposition suitability) was confirmed. That is, from the above results, it is shown that the photoelectric conversion element of the present invention has excellent photoelectric conversion efficiency and has stable performance even when vapor-deposited using a vapor-deposited material that is continuously subjected to vapor deposition for a long time. Was done.
  • both Ar 1 and Ar 4 in the formula (1) may independently have an aryl group and a substituent which may have a substituent. It was confirmed that the photoelectric conversion efficiency of the photoelectric conversion element is more excellent when it has one or more substituents selected from the group consisting of good heteroaryl groups. Further, from the comparison of Examples 2 to 4, when A 1 in the formula (1) represents any of the structures represented by the formulas (1-B) and the formula (1-C), the photoelectric conversion element is used. It was confirmed that the photoelectric conversion efficiency was better. Further, from the comparison of the examples, it was confirmed that the photoelectric conversion efficiency of the photoelectric conversion element is more excellent when the equation (1) satisfies the condition 1 or the condition 2 shown below.
  • a 1 represents any of the structures represented by the equations (1-B) and (1-C), and both Ar 2 and Ar 3 are independent of each other.
  • an alkyl group having 6 or less carbon atoms which may have a substituent an alkoxy group having 6 or less carbon atoms which may have a substituent, and an alkylthio group having 6 or less carbon atoms which may have a substituent,
  • a 1 represents one of the structures represented by the formulas (1-B) and (1-C), and both Ar 2 and Ar 3 are independent of each other.
  • It has one or more substituents selected from the group consisting of an aryl group which may have a substituent, a heteroaryl group which may have a substituent, a silyl group which may have a substituent, and a halogen atom. It may represent a monocyclic aromatic hydrocarbon ring (preferably a benzene ring), and both Ar 1 and Ar 4 may independently have an aryl group and a substituent which may have a substituent. It has one or more substituents selected from the group consisting of heteroaryl groups which may have.
  • the photoelectric conversion element of the comparative example did not meet the desired requirements for both excellent photoelectric conversion efficiency and continuous vapor deposition suitability.

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  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Light Receiving Elements (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un élément de conversion photoélectrique ayant une excellente efficacité de conversion photoélectrique, et ayant une performance stable même lorsqu'un film de conversion photoélectrique est produit par dépôt en phase vapeur à l'aide d'un matériau de dépôt en phase vapeur utilisé pour le dépôt en phase vapeur pendant une longue période de temps. Les autres problèmes adressés par la présente invention concernent un élément d'imagerie, un capteur optique, un matériau pour un élément de conversion photoélectrique, un matériau pour un élément d'imagerie, et un matériau pour un capteur optique.　L'élément de conversion photoélectrique est obtenu par stratification d'un film électriquement conducteur, d'un film de conversion photoélectrique et d'un film électriquement conducteur transparent dans cet ordre, le film de conversion photoélectrique contenant un composé représenté par la formule (1) et un matériau semi-conducteur de type n.
PCT/JP2020/012327 2019-03-29 2020-03-19 Élément de conversion photoélectrique, élément d'imagerie, capteur optique, matériau pour élément de conversion photoélectrique, matériau pour élément d'imagerie, et matériau pour capteur optique WO2020203355A1 (fr)

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JP2011254071A (ja) * 2010-05-07 2011-12-15 Sumitomo Chemical Co Ltd 有機光電変換素子
JP2012049352A (ja) * 2010-08-27 2012-03-08 Konica Minolta Holdings Inc 有機光電変換素子、それを用いた太陽電池、及び光センサアレイ
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