WO2014050764A1 - 光電変換素子、撮像素子、光センサ - Google Patents

光電変換素子、撮像素子、光センサ Download PDF

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WO2014050764A1
WO2014050764A1 PCT/JP2013/075564 JP2013075564W WO2014050764A1 WO 2014050764 A1 WO2014050764 A1 WO 2014050764A1 JP 2013075564 W JP2013075564 W JP 2013075564W WO 2014050764 A1 WO2014050764 A1 WO 2014050764A1
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group
photoelectric conversion
film
ring
compound
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PCT/JP2013/075564
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French (fr)
Japanese (ja)
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伊勢　俊大
知昭 吉岡
陽介 山本
大悟 澤木
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富士フイルム株式会社
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Priority to KR1020157006933A priority Critical patent/KR101635332B1/ko
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B3/00—Dyes with an anthracene nucleus condensed with one or more carbocyclic rings
    • C09B3/78—Other dyes in which the anthracene nucleus is condensed with one or more carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/004—Diketopyrrolopyrrole dyes
    • 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
    • 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
    • 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
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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

Definitions

  • the present invention relates to a photoelectric conversion element, an imaging element, and an optical sensor.
  • a conventional photosensor is an element in which a photodiode (PD) is formed in a semiconductor substrate such as silicon (Si), and as a solid-state imaging element, PDs are two-dimensionally arrayed and signal charges generated in each PD
  • PDs are two-dimensionally arrayed and signal charges generated in each PD
  • Si silicon
  • a structure in which a color filter for transmitting light of a specific wavelength is disposed on the light incident surface side of the planar 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 of the two-dimensionally arrayed PDs widely used in digital cameras etc.
  • Single-plate solid-state imaging devices are well known. In this single-plate solid-state imaging device, the light not transmitted through the color filter is not used and the light utilization efficiency is poor.
  • the number of pixels has been increased, the pixel size has become smaller, and the reduction of the aperture ratio and the reduction of the light collection efficiency have become problems.
  • Patent Document 1 a photoelectric conversion film including a compound (3) or the like represented by the following formula is disclosed in the Example column, and it is described that the photoelectric conversion efficiency is high. Further, Patent Documents 2 and 3 also disclose a photoelectric conversion element containing a diketopyrrolopyrrole compound.
  • the present inventors prepared a photoelectric conversion film using a compound (for example, the above-mentioned compound 3) specifically disclosed in Patent Documents 1 to 3, and it was found that the heat resistance and the response speed were not necessarily obtained. It has been found that it has not reached the level required nowadays and further improvement is necessary.
  • a compound for example, the above-mentioned compound 3 specifically disclosed in Patent Documents 1 to 3
  • An object of this invention is to provide the photoelectric conversion element provided with the photoelectric conversion film which shows the outstanding heat resistance and responsiveness in view of the said situation.
  • Another object of the present invention is to provide an imaging device and a photosensor including a photoelectric conversion device.
  • a photoelectric conversion element obtained by laminating a conductive film, a photoelectric conversion film containing a photoelectric conversion material, and a transparent conductive film in this order The photoelectric conversion material is selected from the group consisting of a compound represented by General Formula (1) described later, a compound represented by General Formula (2) described later, and a compound represented by General Formula (3) described later Photoelectric conversion element containing at least one compound X.
  • the photoelectric conversion element provided with the photoelectric conversion film which shows the outstanding heat resistance and responsiveness can be provided. Further, according to the present invention, it is possible to provide an imaging device and a photosensor including the photoelectric conversion device.
  • FIG. 1A and FIG. 1B are schematic cross-sectional views showing one structural example of the photoelectric conversion element. It is a cross-sectional schematic diagram for one pixel of an image pick-up element.
  • a diketopyrrolopyrrole compound contained in the photoelectric conversion film or a compound obtained by condensing an aromatic ring between two pyrrole rings of diketopyrrolopyrrole is used to provide an aromatic at a predetermined position. It has been found that by introducing a group ring containing amine group, the desired effect can be obtained.
  • the photoelectric conversion element 10b shown in FIG. 1B 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 stacked in this order on the lower electrode 11. Have.
  • the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1A and 1B may be reversed depending on the application and characteristics. For example, the positions of the electron blocking film 16A and the photoelectric conversion film 12 may be reversed.
  • the photoelectric conversion element 10 a (10 b) light is preferably incident on the photoelectric conversion film 12 through the transparent conductive film 15. Moreover, when using photoelectric conversion element 10a (10b), an electric field can be applied.
  • 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. From the viewpoint of performance and power consumption, an electric field of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 6 V / cm is preferable, and an electric field of 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 5 V / cm is particularly preferable.
  • the voltage application method in FIGS.
  • the electron blocking film 16A side is a cathode and the photoelectric conversion film 12 side is an anode.
  • the photoelectric conversion element 10a (10b) is used as an optical sensor, and also when it is incorporated in an imaging element, voltage application can be performed by the same method.
  • the photoelectric conversion film 12 is a compound represented by General Formula (1) described later as a photoelectric conversion material, a compound represented by General Formula (2) described later, and a compound represented by General Formula (3) described later A membrane comprising at least one compound X selected from the group consisting of By using the compound X, a photoelectric conversion film exhibiting excellent heat resistance and fast response can be obtained.
  • the compounds represented by the general formulas (1) to (3) used in the photoelectric conversion film 12 will be described in detail.
  • aryl group examples include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthrenyl group, methylphenyl group, dimethylphenyl group, biphenyl group, fluorenyl group and the like, and phenyl group, naphthyl group or anthryl group is exemplified. preferable.
  • the number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 3 to 30, and more preferably 3 to 18 in that the characteristics (heat resistance and response) of the photoelectric conversion film are more excellent. Is more preferred.
  • the heteroaryl group may have a substituent W described later.
  • Heteroaryl groups include hetero atoms other than carbon atom and hydrogen atom, and as hetero atoms, for example, nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, phosphorus atom, silicon atom, or boron atom
  • a nitrogen atom, a sulfur atom or an oxygen atom is mentioned.
  • the number of heteroatoms contained in the heteroaryl group is not particularly limited, and is usually about 1 to 10, preferably 1 to 4.
  • the number of ring members of the heteroaryl group is not particularly limited, but is preferably a 3- to 8-membered ring, more preferably a 5- to 7-membered ring, and particularly preferably a 5- to 6-membered ring.
  • heteroaryl group examples include pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthrizinyl group, pteridinyl group, pyrazinyl group, quinoxalinyl group, pyrimidinyl group, quinazolyl group, pyridazinyl group, cinnolinyl group, phthalazinyl group, and the like.
  • the substituent W in the present specification is described.
  • 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 and a heterocyclic ring Group (may be referred to as hetero ring group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxy carbonyloxy group , Aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamin
  • R 11 , R 12 , R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group.
  • at least one of R 11 and R 12 and at least one of R 13 and R 14 represent an aryl group or a heteroaryl group.
  • R 11, R 12, R 13 and R 14 are aryl groups.
  • the definitions and preferred embodiments of the alkyl group, aryl group and heteroaryl group represented by R 11 , R 12 , R 13 and R 14 are the same as the alkyl group, aryl group and heteroaryl group represented by R 1 and R 2 above. Are the same as the definition and preferred embodiment of
  • Ar 1 and Ar 2 each independently represent an arylene group or a heteroarylene group.
  • Ar 1 and Ar 2 are preferably arylene groups in that the characteristics (heat resistance and responsiveness) of the photoelectric conversion film are more excellent.
  • the number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 30, and more preferably 6 to 20 in that the characteristics (heat resistance and response) of the photoelectric conversion film are more excellent.
  • the number of carbon atoms in the heteroarylene group is not particularly limited, but is preferably 1 to 20 and more preferably 2 to 12 in that the characteristics (heat resistance and response) of the photoelectric conversion film are more excellent.
  • the heteroarylene group include pyridylene group, quinolylene group, isoquinolylene group, acridine diyl group, phenanthridine diyl group, pyrazine diyl group, quinoxaline diyl group, pyrimidine diyl group, triazine diyl group, imidazole diyl group, pyrazole diyl group, Examples include oxadiazole diyl group, triazole diyl group, furylene group, thienylene group, pyrrol diyl group, indole diyl group, carbazole diyl group and the like.
  • X 1 and X 2 are each independently, O (oxygen atom), S (sulfur atom), or an NR A. Among them, O (oxygen atom) or S (sulfur atom) is preferable, and O (oxygen atom) is more preferable, in that the characteristics (heat resistance and responsiveness) of the photoelectric conversion film are more excellent.
  • R A represents an alkyl group, an aryl group or a heteroaryl group. Especially, an alkyl group is preferable at the point which the characteristic (heat resistance and responsiveness) of a photoelectric conversion film is more excellent.
  • the definitions and the preferred embodiments of the alkyl group, the aryl group and the heteroaryl group represented by R A are the same as the definitions and the preferred embodiment of the alkyl group, the aryl group and the heteroaryl group represented by R 1 and R 2 above. .
  • Q represents a group represented by formula (A), a group represented by formula (B), a group represented by formula (C), a group represented by formula (D), and It is any one group selected from the group consisting of a group represented by formula (E).
  • each of R Q1 to R Q22 independently represents a hydrogen atom or a substituent.
  • the substituent include the above-mentioned substituent W, and examples include an alkyl group, an alkoxy group, a halogen atom and the like. Among them, it is preferable that R Q1 to R Q22 be a hydrogen atom in that the characteristics (heat resistance or response) of the photoelectric conversion element are more excellent.
  • the carbon atoms represented by * 1 to * 4 in the general formulas (A) to (E) are represented by * 1 to * 4 in the general formulas (1) to (3), respectively. Corresponds to a carbon atom. More specifically, examples of structural formulas when groups represented by general formulas (A) to (E) below are introduced into Q in general formulas (1) to (3) Indicates
  • the heat resistance of the compounds represented by the general formulas (1) to (3) is improved, and the photoelectric conversion element can be produced at a high deposition rate under high temperature conditions. And the responsiveness is further improved.
  • the structure of the linking group is not particularly limited, and examples thereof include oxygen atom, sulfur atom, alkylene group, silylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, arylene group, divalent heterocyclic group, imino group, and the like. Or the group which combined these is mentioned, These may have a substituent further.
  • the structure of the ring formed is not particularly limited, and examples thereof include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, Oxazole ring, Thiazole ring, Pyridine ring, Pyrazine ring, Pyrimidine ring, Pyridazine ring, Indolizine ring, Indole ring, Indole ring, Benzofuran ring, Benzothiophene ring, Isobenzofuran ring, Quinolizine ring, Quinoline ring, Phthal
  • At least one of Ar 1 and R 11 , Ar 1 and R 12 , and R 11 and R 12 combine with each other to form a ring, and Ar 2 and R 13 , Ar 2 and R 14 , and R Preferably, at least one of 13 and R 14 is bonded to each other to form a ring.
  • the heat resistance and response of the photoelectric conversion film are further improved.
  • n 0 or 1; Among them, n is preferably 0 in terms of more excellent characteristics (heat resistance or response) of the photoelectric conversion element.
  • n 1
  • the compounds represented by the above general formulas (1A) to (3E) are exemplified.
  • the definition of each group in the general formulas (4) to (6) is as described above.
  • the compound represented by General formula (4) is especially preferable at the point which the effect of this invention is more excellent.
  • the compound represented by the general formula (4) is a so-called diketopyrrolopyrrole compound.
  • the compounds represented by the general formulas (1) to (3) are exemplified below.
  • the compounds represented by the general formula (1) to the general formula (3) have an absorption maximum at 400 nm or more and less than 720 nm in the UV-visible absorption spectrum, and the molar absorption coefficient of the absorption maximum wavelength is 10000 mol ⁇ 1 ⁇ l ⁇ cm It is preferably -1 or more.
  • a material having a large molar absorption coefficient is preferable.
  • the compounds represented by the general formulas (1) to (3) are more difficult to be decomposed during deposition as the difference between the melting point and the deposition temperature (melting point-deposition temperature) increases, and the deposition rate increases with an increase in temperature. can do.
  • the difference between the melting point and the vapor deposition temperature (melting point-vapor deposition temperature) is preferably 40 ° C. or more, more preferably 50 ° C. or more, still more preferably 60 ° C. or more, and particularly preferably 80 ° C. or more.
  • the molecular weight of the compound represented by the general formula (1) to the general formula (3) is preferably 300 to 1,500, more preferably 500 to 1000, and particularly preferably 500 to 900. If the molecular weight of the compound is 1,500 or less, the deposition temperature does not increase, and decomposition of the compound does not easily occur. If the molecular weight of the compound is 300 or more, the glass transition point of the deposited film does not decrease, and the heat resistance of the device does not easily decrease.
  • glass transition point (Tg) of the compound represented by General formula (1)-General formula (3) 110 degreeC or more is more preferable, 135 degreeC or more is more preferable, and 150 degreeC or more is especially preferable
  • Tg glass transition point
  • 160 ° C. or more is the most preferable. It is preferable that the glass transition point becomes high because the heat resistance of the element is improved.
  • the compounds represented by the general formula (1) to the general formula (3) are particularly useful as a material of a photoelectric conversion film used for an imaging device, an optical sensor, or a photovoltaic cell.
  • the compound represented by General formula (1) functions as an organic p-type compound in a photoelectric conversion film.
  • it can also be used as a coloring material, a liquid-crystal material, an organic-semiconductor material, an organic light emitting element material, a charge transport material, a pharmaceutical material, a fluorescence diagnostic agent material etc. as another use.
  • the photoelectric conversion film may further contain a photoelectric conversion material of an organic p-type compound or an organic n-type compound.
  • the organic p-type semiconductor (compound) is a donor type organic semiconductor (compound), mainly represented by a hole transporting organic compound, and refers to an organic compound having a property of easily giving an electron. More specifically, it refers to an organic compound having a smaller ionization potential when used in contact with two organic materials. Therefore, as the donor organic compound, any organic compound having an electron donating property can be used. For example, triarylamine compounds, benzidine compounds, pyrazoline compounds, styrylamine compounds, hydrazone compounds, triphenylmethane compounds, carbazole compounds and the like can be used.
  • the organic n-type semiconductor is an acceptor-type organic semiconductor, mainly represented by an electron-transporting organic compound, and refers to an organic compound having a property of easily accepting an electron. More specifically, when the two organic compounds are brought into contact with each other and used, the organic compound having higher electron affinity is used. Therefore, as the acceptor-type organic semiconductor, any organic compound can be used as long as it is an electron-accepting organic compound.
  • the organic n-type compound is preferably a fullerene selected from the group consisting of a fullerene and a fullerene derivative.
  • fullerenes fullerenes, 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 240 , fullerene C 540 , mixed Represents a fullerene, and a fullerene derivative represents a compound to which a substituent is added.
  • a substituent an alkyl group, an aryl group or a heterocyclic group is preferable.
  • the fullerene derivative compounds described in JP-A-2007-123707 are preferable.
  • the photoelectric conversion film preferably has a bulk hetero structure formed by mixing the compound X and a fullerene.
  • the bulk hetero structure is a layer in which a p-type organic semiconductor (compound X) and an n-type organic semiconductor are mixed and dispersed in the photoelectric conversion film, and can be formed by either a wet method or a dry method. Preferred.
  • a p-type organic semiconductor compound X
  • an n-type organic semiconductor are mixed and dispersed in the photoelectric conversion film, and can be formed by either a wet method or a dry method. Preferred.
  • the bulk heterojunction structure is described in detail in, for example, [0013] to [0014] of JP-A-2005-303266.
  • the molar ratio of the organic n-type compound to the compound X (organic n-type compound / the compound X) in the photoelectric conversion film is preferably 1.0 or more, more preferably 1 or more and 10 or less, and 2 or more More preferably, it is 8 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 formation method include physical vapor deposition methods such as vacuum deposition, sputtering, ion plating, and MBE, and CVD methods such as plasma polymerization.
  • a wet film formation method a cast method, a spin coat method, a dipping method, an LB method or the like is used. It is preferably a dry film formation method, and more preferably a vacuum deposition method.
  • the manufacturing conditions such as the degree of vacuum and the evaporation temperature can be set according to a conventional method.
  • the thickness of the photoelectric conversion film 12 is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 800 nm or less, and particularly preferably 100 nm or more and 500 nm or less.
  • a suitable dark current suppression effect can be obtained, and by setting the thickness to 1000 nm or less, preferable photoelectric conversion efficiency can be obtained.
  • the electrodes are made of 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 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), zinc indium oxide (IZO), etc.
  • 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) is mentioned), and these metals and conductive properties 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 .
  • TiN titanium nitride
  • the method of forming the electrode is not particularly limited, and can be appropriately selected according to the electrode material. Specifically, it can be formed by a printing method, a wet method such as a coating method, a physical method such as a vacuum evaporation method, a sputtering method, an ion plating method, or a chemical method such as CVD or plasma CVD.
  • a printing method a wet method such as a coating method
  • a physical method such as a vacuum evaporation method, a sputtering method, an ion plating method, or a chemical method such as CVD or plasma CVD.
  • the material of the electrode is ITO, it can be formed by an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (sol-gel method etc.), application of a dispersion of indium tin oxide, or the like.
  • UV-ozone treatment, plasma treatment, and the like can be performed on a film manufactured using
  • the photoelectric conversion element of the present invention may have a charge blocking film. By having the film, the characteristics (photoelectric conversion efficiency, response speed, etc.) of the obtained photoelectric conversion element are more excellent.
  • Examples of the charge blocking film include an electron blocking film and a hole blocking film. Below, each film is explained in full detail.
  • An electron donating organic material can be used for the electron blocking film.
  • low molecular weight materials such as N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) and 4,4'-bis [N Aromatic diamine compounds such as-(naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), oxazole, oxadiazole, triazole, imidazole, imidazolone, stilbene derivative, pyrazoline derivative, tetrahydroimidazole, polyarylalkane, butadiene
  • Porphyrins such as 4,4 ′, 4 ′ ′ tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), porphyrin, tetraphenylporphyrin copper, phthalocyanine, copper phthalo
  • polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene and derivatives thereof and derivatives thereof can be used. Any compound having transportability can be used, and specifically, the compounds described in [0083] to [0089] of JP-A-2008-72090 are preferable.
  • the electron blocking film preferably also contains a compound represented by Formula (F-1).
  • F-1 a compound represented by Formula (F-1).
  • R ′ 1 to R ′ 3 each independently represent a hydrogen atom or an alkyl group.
  • R a "11 ⁇ R" 18, R '11 ⁇ R' 18 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, Or a mercapto group, which may further have a substituent.
  • the substituent represented by general formula (A-1) is preferably independently substituted to R ′ ′ 12 and R ′ 12 respectively, and the substituent represented by general formula (A-1) is R ′ ′ 12 and 'replaced independently to 12, R "11, R" 13 ⁇ R “18, R' R 11, R '13 ⁇ R' 18 is hydrogen atom, optionally 1 carbon atoms which may ⁇ have a substituent more preferably 18 alkyl group, particularly preferably a substituent represented by the general formula (a-1) is "substituted independently on 12 and R '12, R" R 11 , R “13 ⁇ R ′ ′ 18 , R ′ 11 and R ′ 13 to R ′ 18 are hydrogen atoms.
  • Y each independently represents a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom, and these may further have a substituent. That is, Y represents a divalent linking group consisting of carbon atom, nitrogen atom, oxygen atom, sulfur atom, or silicon atom.
  • R ′ 20 to R ′ 24 are preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group, or a heterocyclic group, and more preferably a hydrogen atom or a substituent.
  • each of Ra 1 to Ra 8 independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group, a heterocyclic group, a hydroxyl group, an amino group, or Represents a mercapto group.
  • Specific examples of the further substituent include the substituent W. Also, a plurality of these substituents may be bonded to each other to form a ring.
  • Each of Ra 1 to Ra 8 is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heterocyclic group having 4 to 16 carbon atoms.
  • An alkyl group of 1 to 12 or an aryl group having 6 to 14 carbon atoms is more preferable, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms is more preferable.
  • the alkyl group may be branched.
  • Xa represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group, or an imino group, which are further substituted May be included.
  • R ′ 1 represents a hydrogen atom or an alkyl group.
  • R ′ 1 is preferably a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group or a tert-butyl group, and more preferably a methyl group, an ethyl group, a propyl group, an iso-propyl group or It is a tert-butyl group, more preferably a methyl group, an ethyl group, an iso-propyl group or a tert-butyl group, and particularly preferably a methyl group, an ethyl group or a tert-butyl group.
  • R ′ 2 represents a hydrogen atom or an alkyl group.
  • R ′ 2 is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group or a tert-butyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group And more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
  • R '3 represents a hydrogen atom or an alkyl group.
  • R ′ 3 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
  • R ′ 1 to R ′ 3 may be bonded to each other to form a ring.
  • the number of ring members is not particularly limited, but it is preferably a 5- or 6-membered ring, more preferably a 6-membered ring.
  • each of Ra 33 to Ra 38 , Ra 41 , Ra 44 to Ra 48 , Ra 51 , Ra 52 , and Ra 55 to Ra 58 independently represents a hydrogen atom or It represents a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) or an alkyl group. It is preferable that it is a hydrogen atom or an alkyl group from the viewpoint that it is advantageous to transport of a hole that the substituent is a low polarity substituent, and a hydrogen atom is more preferable.
  • the ring includes the aforementioned ring R.
  • the ring is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring and the like.
  • Xc 1 , Xc 2 and Xc 3 each independently represent a single bond, an oxygen atom, a sulfur atom, an alkylene group, a silylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group Or an imino group.
  • Xc 1 , Xc 2 and Xc 3 each represent an alkylene group, a silylene group, an alkenylene group, a cycloalkylene group, a cycloalkenylene group, an arylene group, a divalent heterocyclic group or an imino group, these further have a substituent You may have.
  • the additional substituent includes a substituent W.
  • Xc 1 , Xc 2 and Xc 3 each represents a single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, an arylene group having 6 to 14 carbon atoms, or a heterocyclic group having 4 to 13 carbon atoms
  • an imino group eg, phenylimino group, methylimino group, t-butylimino group
  • an oxygen atom, a sulfur atom, or a hydrocarbon group having 1 to 12 carbon atoms (preferably an aryl group or an alkyl group) is preferable, a single bond
  • An alkylene group having 1 to 6 carbon atoms eg, methylene group, 1,2-ethylene group, 1,1-dimethyl methylene group
  • an alkenylene group having 2 carbon atoms eg, -CH 2 CHCH 2-
  • An arylene group of 6 to 10 eg, a 1,2-pheny
  • Z 31 , Z 41 and Z 51 each independently represent a cycloalkyl ring, an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • Z 31 , Z 41 and Z 51 are fused to a benzene ring.
  • Z 31 , Z 41 and Z 51 are preferably aromatic hydrocarbon rings from the viewpoint that high heat resistance and high hole transportability of the photoelectric conversion element can be expected.
  • Porphyrin compounds such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran), 4H pyran compounds can be used.
  • styryl compounds such as DCM (4-dicyanomethylene-2-methyl-6- (4- (dimethylaminostyryl))-4H pyran
  • 4H pyran compounds can be used.
  • compounds described in paragraphs [0073] to [0078] of JP-A-2008-72090 are preferable.
  • the method for producing the charge blocking film is not particularly limited, and the film can be formed by a dry film forming method or a wet film forming method.
  • a vapor deposition method, a sputtering method, etc. can be used as a dry film forming method.
  • the vapor deposition may be 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
  • a 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 preferred.
  • the thickness of the charge blocking film is preferably 10 to 200 nm, more preferably 30 to 150 nm, and particularly preferably 50 to 100 nm. When this thickness is too thin, the dark current suppressing effect is reduced, and when it is too thick, the photoelectric conversion efficiency is reduced.
  • sealing layer materials may be selected and manufactured according to the description in paragraphs [0210] to [0215] of JP-A-2011-082508.
  • a photoelectric conversion element of the present invention As a use of a photoelectric conversion element, although a photovoltaic cell and an optical sensor are mentioned, for example, it is preferred to use a photoelectric conversion element of the present invention as an optical sensor. As an optical sensor, what was used by the said photoelectric conversion element independently may be used, and what has a form of the line sensor which distribute
  • the photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a driving unit such as a scanner in a line sensor, and the two-dimensional sensor converts optical image information into an optical signal as an imaging module.
  • the system functions as an imaging element by forming an image on a sensor and converting it into an electric signal. Since a photovoltaic cell is a power generation device, the efficiency of converting light energy into electrical energy is an important performance, but the dark current, which is the current in a dark place, does not pose a functional problem. Furthermore, there is no need for a subsequent heating process such as color filter installation. Since it is important that the light sensor convert light and dark signals into electrical signals with high accuracy, the efficiency of converting the amount of light into current is also an important performance, but outputting a signal in a dark place causes noise, Low dark current is required. Furthermore, resistance to the subsequent steps is also important.
  • FIG. 2 is a schematic cross-sectional view showing a schematic configuration of an imaging device for describing an embodiment of the present invention.
  • the image pickup device is used by being mounted on an image pickup apparatus such as a digital camera or a digital video camera, an image pickup module such as an electronic endoscope, or a mobile phone.
  • This imaging device has a plurality of photoelectric conversion devices configured as shown in FIG. 1 and a circuit board on which a readout circuit for reading out a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion device is formed.
  • a plurality of photoelectric conversion elements are arranged in a one-dimensional or two-dimensional manner on the same plane above the circuit board.
  • the imaging device 100 illustrated in FIG. 2 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and an opposite electrode.
  • the pixel electrode 104 has the same function as the lower electrode 11 of the photoelectric conversion element 10a shown in FIG.
  • the counter electrode 108 has the same function as the upper electrode 15 of the photoelectric conversion element 10 a shown in FIG. 1.
  • the photoelectric conversion film 107 has the same configuration as the layer provided between the lower electrode 11 and the upper electrode 15 of the photoelectric conversion element 10 a shown in FIG. 1.
  • 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 on the connection electrode 103 disposed outside the photoelectric conversion film 107 and is electrically connected to the connection electrode 103.
  • connection portion 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 portion 115.
  • the counter electrode voltage supply unit 115 is formed on the substrate 101, and applies a predetermined voltage to the counter electrode 108 through the connection portion 106 and the connection electrode 103.
  • the power supply voltage is boosted by a charge pump or other booster circuit 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 formed of, for example, a CCD, a CMOS circuit, or a TFT circuit, and is shielded from light 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 portion 105.
  • the light shielding layer 113 is formed on the sealing layer 110 except the area where the color filter 111 and the partition wall 112 are provided, and prevents light from entering the photoelectric conversion film 107 formed in areas other than the effective pixel area.
  • the protective layer 114 is formed on the color filter 111, the partition wall 112, and the light shielding layer 113, and protects the entire imaging element 100.
  • the imaging device 100 when light is incident, the light is incident on the photoelectric conversion film 107, and a charge is generated here. Holes among 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 imaging element 100 by the readout circuit 116.
  • the method of manufacturing the imaging device 100 is as follows.
  • the connection portions 105 and 106, the plurality of connection electrodes 103, the plurality of pixel electrodes 104, and the insulating layer 102 are formed on the circuit substrate on which the counter electrode voltage supply portion 115 and the readout circuit 116 are formed.
  • the plurality of pixel electrodes 104 are arranged on the surface of the insulating layer 102 in, for example, a square lattice.
  • the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum heating evaporation method.
  • the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum, for example, by sputtering.
  • the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum heating evaporation method.
  • the protective layer 114 is formed, and the imaging device 100 is completed.
  • the compounds D1 to D2 and D4 to D14 described later were synthesized with reference to the synthesis method of the compound D3 and a known method.
  • the compounds (D1 to D14, RD1 to RD4) used in this example and the comparative example are collectively shown below.
  • the photoelectric conversion element of the form of Fig.1 (a) was produced.
  • the photoelectric conversion element includes the lower electrode 11, the electron blocking film 16 A, the photoelectric conversion film 12, and the upper electrode 15.
  • amorphous ITO is deposited 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
  • the film was formed by vapor deposition to form an electron blocking film 16A (thickness: 100 nm).
  • the above compounds (D1 to D14, RD1 to RD4) and fullerene (C 60 ) become 100 nm and 300 nm in single layer conversion, respectively, on the electron blocking film 16A.
  • the film was co-deposited by vacuum heating deposition to form a film, and the photoelectric conversion film 12 was formed.
  • amorphous ITO was formed into a film on the photoelectric conversion film 12 by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
  • an aluminum oxide (Al 2 O 3 ) layer was formed thereon by an ALCVD method, and a photoelectric conversion element was produced.
  • Example 1 [Rise time from 0 to 98% signal strength in the embodiment (or comparative example) X] / [rise time from 0 to 98% signal strength in the embodiment 1] In practice, it is preferably 20 or less, and more preferably 5 or less.
  • Example 3 when X 1 and X 2 are O (oxygen atom) (corresponding to Example 3), it is confirmed that the response speed and the heat resistance are more excellent.
  • X 1 and X 2 are O (oxygen atom) (corresponding to Example 3)
  • Ar 1 and Ar 2 are arylene groups (it corresponds to Example 1), it turned out that a response is more excellent so that comparison with Example 1 and Example 8 may show.
  • RD4 which does not have an amino group
  • RD2 and RD3 correspond to the exemplified compounds (19) and (71) exemplified in JP-A-2010-192782, and RD4 is used in Example 6 of JP-A-2003-346926. It corresponds to a compound.
  • Imaging device similar to that shown in FIG. 2 was produced. That is, after depositing amorphous TiN 30 nm on a CMOS substrate by sputtering, it is patterned by photolithography so that one pixel exists on each of the photodiodes (PD) on the CMOS substrate to form a lower electrode. After the film formation of the electron blocking material, it was manufactured in the same manner as in Examples 1 to 14 and Comparative Examples 1 to 4. The evaluation was also conducted similarly, and the same results as in Table 1 were obtained, and it was found that the imaging device is also suitable for production and shows excellent performance.

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