WO2014157238A1 - Matériau de conversion photoélectrique, élément de conversion photoélectrique et procédé d'utilisation de ce dernier, capteur optique et élément de capture d'image - Google Patents

Matériau de conversion photoélectrique, élément de conversion photoélectrique et procédé d'utilisation de ce dernier, capteur optique et élément de capture d'image Download PDF

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WO2014157238A1
WO2014157238A1 PCT/JP2014/058345 JP2014058345W WO2014157238A1 WO 2014157238 A1 WO2014157238 A1 WO 2014157238A1 JP 2014058345 W JP2014058345 W JP 2014058345W WO 2014157238 A1 WO2014157238 A1 WO 2014157238A1
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photoelectric conversion
ring
substituent
group
formula
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PCT/JP2014/058345
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Japanese (ja)
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陽介 山本
野村　公篤
孝彦 一木
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富士フイルム株式会社
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Priority to KR1020157025645A priority Critical patent/KR101632161B1/ko
Publication of WO2014157238A1 publication Critical patent/WO2014157238A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/92—Naphthofurans; Hydrogenated naphthofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • 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
    • C07D333/26—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/36—Nitrogen atoms
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide

Definitions

  • the present invention relates to a photoelectric conversion material, a photoelectric conversion element, a method for using the photoelectric conversion element, an optical sensor, and an imaging element.
  • a conventional optical sensor is an element in which a photodiode (PD) is formed in a semiconductor substrate such as silicon (Si).
  • PD photodiode
  • Si silicon
  • signal charges generated in each PD are arranged in two dimensions. Are widely used.
  • a structure in which a color filter that transmits light of a specific wavelength is arranged on the light incident surface side of the flat solid-state imaging device is generally used.
  • Color filters that transmit blue (B) light, green (G) light, and red (R) light are regularly arranged on each two-dimensionally arranged PD that is currently widely used in digital cameras and the like.
  • Single-plate solid-state imaging devices are well known.
  • Patent Document 1 and Patent Document 2 disclose materials having a specific structure as a photoelectric conversion material used for a photoelectric conversion element.
  • the vapor deposition process can be carried out continuously at a high vapor deposition rate for a long time.
  • the heat load applied to the material at a low vapor deposition rate is compared with the heat load applied to the material at a high vapor deposition rate, the latter heat load is greater. Therefore, in order to maintain a high vapor deposition rate, it is necessary that the photoelectric conversion material in the crucible be difficult to be decomposed even when exposed to a high temperature environment for a long time. That is, the photoelectric conversion material is required to have excellent heat resistance.
  • Patent Document 1 The inventors of the present invention have studied the photoelectric conversion materials disclosed in Patent Document 1 and Patent Document 2, and have not yet reached the level required recently in terms of heat resistance and vapor deposition stability, and further improvements are necessary. I found out.
  • An object of this invention is to provide the photoelectric conversion material which is excellent in heat resistance and vapor deposition stability in view of the said situation.
  • Another object of the present invention is to provide a photoelectric conversion element using the photoelectric conversion material, a method for using the photoelectric conversion element, and an optical sensor and an imaging element including the photoelectric conversion element.
  • the photoelectric conversion material which is the compound (A) represented by the formula (1) described later, is excellent in heat resistance and vapor deposition stability.
  • the present inventors have found that the above problem can be solved by the following configuration.
  • a photoelectric conversion material which is a compound (A) represented by the following formula (1).
  • Ar 11 and Ar 12 represent an aryl group or a heteroaryl group which may have a substituent. At least one of Ar 11 and Ar 12 represents the following formula (2 Ar 11 and Ar 12 may be bonded to each other through a divalent organic group to form a ring.
  • Z 1 represents a ring containing at least three carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring.
  • Ar 13 and Ar 14 represent an aryl group or a heteroaryl group which may have a substituent.
  • Ar 13 and / or Ar 14 represents Ar 11 in the above formula (1). or Ar 12 and may be bonded to each other to form a ring.
  • * Represents a binding position.
  • L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. .
  • L 1 is a single bond, the nitrogen atom in formula (2) is directly bonded to Ar 11 and / or Ar 12 .
  • R 11 to R 24 represent a hydrogen atom or a substituent. At least one of R 11 to R 24 is a group represented by the following formula (4): R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring. a and b represent an integer of 0 or more. Z 1 represents a ring containing at least three carbon atoms and a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. )
  • Ar 13 and Ar 14 represent an aryl group or a heteroaryl group which may have a substituent.
  • Ar 13 and / or Ar 14 represents R 11 in the above formula (3).
  • At least one of -R 24 may be bonded to each other to form a ring.
  • * Represents a binding position.
  • L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. .
  • L 1 is a single bond, the nitrogen atom in the formula (4) is directly bonded to at least one of R 11 to R 24 .
  • Z 2 represents a ring containing at least 3 carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. (* Represents a bonding position.)
  • R 11 to R 24 represent a hydrogen atom or a substituent. At least one of R 11 to R 24 is a group represented by the following formula (6): R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring. a and b represent an integer of 0 or more.
  • R 51 to R 54 represent a hydrogen atom or a substituent. R 51 and R 52 , R 52 and R 53 , and R 53 and R 54 may be bonded to each other to form a ring.
  • Ar 13 and Ar 14 represent an aryl group or a heteroaryl group which may have a substituent.
  • Ar 13 and / or Ar 14 represents R 11 in the above formula (5).
  • At least one of -R 24 may be bonded to each other to form a ring.
  • * Represents a binding position.
  • L 1 represents a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or a divalent heteroaryl group which may have a substituent. .
  • L 1 is a single bond, the nitrogen atom in the formula (6) is directly bonded to at least one of R 11 to R 24 .
  • a photoelectric conversion element comprising a conductive film, a photoelectric conversion film containing the photoelectric conversion material according to any one of (1) to (10), and a transparent conductive film in this order.
  • the film thickness + the film thickness of the fullerenes in terms of a single layer)) is 50% by volume or more.
  • this invention can provide the photoelectric conversion element using the said photoelectric conversion material, the usage method of the said photoelectric conversion element, and the optical sensor and imaging device containing a photoelectric conversion element.
  • FIG. 1A and FIG. 1B are schematic cross-sectional views each showing a configuration example of a photoelectric conversion element. It is a cross-sectional schematic diagram for 1 pixel of an image pick-up element.
  • 1 is a 1 H-NMR spectrum of a compound (1).
  • (5) it is a 1 H-NMR spectrum of the compound of.
  • It is a 1 H-NMR spectrum of compound (12).
  • the photoelectric conversion material of this invention is a compound (A) represented by Formula (1) mentioned later.
  • the compound (A) has two aromatic hydrocarbon rings and / or aromatic heterocycles bonded to the ring represented by Z 1.
  • Z 1 There are no hydrogen atoms with high acidity or hydrogen atoms on alkyl groups with relatively high acidity. For this reason, even when exposed to a high temperature environment for a long time, structural changes such as decomposition hardly occur, and it is considered that excellent heat resistance and vapor deposition stability are exhibited.
  • the photoelectric conversion element manufactured using the said compound (A) excellent in heat resistance and vapor deposition stability has a small performance (responsiveness) difference between manufacturing lots, and is excellent in manufacturing aptitude.
  • the compound (A) which is the photoelectric conversion material of the present invention is represented by the following formula (1).
  • Ar ⁇ 11 > and Ar ⁇ 12 > represent the aryl group or heteroaryl group which may have a substituent. Especially, the aryl group which may have a substituent is preferable from the reason which heat resistance and vapor deposition stability are more excellent.
  • Ar 11 or Ar 12 is an aryl group
  • an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable.
  • Preferred examples of the aryl group include, for example, a phenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, a fluorenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, and a biphenyl group (two phenyl groups can be connected in any connection manner).
  • a terphenyl group (three phenyl groups may be connected in an arbitrary connection manner), and a phenyl group or a naphthyl group is more preferable.
  • substituent of the aryl group include a substituent W described later.
  • Ar 11 or Ar 12 is a heteroaryl group
  • a heteroaryl group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is preferred.
  • the hetero atom contained in the heteroaryl group include an oxygen atom, a sulfur atom, and a nitrogen atom.
  • ring constituting the heteroaryl group examples include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, and an imidazolidine.
  • At least one of Ar 11 and Ar 12 has a group represented by the following formula (2) as a substituent.
  • Ar ⁇ 13 > and Ar ⁇ 14 > represent the aryl group or heteroaryl group which may have a substituent.
  • Specific examples and preferred embodiments of Ar 13 and Ar 14 are the same as Ar 11 and Ar 12 described above.
  • Ar 13 and Ar 14 are preferably aryl groups which may have a substituent.
  • Ar 13 and / or Ar 14 may combine with Ar 11 or Ar 12 in the above formula (1) to form a ring.
  • the ring formed include a ring R described later.
  • the ring formed may have a substituent.
  • the substituent include a substituent W described later.
  • Ar 13 and / or Ar 14 are preferably bonded to Ar 11 and / or Ar 12 in formula (1) to form a ring.
  • L 1 is a single bond, an alkenylene group (preferably having 2 to 4 carbon atoms) which may have a substituent, a divalent aryl group which may have a substituent, or The divalent heteroaryl group which may have a substituent is represented. Examples of the substituent include a substituent W described later.
  • L 1 is a divalent aryl group, an aryl group having 6 to 30 carbon atoms is preferable, and an aryl group having 6 to 20 carbon atoms is more preferable.
  • the ring constituting the aryl group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a triphenylene ring, a naphthacene ring, and a biphenyl ring. Or a terphenyl ring (the three phenyl groups may be connected in any connection manner).
  • the aryl group may be bonded to Ar 11 or Ar 12 to form a ring.
  • L 1 is a divalent heteroaryl group
  • a heteroaryl group consisting of a 5-membered, 6-membered or 7-membered ring or a condensed ring thereof is preferred.
  • Specific examples of the hetero atom contained in the heteroaryl group are the same as those in the case where Ar 11 or Ar 12 described above is a heteroaryl group.
  • Specific examples of the ring constituting the heteroaryl group are the same as those in the case where Ar 11 or Ar 12 described above is a heteroaryl group.
  • the heteroaryl group may be bonded to Ar 11 or Ar 12 to form a ring.
  • L 1 may be a single bond, a divalent aryl group that may have a substituent, or a divalent heteroaryl group that may have a substituent, because the deposition stability is more excellent.
  • a single bond or a divalent aryl group which may have a substituent is more preferable, and a single bond is more preferable.
  • Ar 11 and Ar 12 may be bonded to each other via a divalent organic group to form a ring.
  • the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (for example, an alkylene group, preferably 1 to 8 carbon atoms), a substituted or unsubstituted divalent aromatic hydrocarbon group ( For example, an arylene group, preferably having 6 to 12 carbon atoms, —O—, —S—, —SO 2 —, —NR— (R: substituent W described later), —SiR 1 R 2 — (R 1 and R 2 : Substituent W), -CO-, -NH-, -COO-, -CONH-, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.) Etc.
  • a substituted or unsubstituted alkylene group for example, an alky
  • Ar 11 and Ar 12 are preferably not bonded to each other to form a ring for the reason that photoelectric conversion efficiency is excellent and heat resistance and vapor deposition stability are more excellent.
  • Z 1 represents a ring containing at least 3 carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring.
  • a ring what is normally used as an acidic nucleus with a merocyanine dye is preferable, and specific examples thereof include the following.
  • (A) 1,3-dicarbonyl nucleus for example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6 -Dione etc.
  • (B) pyrazolinone nucleus for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -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, etc.
  • (D) Oxindole nucleus For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
  • Examples of 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 diphenyl, 1,3-di (p-chlorophenyl), 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl such as 1-ethyl-3-phenyl And 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like.
  • 2-thio-2,4-thiazolidinedione nucleus for example, rhodanine and derivatives thereof.
  • Examples of the derivatives include 3-alkyl rhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl). ) 3-position heterocyclic substituted rhodanine such as rhodanine.
  • (J) 2,4-thiazolidinedione nucleus: for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
  • (M) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidine Zeon etc.
  • (N) Imidazolin-5-one nucleus For example, 2-propylmercapto-2-imidazolin-5-one and the like.
  • (O) 3,5-pyrazolidinedione nucleus for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc.
  • Benzothiophen-3-one nucleus for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-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, etc.
  • Z 1 may have a substituent.
  • substituents include a substituent W described later.
  • Z 1 is preferably a group represented by the following formula (Z1) from the viewpoint that the characteristics of the photoelectric conversion element such as response, sensitivity, and heat resistance are more excellent.
  • Z 2 represents a ring containing at least 3 carbon atoms, and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring.
  • * represents a bonding position with the carbon atom to which Ar 11 and Ar 12 in the above formula (1) are bonded.
  • a preferred embodiment of the compound (A) is, for example, a compound (a1) represented by the following formula (3).
  • R 11 to R 24 represent a hydrogen atom or a substituent.
  • substituents include a substituent W described later.
  • At least one of R 11 to R 24 is a group represented by the following formula (4).
  • Ar ⁇ 13 > and Ar ⁇ 14 > represent the aryl group or heteroaryl group which may have a substituent.
  • Specific examples and preferred embodiments of Ar 13 and Ar 14 is the same as Ar 13 and Ar 14 in the formula (2).
  • Ar 13 and / or Ar 14 may be bonded to at least one of R 11 to R 24 in the above formula (3) to form a ring.
  • the ring formed include a ring R described later.
  • the ring formed may have a substituent.
  • the substituent include a substituent W described later.
  • Ar 13 and / or Ar 14 are preferably bonded to at least one of R 11 to R 24 in the above formula (3) to form a ring.
  • * represents a bonding position
  • L 1 is a single bond, an alkenylene group which may have a substituent, a divalent aryl group which may have a substituent, or 2 which may have a substituent. Represents a valent heteroaryl group. Specific examples and preferred embodiments of L 1 are as described above. When L 1 is a single bond, the nitrogen atom in the formula (4) is directly bonded to at least one of R 11 to R 24 .
  • R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring. Specific examples and preferred embodiments of the divalent organic group are as described above. R 17 and R 18 are preferably not bonded to each other to form a ring for the reason of better heat resistance and vapor deposition stability.
  • a and b represent an integer greater than or equal to 0.
  • an integer of 0 to 2 preferably 0 to 1, and more preferably 0 is preferable because the heat resistance and the deposition stability are more excellent.
  • a and b represent the number of connected benzene rings.
  • Z 1 represents a ring containing at least 3 carbon atoms and represents a 5-membered ring, a 6-membered ring, or a condensed ring containing at least one of a 5-membered ring and a 6-membered ring. . Specific examples and preferred embodiments of Z 1 are as described above.
  • Z 1 is preferably a group represented by the following formula (Z1) from the viewpoint that the characteristics of the photoelectric conversion element such as response, sensitivity, and heat resistance are more excellent.
  • a preferred embodiment of the compound (a1) is, for example, a compound (a2) represented by the following formula (5).
  • R 11 to R 24 represent a hydrogen atom or a substituent.
  • substituents include a substituent W described later.
  • At least one of R 11 to R 24 is a group represented by the following formula (6).
  • R 17 and R 18 may be bonded to each other via a divalent organic group to form a ring. Specific examples and preferred embodiments of the divalent organic group are as described above. R 17 and R 18 are preferably not bonded to each other to form a ring for the reason of better heat resistance and vapor deposition stability.
  • R 51 to R 54 represent a hydrogen atom or a substituent.
  • substituents include a substituent W described later.
  • R 51 and R 52 , R 52 and R 53 , and R 53 and R 54 may be bonded to each other to form a ring.
  • examples of the ring formed include a ring R described later.
  • the ring formed may have a substituent.
  • substituent W described later examples of the substituent W described later.
  • Substituent W It describes about the substituent W in this specification.
  • substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, Heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl Oxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonyloxy
  • Ring R It describes about the ring R in this specification.
  • examples of the ring R include an aromatic hydrocarbon ring, an aromatic heterocycle, a non-aromatic hydrocarbon ring, a non-aromatic heterocycle, or a polycyclic fused ring formed by combining these.
  • Compound (A) can be produced by carrying out a partial modification according to a known method. Specific examples of the compound represented by the compound (A) are shown below, but the present invention is not limited thereto.
  • the ionization potential (hereinafter sometimes abbreviated as IP) of the compound (A) is preferably 6.0 ev or less, more preferably 5.8 eV or less, and particularly preferably 5.6 eV or less. If it is this range, when an electrode and another material exist, it is preferable in order to perform transfer of the electron with the material with small electrical resistance. IP can be obtained using AC-2 manufactured by Riken Keiki Co., Ltd.
  • the compound (A) preferably has an absorption maximum at 400 nm or more and less than 720 nm in the UV-visible absorption spectrum, and the peak wavelength (absorption maximum wavelength) of the absorption spectrum is 450 nm or more and 700 nm from the viewpoint of broadly absorbing light in the visible region.
  • the following is preferable, 480 nm to 700 nm is more preferable, and 510 nm to 680 nm is further preferable.
  • the absorption maximum wavelength of the compound (A) can be measured with a chloroform solution of the compound (A) using, for example, UV-2550 manufactured by Shimadzu Corporation.
  • Concentration of the chloroform solution is preferably from 5 ⁇ 10 -5 ⁇ 1 ⁇ 10 -7 mol / l, more preferably 3 ⁇ 10 -5 ⁇ 2 ⁇ 10 -6 mol / l, 2 ⁇ 10 -5 ⁇ 5 ⁇ 10 - 6 mol / l is particularly preferred.
  • the compound (A) preferably has an absorption maximum at 400 nm or more and less than 720 nm in the ultraviolet-visible absorption spectrum, and the molar extinction coefficient at the absorption maximum wavelength is 10,000 mol ⁇ 1 ⁇ l ⁇ cm ⁇ 1 or more.
  • a material having a large molar extinction coefficient is preferable.
  • 10000mol -1 ⁇ l ⁇ cm -1 or more molar extinction coefficient of the compound (A) more preferably 30000mol -1 ⁇ l ⁇ cm -1 or more, 50000mol -1 ⁇ l ⁇ cm -1 or more is particularly preferred .
  • the molar extinction coefficient of compound (A) is measured with a chloroform solution.
  • the difference between the melting point and the deposition temperature (melting point ⁇ deposition temperature) is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and still more preferably 60 ° C. or higher.
  • 240 degreeC or more is preferable, as for melting
  • the vapor deposition temperature of the compound is such that the crucible is heated at a vacuum of 4 ⁇ 10 ⁇ 4 Pa or less and the vapor deposition rate reaches 0.4 angstrom / s (0.4 ⁇ 10 ⁇ 10 m / s).
  • the glass transition point (Tg) of the compound (A) is preferably 95 ° C. or higher, more preferably 110 ° C. or higher, further preferably 135 ° C. or higher, particularly preferably 150 ° C. or higher, and most preferably 160 ° C. or higher.
  • the molecular weight of the compound (A) is preferably 300 to 1500, more preferably 400 to 1000, and particularly preferably 500 to 900.
  • the molecular weight of the compound is 1500 or less, the deposition temperature does not increase and the compound is hardly decomposed. If the molecular weight of the compound is 300 or more, the glass transition point of the deposited film is not lowered, and the heat resistance of the device is hardly lowered.
  • Compound (A) is particularly useful as a material for a photoelectric conversion film used for an image sensor, a photosensor, or a photovoltaic cell.
  • the compound (A) functions as an organic p-type semiconductor (compound) in the photoelectric conversion film.
  • it can also be used as a coloring material, liquid crystal material, organic semiconductor material, organic light emitting device material, charge transport material, pharmaceutical material, fluorescent diagnostic material, and the like.
  • the photoelectric conversion element of this invention will not be restrict
  • a photoelectric conversion element provided with the conductive film, the photoelectric conversion film containing the photoelectric conversion material of this invention, and a transparent conductive film in this order is mentioned.
  • FIG. 1 the cross-sectional schematic diagram of one Embodiment of the photoelectric conversion element of this invention is shown.
  • a photoelectric conversion element 10a shown in FIG. 1A includes a conductive film (hereinafter also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking layer 16A formed on the lower electrode 11, and an electron blocking layer 16A.
  • the photoelectric conversion film 12 formed above and a transparent conductive film (hereinafter also referred to as an upper electrode) 15 functioning as an upper electrode are stacked in this order.
  • FIG. 1B shows a configuration example of another photoelectric conversion element.
  • FIGS. 1A and 1B has a configuration in which an electron blocking layer 16A, a photoelectric conversion film 12, a hole blocking layer 16B, and an upper electrode 15 are stacked in this order on a lower electrode 11. Have. Note that the stacking order of the electron blocking layer 16A, the photoelectric conversion film 12, and the hole blocking layer 16B in FIGS. 1A and 1B may be reversed depending on the application and characteristics.
  • the photoelectric conversion element 10 a (10 b) it is preferable that light is incident on the photoelectric conversion film 12 through the transparent conductive film 15. Moreover, when using the photoelectric conversion element 10a (10b), an electric field can be applied. In this case, it is preferable that the conductive film 11 and the transparent conductive film 15 form a pair of electrodes, and an electric field of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 7 V / cm is applied between the pair of electrodes, It is more preferable to apply an electric field of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 7 V / cm.
  • an electric field of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 6 V / cm is preferably applied, and an electric field of 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 5 V / cm is preferably applied. More preferred.
  • the voltage application method, in FIG. 1 (a) and (b) it is preferable to apply so that the electron blocking layer 16A side may become a cathode and the photoelectric converting film 12 side may become an anode.
  • the photoelectric conversion element 10a (10b) is used as an optical sensor, or when it is incorporated into an image sensor, voltage can be applied by the same method.
  • each layer (a photoelectric conversion film, a lower electrode, an upper electrode, an electron blocking layer, a hole blocking layer, etc.) which comprises the photoelectric conversion element 10a (10b) is explained in full detail.
  • the photoelectric conversion film will be described in detail.
  • the photoelectric conversion film is a film containing the compound (A) as a photoelectric conversion material.
  • the compound (A) is as described above.
  • the photoelectric conversion film may further contain an organic p-type semiconductor (compound) or an organic n-type semiconductor (compound) photoelectric conversion material.
  • the organic p-type semiconductor (compound) is a donor-type organic semiconductor (compound), which is mainly represented by a hole-transporting organic compound and refers to an organic compound having a property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound.
  • a triarylamine compound a benzidine compound, a pyrazoline compound, a styrylamine compound, a hydrazone compound, a triphenylmethane compound, a carbazole compound, or the like can be used.
  • Organic n-type semiconductors are acceptor organic semiconductors, which are typically represented by electron-transporting organic compounds and refer to organic compounds that easily accept electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, any organic compound may be used as the acceptor organic semiconductor as long as it is an organic compound having an electron accepting property.
  • fullerenes selected from the group consisting of fullerenes and derivatives thereof, condensed aromatic carbocyclic compounds (naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives), nitrogen atoms, oxygen Heterocyclic compounds containing atoms and sulfur atoms (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole , Oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole
  • fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferable.
  • the fullerene, fullerene C 60, fullerene C 70, fullerene C 76, fullerene C 78, fullerene C 80, fullerene C 82, fullerene C 84, fullerene C 90, fullerene C 96, fullerene C 240, fullerene C 540, mixed Fullerene is represented, and its derivative (fullerene derivative) represents a compound having a substituent added thereto.
  • the substituent an alkyl group, an aryl group, or a heterocyclic group is preferable.
  • the fullerene derivative compounds described in JP-A-2007-123707 are preferred.
  • the photoelectric conversion film preferably has a bulk heterostructure formed by mixing the compound (A) and fullerenes.
  • a bulk heterostructure is a film in which an organic p-type compound (for example, compound (A)) and an organic n-type compound are mixed and dispersed in a photoelectric conversion film, and can be formed by either a wet method or a dry method. Those formed by vapor deposition are preferred.
  • the heterojunction structure it is possible to make up for the disadvantage that the carrier diffusion length of the photoelectric conversion film is short, and to improve the photoelectric conversion efficiency of the photoelectric conversion film.
  • the bulk heterojunction structure is described in detail in JP-A-2005-303266, [0013] to [0014].
  • the content of fullerenes relative to the total content of the compound (A) and fullerenes is preferably 50% by volume or more, and more preferably 60% by volume or more.
  • the upper limit is not particularly limited, but is preferably 95% by volume or less, and more preferably 90% by volume or less.
  • the photoelectric conversion film (in which an organic n-type compound may be mixed) containing the compound (A) of the present invention is a non-light-emitting film and has characteristics different from those of an organic electroluminescent element (OLED).
  • the non-light-emitting film is a film having an emission quantum efficiency of 1% or less, more preferably 0.5% or less, and still more preferably 0.1% or less.
  • the photoelectric conversion film 12 can be formed by a dry film formation method or a wet film formation method.
  • the dry film forming method include a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, and an MBE method, or a CVD method such as plasma polymerization.
  • a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, and an MBE method, or a CVD method such as plasma polymerization.
  • a wet film forming method a casting method, a spin coating method, a dipping method, an LB method, or the like is used.
  • a dry film forming method is preferred, and a vacuum deposition method is more preferred.
  • the production conditions such as the degree of vacuum and the deposition temperature can be set according to conventional methods.
  • the thickness of the photoelectric conversion film 12 is preferably 10 nm to 1000 nm, more preferably 50 nm to 800 nm, and particularly preferably 100 nm to 500 nm. By setting it to 10 nm or more, a suitable dark current suppressing effect is obtained, and by setting it to 1000 nm or less, suitable photoelectric conversion efficiency is obtained.
  • the electrodes are made of a conductive material.
  • a conductive material a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Since light is incident from the upper electrode 15, the upper electrode 15 needs to be sufficiently transparent to the light to be detected.
  • conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metal thin films such as gold, silver, chromium, nickel, etc., and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organics such as polyaniline, polythiophene, and polypyrrole Examples thereof include conductive materials and laminates of these with ITO. Among these, a transparent conductive metal oxide is preferable from the viewpoint of high conductivity, transparency, and the like.
  • a transparent conductive film such as TCO When a transparent conductive film such as TCO is used as the upper electrode 15, a DC short circuit or an increase in leakage current may occur.
  • a dense film such as TCO
  • conduction with the lower electrode 11 on the opposite side is increased. Therefore, in the case of an electrode having a relatively poor film quality such as aluminum, an increase in leakage current is unlikely to occur.
  • the thickness of the upper electrode 15 is desirably 1/5 or less, preferably 1/10 or less of the thickness of the photoelectric conversion film 12.
  • the sheet resistance is preferably 100 to 10,000 ⁇ / ⁇ .
  • the degree of freedom in the range of film thickness that can be made thin is great.
  • the thickness of the upper electrode (transparent conductive film) 15 decreases, the amount of light absorbed decreases, and the light transmittance generally increases.
  • An increase in light transmittance is very preferable because it increases the light absorption in the photoelectric conversion film 12 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. It is desirable.
  • the lower electrode 11 may have transparency, or conversely, may use a material that does not have transparency and reflects light.
  • conductive metal oxides such as tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), Metals such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides and nitrides of these metals (for example, titanium nitride (TiN)), and these metals and conductivity Examples include mixtures or laminates with metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO or titanium nitride. .
  • the method for forming the electrode is not particularly limited, and can be appropriately selected in consideration of suitability with the electrode material. Specifically, it can be formed by a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method.
  • a wet method such as a printing method or a coating method
  • a physical method such as a vacuum deposition method, a sputtering method or an ion plating method
  • a chemical method such as CVD or plasma CVD method.
  • the electrode material is ITO
  • it can be formed by a method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), or a dispersion of indium tin oxide.
  • UV-ozone treatment, plasma treatment, or the like can be performed on a film formed using ITO.
  • the electrode material is TiN
  • various methods including a reactive sputtering method can be used, and further, UV-ozone treatment, plasma treatment, and the like can be performed.
  • the photoelectric conversion element of the present invention may have a charge blocking layer. By having this layer, the characteristics (photoelectric conversion efficiency, response speed, etc.) of the obtained photoelectric conversion element are more excellent.
  • Examples of the charge blocking layer include an electron blocking layer and a hole blocking layer. Below, each layer is explained in full detail.
  • An electron donating organic material can be used for the electron blocking layer.
  • the molecular material polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof can be used.
  • the electron affinity of the n-type semiconductor used for the photoelectric conversion film and the electron block adjacent to the photoelectric conversion film can be used.
  • the difference from the ionization potential of the material used for the rocking layer is preferably 1 eV or more
  • fullerene (C60) is used as the n-type semiconductor
  • the electron affinity of fullerene (C60) is 4.2 eV, so that adjacent electron blocking is performed.
  • the material used for the layer preferably has an ionization potential of 5.2 eV or more, specifically, [0083] to [0089] of JP-A-2008-72090, and [0049] to [0049] of JP-A-2011-176259. [0063]
  • the compounds described in JP2011-228614A [0121] to [0156] and JP2011-228615A [0108] to [0156] are preferred.
  • the electron blocking layer may be composed of a plurality of layers.
  • An inorganic material can also be used as the electron blocking layer.
  • Materials that can be used as an electron blocking layer include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, indium copper oxide, and oxide. Examples include indium silver and iridium oxide.
  • the layer can be a layer made of an inorganic material, or in the case of a plurality of layers, one or more layers can be a layer made of an inorganic material. .
  • An electron-accepting organic material can be used for the hole blocking layer.
  • electron-accepting materials include 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7) and other oxadiazole derivatives, anthraquinodimethane derivatives, and diphenylquinone derivatives.
  • a porphyrin compound or a styryl compound such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran) or a 4H pyran compound can be used.
  • DCM dimethylaminostyryl
  • a 4H pyran compound can be used.
  • compounds described in [0073] to [0078] of JP-A-2008-72090 are preferable.
  • the method for producing the charge blocking layer is not particularly limited, and can be formed by a dry film forming method or a wet film forming method.
  • a dry film forming method a vapor deposition method, a sputtering method, or the like can be used.
  • the vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), but physical vapor deposition such as vacuum vapor deposition is preferred.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the wet film forming method 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, a gravure coating method, etc. can be used. From the viewpoint of high-precision patterning, the inkjet method is preferable.
  • the thickness of the charge blocking layer is preferably 10 to 200 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 50 nm. This is because if the thickness is too thin, the dark current suppressing effect is lowered, and if it is too thick, the photoelectric conversion efficiency is lowered.
  • the photoelectric conversion element of the present invention may further include a substrate.
  • the type of the substrate used is not particularly limited, and a semiconductor substrate, a glass substrate, or a plastic substrate can be used.
  • the position of the substrate is not particularly limited, but usually a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.
  • the photoelectric conversion element of the present invention may further include a sealing layer.
  • the performance of photoelectric conversion materials may deteriorate significantly due to the presence of deterioration factors such as water molecules. Ceramics such as dense metal oxides, metal nitrides, and metal nitride oxides that do not penetrate water molecules and diamond-like materials Covering and sealing the entire photoelectric conversion film with a sealing layer such as carbon (DLC) can prevent the deterioration.
  • the material for the sealing layer may be selected and manufactured according to paragraphs [0210] to [0215] of JP2011-082508A.
  • the photoelectric conversion element of the present invention is preferably used as an optical sensor.
  • the photoelectric conversion element used alone may be used, or a line sensor in which the photoelectric conversion elements are arranged linearly or a two-dimensional sensor arranged on a plane is preferable.
  • the photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a drive unit like a scanner in a line sensor, and optically converts optical image information like an imaging module in a two-dimensional sensor.
  • the system functions as an image sensor by forming an image on a sensor and converting it into an electrical signal.
  • the photovoltaic cell is a power generation device, the efficiency of converting light energy into electrical energy is an important performance, but dark current, which is a current in a dark place, is not a functional problem. Further, a subsequent heating step such as installation of a color filter is not necessary. Since it is important for optical sensors to convert light and dark signals to electrical signals with high accuracy, the efficiency of converting light intensity into current is also important, but noise is generated when signals are output in the dark. Low dark current is required. In addition, resistance to subsequent processes is also important.
  • An image sensor is an element that converts optical information of an image into an electric signal.
  • a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and an optical signal is converted into an electric signal in each photoelectric conversion element (pixel). That can be output to the outside of the imaging device for each pixel sequentially. Therefore, one pixel is composed of one photoelectric conversion element and one or more transistors.
  • FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention.
  • This imaging device is used by being mounted on an imaging device such as a digital camera or a digital video camera, an imaging module such as an electronic endoscope or a mobile phone, or the like.
  • This imaging element has a plurality of photoelectric conversion elements having the configuration shown in FIG. 1 and a circuit board on which a readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion element is formed.
  • a plurality of photoelectric conversion elements are arranged one-dimensionally or two-dimensionally on the same surface above the circuit board.
  • connection electrode 103 includes a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and a counter electrode.
  • the pixel electrode 104 has the same function as the electrode 11 of the photoelectric conversion element 10a shown in FIG.
  • the counter electrode 108 has the same function as the electrode 15 of the photoelectric conversion element 10a shown in FIG.
  • the photoelectric conversion film 107 has the same configuration as the layer provided between the electrode 11 and the electrode 15 of the photoelectric conversion element 10a illustrated in FIG.
  • the substrate 101 is a glass substrate or a semiconductor substrate such as Si.
  • An insulating layer 102 is formed on the substrate 101.
  • a plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.
  • the photoelectric conversion film 107 is a layer common to all the photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.
  • the counter electrode 108 is one electrode provided on the photoelectric conversion film 107 and common to all the photoelectric conversion elements.
  • the counter electrode 108 is formed up to the connection electrode 103 disposed outside the photoelectric conversion film 107, and is electrically connected to the connection electrode 103.
  • connection part 106 is embedded in the insulating layer 102 and is a plug or the like for electrically connecting the connection electrode 103 and the counter electrode voltage supply part 115.
  • the counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection unit 106 and the connection electrode 103.
  • the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.
  • the readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104.
  • the readout circuit 116 is configured by, for example, a CCD, a CMOS circuit, a TFT circuit, or the like, and is shielded by a light shielding layer (not shown) disposed in the insulating layer 102.
  • the readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection unit 105.
  • the buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108.
  • the sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109.
  • the color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110.
  • the partition wall 112 is provided between the color filters 111 and is for improving the light transmission efficiency of the color filter 111.
  • the light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 are provided on the sealing layer 110, and prevents light from entering the photoelectric conversion film 107 formed outside the effective pixel region.
  • the protective layer 114 is formed on the color filter 111, the partition 112, and the light shielding layer 113, and protects the entire image sensor 100.
  • the imaging device 100 when light is incident, the light is incident on the photoelectric conversion film 107, and charges are generated here. Holes in the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image sensor 100 by the readout circuit 116.
  • the manufacturing method of the image sensor 100 is as follows. On the circuit board on which the common electrode voltage supply unit 115 and the readout circuit 116 are formed, the connection units 105 and 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed. The plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in a square lattice pattern, for example.
  • a photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating deposition method.
  • the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum by, for example, sputtering.
  • the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum heating deposition method.
  • the protective layer 114 is formed, and the imaging element 100 is completed.
  • Example 1 The following compound (1) (photoelectric conversion material) was synthesized according to the synthesis scheme shown below. The compound was identified by MS measurement and 1 H-NMR measurement. FIG. 3 shows a 1 H-NMR spectrum of the compound (1).
  • the photoelectric conversion element includes the lower electrode 11, the electron blocking layer 16 ⁇ / b> A, the photoelectric conversion film 12, and the upper electrode 15.
  • an amorphous ITO film is formed on a glass substrate by sputtering to form the lower electrode 11 (thickness: 30 nm), and the following compound (EB-1) is vacuum-heated on the lower electrode 11
  • An electron blocking layer 16 ⁇ / b> A was formed by a deposition method.
  • the obtained photoelectric conversion material and fullerene (C 60 ) are vacuum-heat-deposited on the electron blocking layer 16A so as to be 114 nm and 286 nm, respectively, in single layer conversion.
  • the film was co-evaporated to form a photoelectric conversion film 12.
  • vapor deposition was performed by heating the crucible containing the obtained photoelectric conversion material (compound of the following (1)) under vacuum (degree of vacuum of 4 ⁇ 10 ⁇ 4 Pa or less).
  • the vapor deposition rate of the obtained photoelectric converting material (compound of following (1)) might be set to 0.4 (angstrom) / sec (0.4 * 10 ⁇ -10 > m / sec).
  • an amorphous ITO film was formed on the photoelectric conversion film 12 by sputtering to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
  • An SiO film was formed as a sealing layer on the upper electrode 15 by heat evaporation, and then an aluminum oxide (Al 2 O 3 ) layer was formed thereon by ALCVD to produce a photoelectric conversion element (1st element).
  • the crucible used when the 1st element was produced (the one containing the remaining photoelectric conversion material) was used as it was, and the deposition rate was 3.0 ⁇ / second (3.0 ⁇ 10 ⁇ 10 m / second). Except for the above, a photoelectric conversion element (2nd) was produced according to the same procedure as the 1st element.
  • Examples 2 and 7 in which Ar 13 and / or Ar 14 in the above formula (2) are bonded to Ar 11 and / or Ar 12 in the above formula (1) to form a ring are as follows: Furthermore, it showed excellent heat resistance and deposition stability. From the comparison between Examples 1 and 5 and the comparison between Examples 6 and 8, Examples 1 and 6 in which a and b in the above formula (3) are 0 are more excellent in heat resistance and vapor deposition. Showed stability.
  • Comparative Examples 1 to 4 which are compounds different from the compound (A), were insufficient in heat resistance and vapor deposition stability.
  • An image sensor similar to that shown in FIG. 2 was produced. That is, after forming amorphous TiN 30 nm on a CMOS substrate by sputtering, patterning is performed so that one pixel exists on each photodiode (PD) on the CMOS substrate by photolithography to form a lower electrode, After the formation of the electron blocking material, it was produced in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 3. The evaluation was performed in the same manner, and the same results as in Table 1 were obtained.

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Abstract

La présente invention aborde le problème de la fourniture d'un matériau de conversion photoélectrique qui présente une excellente résistance à la chaleur et une excellente stabilité de dépôt en phase vapeur, d'un élément de conversion photoélectrique qui utilise le matériau de conversion photoélectrique, d'un procédé d'utilisation de l'élément de conversion photoélectrique, ainsi que d'un capteur optique et d'un élément de capture d'image qui comprennent l'élément de conversion photoélectrique. Ce matériau de conversion photoélectrique est un composé (A) représenté par la formule (1).
PCT/JP2014/058345 2013-03-28 2014-03-25 Matériau de conversion photoélectrique, élément de conversion photoélectrique et procédé d'utilisation de ce dernier, capteur optique et élément de capture d'image WO2014157238A1 (fr)

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