WO2017138363A1 - 有機光電変換素子、光エリアセンサ、撮像素子及び撮像装置 - Google Patents

有機光電変換素子、光エリアセンサ、撮像素子及び撮像装置 Download PDF

Info

Publication number
WO2017138363A1
WO2017138363A1 PCT/JP2017/002692 JP2017002692W WO2017138363A1 WO 2017138363 A1 WO2017138363 A1 WO 2017138363A1 JP 2017002692 W JP2017002692 W JP 2017002692W WO 2017138363 A1 WO2017138363 A1 WO 2017138363A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
substituted
formula
unsubstituted
photoelectric conversion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/002692
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
鎌谷　淳
山田　直樹
博揮 大類
賢悟 岸野
岩脇　洋伸
塩原　悟
智奈 山口
真澄 板橋
洋祐 西出
広和 宮下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Publication of WO2017138363A1 publication Critical patent/WO2017138363A1/ja
Priority to US16/056,270 priority Critical patent/US11121182B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/10—Integrated devices
    • H10F39/12—Image sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • H10K39/32—Organic image sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
    • 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
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • 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
    • H10K85/6572—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
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/80—Constructional details of image sensors
    • H10F39/805—Coatings
    • H10F39/8053—Colour filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/80—Constructional details of image sensors
    • H10F39/806—Optical elements or arrangements associated with the image sensors
    • H10F39/8063—Microlenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/353—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising blocking layers, e.g. exciton blocking layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to an organic photoelectric conversion element, and an optical area sensor, an imaging element and an imaging apparatus using the same.
  • Patent Document 1 discloses that in order to obtain an organic photoelectric conversion element having good sensitivity, a photoelectric conversion layer constituting the element includes a fullerene and a light absorbing material.
  • Patent Document 2 discloses a solar cell using a dibenzofluoranthene compound and fullerene.
  • JP2013-236008A International Publication No. 2011/093067
  • the organic photoelectric conversion element disclosed in Patent Document 1 since the constituent material of the photoelectric conversion layer does not have a partial structure common to each molecule, the efficiency of charge separation in the charge separation process is low and there is room for improvement. . Further, the solar cell disclosed in Patent Document 2 also has room for improvement in terms of photoelectric conversion efficiency.
  • This invention is made
  • the organic photoelectric conversion element of the present invention is an organic photoelectric conversion device including an electron collection electrode, a hole collection electrode, and a photoelectric conversion unit disposed between the electron collection electrode and the hole collection electrode.
  • a conversion element, The photoelectric conversion unit has a first organic compound layer, A second organic compound layer is disposed between the hole collection electrode and the photoelectric conversion unit, The first organic compound layer includes at least a first compound having a fullerene skeleton and a second compound having a fluoranthene skeleton.
  • the organic photoelectric conversion element of the present invention has at least two kinds of compounds (first compound and second compound) contained in the photoelectric conversion part, each having a common fluoranthene structure. For this reason, according to this invention, the organic photoelectric conversion element with improved photoelectric conversion efficiency can be provided.
  • the organic photoelectric conversion element of the present invention includes an electron collection electrode, a hole collection electrode, and a photoelectric conversion unit disposed between the electron collection electrode and the hole collection electrode. Yes.
  • a photoelectric conversion part has a 1st organic compound layer, and the 2nd organic compound layer is arrange
  • the first organic compound layer includes at least a first compound having a fullerene skeleton and a second compound having a fluoranthene skeleton.
  • the process from photoexcitation to charge separation is important.
  • a molecule that absorbs and excites light having a wavelength in the visible region and a molecule that generates excitation (hole, electron) by receiving excitation energy from the excited molecule (for example, fullerene).
  • a molecule with a small rearrangement energy such as
  • the intermolecular interaction between the two types of molecules described above is important. At this time, if the two types of molecules described above have a common partial structure, intermolecular interaction is likely to be induced via this partial structure.
  • aromatic functional groups (aryl group, heterocyclic group) have the property of interacting with each other. This is due to the dispersion force between the aromatic rings in the molecule, that is, the London dispersion. Because power works. This London dispersion force tends to stabilize when the aromatic rings are arranged like coins. In addition, this arrangement form of aromatic rings is also called stacking interaction. The effect of this intermolecular interaction tends to become stronger as the number of ⁇ electrons of the aromatic ring involved in the stack increases, and becomes stronger as the structure similarity between the two types of molecules increases.
  • the structure of a fullerene skeleton which is a skeleton often used for charge separation, is a spherical structure in which 5-membered rings and 6-membered rings are alternately condensed as shown in the following general formula (A).
  • A the structure of a fullerene skeleton
  • the smallest unit is benzene, but in order to exhibit a larger intermolecular interaction, the aromatic compound has more ⁇ -electrons than benzene and contains the following general formula (B
  • the present inventors thought that the fluoranthene skeleton of (2) was suitable as a basic unit.
  • the reason why the fluoranthene skeleton formed by the condensation of three six-membered rings and one five-membered ring is suitable as a basic unit is that the LUMO of this fluoranthene skeleton is deep (electron affinity is large), and electron acceptability Is that it is expensive.
  • a compound having a fullerene skeleton has a deep LUMO because it has a fluoranthene skeleton in the fullerene skeleton. Therefore, the fluoranthene skeleton, which is one of the basic units of the aromatic ring contained in this fullerene, is given to both molecules that emit photoexcitation energy and molecules that perform charge separation (generate holes and electrons). .
  • the present inventors have found that the intermolecular interaction between these molecules is increased, and charge separation can be performed more efficiently.
  • the organic photoelectric conversion element of the present invention exhibit intermolecular interaction.
  • a voltage is applied to the electrode, a current flows without irradiating light. This becomes a dark current, which is a serious problem in terms of device characteristics.
  • This problem can be solved by providing an electron blocking layer between the electrode and the photoelectric conversion unit. Since the dark current is generated when the energy levels of the electrode and the photoelectric conversion unit are close to each other, an electron blocking layer is provided between the electrode and the photoelectric conversion unit in order to eliminate the proximity relationship between the energy levels. For this reason, as for the organic photoelectric conversion element of this invention, it is desirable to provide not only a photoelectric conversion part but an electron blocking layer between an electrode and a photoelectric conversion part.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the organic photoelectric conversion device of the present invention.
  • the organic photoelectric conversion element 1 in FIG. 1 is disposed between an electron collection electrode (anode) 13, a hole collection electrode (cathode) 14, and an electron collection electrode 13 and a hole collection electrode 14. And the first organic compound layer 10.
  • the hole collecting electrode 14 constituting the organic photoelectric conversion element 1 in FIG. 1 is an electrode that collects holes that are one of the charges generated in the first organic compound layer 10.
  • the hole collection electrode 14 corresponds to a pixel electrode.
  • the electron collection electrode 13 corresponds to a pixel electrode.
  • the electron collection electrode 13 is disposed closer to the pixel circuit (for example, the readout circuit 15) than the hole collection electrode 14.
  • the collecting electrode 14 may be disposed on the side closer to the pixel circuit.
  • the first organic compound layer 10 has a compound that is excited by receiving light in the layer.
  • the first organic compound layer 10 also has a role of transporting charges generated after the molecules of the compound are excited by light, that is, electrons and holes, to the electron collecting electrode 13 and the hole collecting electrode 14, respectively. Plays. Since the first organic compound layer 10 contains an organic compound that converts light into electric charges as will be described later, the first organic compound layer 10 is a layer constituting a photoelectric conversion layer or a photoelectric conversion unit.
  • the photoelectric conversion part constituting the organic photoelectric conversion element is not limited to the first organic compound layer 10 alone.
  • a third organic compound layer 12 described later can also be included in the photoelectric conversion unit.
  • the first organic compound layer 10 is preferably a layer containing a p-type organic semiconductor or an n-type organic semiconductor.
  • the first organic compound layer 10 is more preferably a bulk hetero layer (mixed layer) at least part of which includes a p-type organic semiconductor and an n-type organic semiconductor.
  • the photoelectric conversion efficiency (sensitivity) of the device can be further improved. .
  • the electron mobility in the first organic compound layer 10 and The hole mobility can be increased, and the light response speed of the organic photoelectric conversion element can be further increased.
  • the first organic compound layer 10 is preferably composed of one layer, but may be composed of a plurality of layers. In the present invention, the first organic compound layer 10 preferably does not emit light.
  • the term “non-light-emitting” as used herein refers to a layer having an emission quantum efficiency of 1% or less, preferably 0.5% or less, more preferably 0.1% or less in the visible light region (wavelength 400 nm to 730 nm). It means that.
  • the emission quantum efficiency exceeds 1%, the sensing performance or imaging performance is improved when the organic photoelectric conversion device of the present invention is applied as a constituent member of a sensor or an imaging device. This is not preferable because it affects the operation.
  • the details of the two types of compounds contained in the first organic compound layer 10, that is, the first compound having a fullerene skeleton and the second compound having a fluoranthene skeleton will be described later.
  • a second organic compound layer 11 is provided between the hole collection electrode 14 and the first organic compound layer 10.
  • the second organic compound layer 11 may be composed of a single layer or a plurality of layers.
  • the second organic compound layer 11 may be a bulk hetero layer (mixed layer) having a plurality of types of materials.
  • the second organic compound layer 11 has a role of transporting holes transferred from the first organic compound layer 10 to the hole collecting electrode 14. Further, the second organic compound layer 11 suppresses movement of electrons from the hole collection electrode 14 to the photoelectric conversion unit. That is, the second organic compound layer 11 functions as a hole transport layer or an electron blocking layer, and is a preferable constituent member for solving the above-described problem of dark current.
  • the second organic compound layer 11 is preferably in contact with the hole collection electrode 14.
  • a third organic compound layer 12 may be provided between the electron collection electrode 13 and the first organic compound layer 10.
  • the third organic compound layer 12 is a layer provided between the first organic compound layer 10 and the electron collection electrode 13.
  • the third organic compound layer 12 has a role of transporting electrons moved from the first organic compound layer 10 to the electron collection electrode 13.
  • the third organic compound layer 12 is a layer (hole blocking layer) that suppresses the flow of holes from the electron collection electrode 13 to the first organic compound layer 10, and thus has a high ionization potential. It is preferable.
  • the 3rd organic compound layer 12 may be comprised by the single layer, and may be comprised by the some layer.
  • the third organic compound layer 12 may be a bulk hetero layer (mixed layer) having a plurality of types of materials.
  • the third organic compound layer 12 is disposed between the first organic compound layer 10 and the electron collecting electrode 13 as shown in FIG. It is preferable to touch.
  • the layer disposed between the electron collecting electrode 13 and the hole collecting electrode 14 is composed of the above-described three types of layers (first organic compound layer 10, second organic compound layer 11, first layer). It is not limited to the three organic compound layers 12).
  • An intervening layer can be further provided between the organic compound layer and the hole collecting electrode 14 or between the organic compound layer and the electron collecting electrode 13. This intervening layer is provided for the purpose of improving the injection efficiency of the charge when the generated charge is injected at the electrode, or preventing the charge from being injected into the organic compound layer when the charge is applied.
  • this intervening layer may be an organic compound layer having an organic compound layer or an inorganic compound layer having an inorganic compound.
  • the electron collection electrode 13 is connected to a readout circuit 15.
  • the readout circuit 15 may be connected to the hole collection electrode 14.
  • the readout circuit 15 reads out information based on the charges generated in the first organic compound layer 10 and plays a role of transmitting the information to, for example, a signal processing circuit (not shown) arranged in the subsequent stage.
  • the readout circuit 15 includes, for example, a transistor that outputs a signal based on charges generated in the organic photoelectric conversion element 1.
  • an inorganic protective layer 16 is disposed on the hole collecting electrode 14.
  • the inorganic protective layer 16 includes an electron collection electrode 13, a third organic compound layer 12, a first organic compound layer 10, a second organic compound layer 11, and a hole collection electrode 14. It is a layer for protecting the member laminated
  • the constituent material of the inorganic protective layer 16 include silicon oxide, silicon nitride, and aluminum oxide.
  • the inorganic protective layer 16 can be formed by a known film formation method.
  • a color filter 17 is disposed on the inorganic protective layer 16.
  • the color filter 17 include a color filter that transmits red light of visible light.
  • the color filter 17 may be provided for one organic photoelectric conversion element or for a plurality of organic photoelectric conversion elements. Further, when the color filters 17 are arranged, for example, a Bayer arrangement may be formed with adjacent organic photoelectric conversion elements.
  • an optical member such as a microlens 18 is disposed on the color filter 17.
  • the microlens 18 plays a role of collecting incident light on the first organic compound layer 10 that is a photoelectric conversion unit.
  • the number of microlenses 18 may be one for each organic photoelectric conversion element or one for a plurality of organic photoelectric conversion elements.
  • one microlens 18 is preferably provided for each organic photoelectric conversion element.
  • the organic photoelectric conversion device of the present invention preferably applies a voltage between the hole collection electrode 14 and the electron collection electrode 13 when performing photoelectric conversion.
  • the voltage applied between the electrodes depends on the total film thickness of the organic compound layers (10, 11, 12), but is preferably 1 V or more and 15 V or less. More preferably, it is 2V or more and 10V or less.
  • the organic photoelectric conversion element of the present invention may have a substrate.
  • the substrate include a silicon substrate, a glass substrate, and a flexible substrate.
  • the constituent material of the hole collection electrode 14 is not particularly limited as long as it is a highly conductive material and has transparency.
  • 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, gold,
  • Metal materials such as silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides and nitrides of these metal materials (for example, titanium nitride (TiN)), and these metals and conductive metal oxidation Examples thereof include a mixture or laminate with a material, an inorganic conductive material such as copper iodide and copper sulfide, an organic conductive material such as polyaniline, polythiophene and polypyrrole, and a laminate of these with ITO or titanium nitride.
  • the constituent material of the hole collecting electrode 14 is particularly preferably
  • Electronic collecting electrode electron collecting electrode 13 specifically, ITO, indium zinc oxide, SnO 2, ATO (antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide), GZO (Gallium-doped zinc oxide), TiO 2 , FTO (fluorine-doped tin oxide) and the like.
  • the formation method of the two types of electrodes (13, 14) described above can be appropriately selected in consideration of appropriateness with the electrode material used. 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.
  • An electrode can be formed.
  • the surface of the formed electrode (ITO electrode) may be subjected to UV-ozone treatment, plasma treatment, or the like.
  • various film forming methods including a reactive sputtering method can be used.
  • the formed electrode (TiN electrode) may be subjected to annealing treatment, UV-ozone treatment, plasma treatment, or the like.
  • the first organic compound layer 10 constituting the organic photoelectric conversion element has a first compound having a fullerene skeleton and a second compound having a fluoranthene skeleton. Yes.
  • the first organic compound layer 10 includes a plurality of types of organic compounds, and the first organic compound layer 10 is formed by mixing the first compound and the second compound. It may be a layer.
  • the first organic compound layer 10 may be a laminate in which a layer having a first compound and a layer having a second compound are laminated.
  • the plurality of layers constituting the laminated body have electron collection.
  • the electrodes 14 are preferably stacked in the direction from the hole collecting electrode 13 to the hole collecting electrode 13.
  • the first organic compound layer 10 serving as a photoelectric conversion portion includes a material that mainly absorbs light having a wavelength in the visible light region and a material that performs charge separation (generation of electrons and holes).
  • the material that mainly absorbs light having a wavelength in the visible light region is, for example, a second compound having a fluoranthene skeleton.
  • a compound other than the second compound may be used together with the second compound.
  • the material having charge separation is at least the first compound having a fullerene skeleton.
  • a compound other than the first compound may be used together with the first compound as a material that performs charge separation.
  • fullerene which is a skeleton of the first compound included in the first organic compound layer 10
  • fullerene is a general term for a closed-shell hollow cluster composed of only a large number of carbon atoms.
  • specific examples of the fullerene include C60 and higher-order fullerenes C70, C74, C76, and C78.
  • the first compound includes not only these fullerenes but also fullerene derivatives in which substituents such as alkyl groups, aryl groups, and heterocyclic groups are introduced into fullerenes.
  • fullerenes and fullerene derivatives may be collectively referred to as “fullerenes”.
  • One of these compounds may be selected and used, or a plurality of these compounds may be selected and used.
  • These fullerenes all have a fluoranthene skeleton, and play the role of charge separation and electron transport.
  • skeleton can play the role of an electron conveyance.
  • the compound having two or more fluoranthene skeletons has higher electron acceptability than the compound having one fluoranthene skeleton, the effect of transporting electrons becomes larger.
  • Fullerene is a compound having a large number of fluoranthene skeletons, and thus is particularly preferable as a material for transporting electrons.
  • Fullerenes contained in the first organic compound layer 10 can be used as an n-type organic semiconductor. Further, since the molecules of fullerene cause stacking between the fluoranthene skeletons, each molecule can be connected (oriented) in a certain direction in the first organic compound layer 10. Thereby, since an electron path is formed, the electron transport property is improved, and the high-speed response of the organic photoelectric conversion element is improved.
  • the content of fullerenes contained in the first organic compound layer 10 is preferably 30% by volume or more and 70% by volume or less with respect to the entire first organic compound layer 10.
  • fullerenes fullerene, fullerene derivatives
  • fullerene C60 fullerene C70, fullerene C76, fullerene C78, fullerene C80, fullerene C82, fullerene C84, fullerene C90, fullerene C96, fullerene C240.
  • Fullerene 540 mixed fullerene, fullerene nanotube, and fullerene derivatives shown below.
  • fullerene C60 is preferable.
  • the compound corresponding to the second compound is a compound having a fluoranthene skeleton, and is preferably a compound represented by any one of the following general formulas (1) to (17).
  • R 1 to R 10 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • -CR a CR b R c (I)
  • the details of the vinyl group of the general formula (I) will be described later.
  • alkyl group represented by R 1 to R 10 examples include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, secondary butyl group, octyl group, 1-adamantyl group, and 2-adamantyl group. Examples include, but are not limited to, groups.
  • Examples of the aryl group represented by R 1 to R 10 include a phenyl group, a naphthyl group, an indenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, an anthracenyl group, a pyrenyl group, and a perylenyl group. Is not to be done.
  • heterocyclic group represented by R 1 to R 10 pyridyl group, pyrazyl group, triazyl group, thienyl group, furanyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, carbazolyl group, acridinyl group, phenanthroyl group, A benzothiophenyl group, a dibenzothiophenyl group, etc. are mentioned, but of course, it is not limited to these.
  • the alkyl group, aryl group, heterocyclic group and amino group may have, an alkyl group such as a methyl group, an ethyl group, a propyl group or a tertiary butyl group, an aralkyl group such as a benzyl group, or a phenyl group
  • Aryl groups such as biphenyl group and naphthyl group, heterocyclic groups such as pyridyl group and pyrrolyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, N, N-di- (4- (Tertiarybutylphenyl) amino group such as amino group, alkoxy group such as methoxyl group, ethoxyl group, propoxyl group, aryloxy group such as phenoxyl group, halogen atom such as fluorine, chlorine, bromine and io
  • R a , R b and R c are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a tertiary butyl group, an aralkyl group such as a benzyl group, a phenyl group or a biphenyl group
  • Aryl groups such as naphthyl group, heterocyclic groups such as pyridyl group and pyrrolyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, N, N-di- (4-tertiarybutyl Phenyl) amino group and other amino groups, methoxyl group, ethoxyl group, propoxyl group and other alkoxy groups, phenoxyl group and other
  • R d to R f are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a tertiary butyl group, an aralkyl group such as a benzyl group, a phenyl group, Aryl groups such as biphenyl group and naphthyl group, heterocyclic groups such as pyridyl group and pyrrolyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, N, N-di- (4-tersia) (Ributylphenyl) represents an amino group such as an amino group, an alkoxy group such as
  • any of the substituents of R d to R f is an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, Al
  • the substituent is an alkyl group such as a methyl group, an ethyl group, a propyl group or a tertiary butyl group, an aralkyl group such as a benzyl group, a phenyl group, a biphenyl group or a naphthyl group.
  • Heterocyclic groups such as aryl group, pyridyl group, pyrrolyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, N, N-di- (4-tert-butylphenyl) amino group, etc.
  • An aryloxy group such as an alkoxy group such as an amino group, a methoxyl group, an ethoxyl group or a propoxyl group, a phenoxyl group, a halogen atom such as fluorine, chlorine, bromine or iodine, or a cyano group.
  • R a , R b and R c may be bonded to form a ring structure.
  • the vinyl group is preferably a substituent represented by the following general formulas (21) to (25).
  • R 301 to R 304 are each a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group or a tertiary butyl group, an aralkyl group such as a benzyl group, an aryl group such as a phenyl group, a biphenyl group or a naphthyl group, a pyridyl group Group, heterocyclic group such as pyrrolyl group, amino group such as dimethylamino group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, N, N-di- (4-tert-butylphenyl) amino group, An alkoxy group such as a methoxyl group, an ethoxyl group, or a propoxyl group; an aryloxy group such as a phenoxyl group; a aryloxy group such as a phenoxy
  • R 305 to R 310 each represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.
  • Specific examples of the alkyl group, aralkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group and halogen atom represented by R 305 to R 310 are R 301 in the formula (21). to the same as specific examples of R 304.
  • R 311 to R 316 each represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.
  • Specific examples of the alkyl group, aralkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group and halogen atom represented by R 311 to R 316 are R 301 in the formula (21). to the same as specific examples of R 304.
  • R317 and R318 each represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, a halogen atom or a cyano group.
  • Specific examples of the alkyl group, aralkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group and halogen atom represented by R 317 and R 318 are R 301 in the formula (21). to the same as specific examples of R 304.
  • R 319 to R 321 each represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.
  • Specific examples of the alkyl group, aralkyl group, aryl group, heterocyclic group, amino group, alkoxy group, aryloxy group and halogen atom represented by R 319 to R 321 include R 301 in the formula (21). to the same as specific examples of R 304.
  • vinyl groups represented by general formulas (21) to (24) are shown below. However, in the present invention, the vinyl group represented by any one of the general formulas (21) to (24) is not limited to these specific examples.
  • * represents a bond.
  • R 11 to R 22 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 11 to R 22 , the above-mentioned alkyl group, aryl group, heterocyclic group and amino group may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 23 to R 35 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 36 to R 53 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 36 to R 53 , the above-mentioned alkyl group, aryl group, heterocyclic group and amino group may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 54 to R 69 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 70 to R 83 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 84 to R 95 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 96 to R 107 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 96 to R 107 , the above-mentioned alkyl group, aryl group, heterocyclic group and amino group may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 108 to R 121 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 122 to R 137 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 122 to R 137 , the above-mentioned alkyl group, aryl group, heterocyclic group and amino group may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 138 to R 153 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 138 to R 153 may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 154 to R 167 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 154 to R 167 , the above-mentioned alkyl group, aryl group, heterocyclic group and amino group may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 168 to R 185 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 186 to R 205 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 186 to R 205 may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 206 to R 221 each represent a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the alkyl group, aryl group, heterocyclic group and amino group represented by R 206 to R 221 , the above-described alkyl group, aryl group, heterocyclic group and amino group may have a substituent, and the formula (I Specific examples of the substituents (R a , R b and R c ) in () are the same as the specific examples of R 1 to R 10 in the formula (1).
  • R 222 to R 241 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • R 242 to R 263 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, the following general formula (I ) Represents a vinyl group, a substituted or unsubstituted amino group, or a cyano group.
  • the organic compound represented by any one of the general formulas (1) to (17) serving as the second compound may be used singly or in combination.
  • the second compound having a fluoranthene skeleton is shown.
  • the second compound is not limited to the specific examples shown below.
  • the compounds shown above have a fluoranthene skeleton like fullerenes, these organic compounds absorb the light of a specific wavelength and enter the excited state of the molecules themselves when excited. A compound that can be transferred to one compound.
  • the compound defined by any one of the general formulas (1) to (6) is suitable as a constituent material of an organic photoelectric conversion element having blue to green sensitivity because its basic skeleton has absorption of blue wavelength. ing.
  • the compound defined in any one of the general formulas (1) to (6) introduces a substituent such as an aryl group or a vinyl group to increase the conjugation length of the compound itself, so that green to red or red It can be used as a constituent material of an organic photoelectric conversion element having sensitivity to the outside.
  • the organic photoelectric conversion element having the sensitivity of green to yellow Suitable as a constituent material.
  • the compound defined in any one of the general formulas (7) to (12) can be converted from green to red or red by introducing a substituent such as an aryl group or vinyl group to increase the conjugation length of the compound itself. It can be used as a constituent material of an organic photoelectric conversion element having sensitivity to the outside.
  • the basic skeleton of the compound defined in any one of the general formulas (13) to (17) has red wavelength absorption, it can be used as a constituent material of an organic photoelectric conversion element having red sensitivity. Is possible.
  • a substituent such as an aryl group or a vinyl group to increase the conjugation length of the compound itself, a constituent material of an organic photoelectric conversion element having sensitivity up to red or infrared can be obtained.
  • examples of the constituent material of the second organic compound layer 11 include organic compounds used as a hole transport material or a hole injection material.
  • the constituent material of the third organic compound layer 12 is a material having a high ionization potential, specifically, an electron transport material or an electron injection material.
  • the organic compound used is mentioned. Since the first compound having a fullerene skeleton, which is one of the constituent materials of the first organic compound layer 10, is a material having excellent electron transport properties as described above, the third organic compound layer It can be used as 12 constituent materials.
  • the organic photoelectric conversion element of the present invention can be an organic photoelectric conversion element corresponding to light of different wavelengths by appropriately setting the constituent material of the first organic compound layer. .
  • the “wavelength” here is the wavelength of light received by a predetermined organic photoelectric conversion element.
  • the plurality of types of organic photoelectric conversion elements are stacked in the direction from the hole collection electrode to the electron collection electrode, as shown in FIG. An organic photoelectric conversion device that does not require a color filter is obtained.
  • at least one type of organic photoelectric conversion element is the organic photoelectric conversion element of the present invention.
  • the organic photoelectric conversion element according to the present invention can be used as a constituent member of an optical area sensor by being two-dimensionally arranged in the in-plane direction.
  • the optical area sensor has a plurality of organic photoelectric conversion elements, and a plurality of organic photoelectric conversion elements are arranged in the front direction and the column direction, respectively.
  • the organic photoelectric conversion element according to the present invention can be used as a constituent member of an imaging element.
  • the imaging element has a plurality of organic photoelectric conversion elements each serving as a light receiving pixel, and a transistor connected to each organic photoelectric conversion element.
  • the transistor here is a transistor which reads the electric charge generated from the organic photoelectric conversion element.
  • Information based on the electric charge read by the transistor is transmitted to a sensor unit connected to the image sensor. Examples of the sensor unit include a CMOS sensor and a CCD sensor. An image can be obtained by collecting the information acquired by each light receiving pixel in the sensor unit.
  • the image sensor may have, for example, an optical filter such as a color filter so as to correspond to each light receiving pixel.
  • an optical filter such as a color filter so as to correspond to each light receiving pixel.
  • the organic photoelectric conversion element corresponds to light of a specific wavelength
  • One color filter may be provided for each light receiving pixel, or one color filter may be provided for a plurality of light receiving pixels.
  • the optical filter of the image sensor is not limited to a color filter, and other low-pass filters that transmit wavelengths of infrared rays or more, UV cut filters that transmit wavelengths of ultraviolet rays or less, and long-pass filters can be used.
  • the imaging element may have an optical member such as a microlens so as to correspond to each light receiving pixel, for example.
  • the microlens included in the image sensor is a lens that condenses light from the outside onto a photoelectric conversion unit included in the organic photoelectric conversion element included in the image sensor.
  • One microlens may be provided for each light receiving pixel, or one microlens may be provided for a plurality of light receiving pixels. In the case where a plurality of light receiving pixels are provided, it is preferable that one microlens is provided for a plurality (two or more predetermined numbers) of light receiving pixels.
  • the organic photoelectric conversion element according to the present invention can be used in an imaging apparatus.
  • the imaging apparatus includes an imaging optical system having a plurality of lenses, and an imaging element that receives light that has passed through the imaging optical system.
  • the imaging device may be an imaging device having a joint portion that can be joined to the imaging optical system and an imaging element. More specifically, the imaging device here refers to a digital camera or a digital still camera.
  • the imaging device may further include a receiving unit that receives a signal from the outside.
  • the signal received by the receiving unit is a signal that controls at least one of the imaging range of the imaging apparatus, the start of imaging, and the end of imaging.
  • the imaging device may further include a transmission unit that transmits an image acquired by imaging to the outside.
  • the imaging device can be used as a network camera by including the reception unit and the transmission unit.
  • Example 1 On the substrate, a hole collection electrode, an electron blocking layer (second organic compound layer), a photoelectric conversion part (first organic compound layer), a hole blocking layer (third organic compound layer), and an electron trap.
  • An organic photoelectric conversion element in which the collector electrode was formed in this order was produced by the method described below.
  • an indium zinc oxide film was formed on a substrate (Si substrate) to form a conductive film.
  • the film thickness of the conductive film was 100 nm.
  • this conductive film was processed into a desired shape by patterning to form a hole collecting electrode.
  • substrate with which the hole collection electrode was formed was used at the following processes as a board
  • an organic compound layer and an electrode layer shown in Table 1 below were continuously formed on the substrate with electrodes.
  • the electrode area of the opposing electrode was set to 3 mm 2 .
  • Example 1 the organic photoelectric conversion element was obtained by the method similar to Example 1 except having changed material Z1, Z2, and Z3 as the following Table 2 or Table 3, respectively.
  • the element characteristics (conversion efficiency) of the absorption maximum wavelength are shown in Tables 2 and 3 below.
  • conversion efficiency conversion efficiency
  • the conversion efficiency can be obtained by calculating the ratio of the external quantum efficiency to the light absorption rate inside the device.
  • the light absorptance inside the device is calculated by measuring the light transmittance and light reflectance of the device at a wavelength of 550 nm using an ultraviolet-visible spectrophotometer (device name: Solid Spec-3700, manufactured by Shimadzu Corporation). did.
  • the light incident on the measurement sample is divided into light that passes through the sample (transmitted light), light that is absorbed by the sample (absorbed light), and light that is reflected by the sample (reflected light).
  • the light absorption rate that is, the entire incident light.
  • the ratio of light converted from incident light to absorbed light can be determined.
  • the external quantum efficiency is a monochromatic light having an intensity of 50 ⁇ W / cm 2 corresponding to each wavelength in a state where a voltage of 5 V to 10 V is applied between the hole collecting electrode and the electron collecting electrode. It was calculated by measuring the photocurrent density that flows when the element was irradiated. Here, the photocurrent density was determined by subtracting the dark current density during light shielding from the current density during light irradiation.
  • the monochromatic light used in the measurement of the photocurrent density is white light emitted from a xenon lamp (device name: XB-50101AA-A, manufactured by USHIO), and a monochromator (device name: MC-10N, It is a monochromatic product made by Ritu Applied Optics). Voltage application to the element and current measurement were performed using a source meter (device name: R6243, manufactured by Advantest). Further, in the measurement of the light absorption rate and the external quantum efficiency inside the device, light was incident perpendicularly to the device and from the upper electrode (electron collecting electrode) side.
  • the photoelectric conversion element of the Example in which the compound having a fluoranthene skeleton and the compound having a fullerene skeleton are included in the layer responsible for photoelectric conversion has the conversion efficiency when the applied voltage is 5V and the conversion efficiency when the applied voltage is 10V. It was found that the difference from the conversion efficiency was within 10%. On the other hand, in the photoelectric conversion element of the comparative example, it was shown that the difference between the conversion efficiency when the applied voltage is 5 V and the conversion efficiency when the applied voltage is 10 V is larger than that of the photoelectric conversion element of the example.
  • the fullerene contained in the first organic compound layer (photoelectric conversion part) contains a fluoranthene skeleton, and this fullerene interacts with a compound having a fluoranthene skeleton (material Z2), thereby efficiently separating charges. It can be said that it is done.
  • the improvement of photoelectric conversion efficiency was implement
  • Example 34 In this example, a hole collecting electrode, an electron blocking layer (second organic compound layer), a photoelectric conversion part (first organic compound layer), a hole blocking layer (third organic compound layer) are formed on a substrate. ) And an electron collecting electrode were sequentially formed to produce a photoelectric conversion element by the method described below.
  • an indium zinc oxide film was formed on a substrate (Si substrate) to form a conductive film.
  • the film thickness of the conductive film was 100 nm.
  • this conductive film was processed into a desired shape by patterning to form a hole collecting electrode.
  • substrate with which the hole collection electrode (TiN electrode) was formed was used at the following processes as a board
  • an organic compound layer and an electrode layer shown in Table 4 below were continuously formed on the substrate with electrodes. At this time, the electrode area of the opposing electrode (electron collecting electrode) was set to 3 mm 2 .
  • Example 1 the organic photoelectric conversion element was obtained by the method similar to Example 1 except having changed material Z1, Z2, Z3, and Z4 as shown in following Table 5, respectively. About the obtained element, the characteristic of the organic photoelectric conversion element was measured and evaluated by the same method as Example 1. The results are shown in Table 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nanotechnology (AREA)
  • Electromagnetism (AREA)
  • Light Receiving Elements (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Indole Compounds (AREA)
  • Photovoltaic Devices (AREA)
PCT/JP2017/002692 2016-02-09 2017-01-26 有機光電変換素子、光エリアセンサ、撮像素子及び撮像装置 Ceased WO2017138363A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/056,270 US11121182B2 (en) 2016-02-09 2018-08-06 Organic photoelectric conversion element, optical area sensor, image pickup device, and image pickup apparatus

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-022603 2016-02-09
JP2016022603A JP6700825B2 (ja) 2016-02-09 2016-02-09 有機光電変換素子、光エリアセンサ、撮像素子及び撮像装置

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/056,270 Continuation US11121182B2 (en) 2016-02-09 2018-08-06 Organic photoelectric conversion element, optical area sensor, image pickup device, and image pickup apparatus

Publications (1)

Publication Number Publication Date
WO2017138363A1 true WO2017138363A1 (ja) 2017-08-17

Family

ID=59563885

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/002692 Ceased WO2017138363A1 (ja) 2016-02-09 2017-01-26 有機光電変換素子、光エリアセンサ、撮像素子及び撮像装置

Country Status (3)

Country Link
US (1) US11121182B2 (https=)
JP (1) JP6700825B2 (https=)
WO (1) WO2017138363A1 (https=)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018088325A1 (ja) * 2016-11-11 2018-05-17 キヤノン株式会社 光電変換素子、撮像素子および撮像装置
JP7102114B2 (ja) 2016-11-11 2022-07-19 キヤノン株式会社 光電変換素子、撮像素子および撮像装置
WO2018147202A1 (ja) * 2017-02-07 2018-08-16 キヤノン株式会社 光電変換素子、及びこれを用いた光エリアセンサ、撮像素子、撮像装置
EP3582275B1 (en) 2017-02-07 2023-09-06 Canon Kabushiki Kaisha Photoelectric conversion element, optical area sensor using same, imaging element, and imaging device
JP7046562B2 (ja) * 2017-10-25 2022-04-04 キヤノン株式会社 有機化合物及び光電変換素子
JP7224813B2 (ja) * 2018-08-31 2023-02-20 キヤノン株式会社 有機化合物、有機発光素子、表示装置、撮像装置、電子機器、照明装置及び移動体
JP7541820B2 (ja) * 2019-11-01 2024-08-29 キヤノン株式会社 有機化合物及び有機発光素子
JP7379097B2 (ja) * 2019-11-07 2023-11-14 キヤノン株式会社 有機化合物及び有機発光素子
CN111253301A (zh) * 2020-03-30 2020-06-09 北京燕化集联光电技术有限公司 一种茚并荧蒽结构化合物及应用
CN111233677A (zh) * 2020-03-30 2020-06-05 北京燕化集联光电技术有限公司 一种茚并荧蒽化合物及其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009049278A (ja) * 2007-08-22 2009-03-05 Fujifilm Corp 光電変換素子、光電変換素子の製造方法、固体撮像素子
WO2011093067A1 (ja) * 2010-01-29 2011-08-04 出光興産株式会社 ジベンゾフルオランテン化合物及びそれを用いた有機薄膜太陽電池
JP2013041995A (ja) * 2011-08-16 2013-02-28 Fujifilm Corp 光電変換素子およびその使用方法、撮像素子、光センサ

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5305919B2 (ja) * 2006-11-15 2013-10-02 出光興産株式会社 フルオランテン化合物及びこのフルオランテン化合物を用いた有機エレクトロルミネッセンス素子並びに有機エレクトロルミネッセンス材料含有溶液
US20130174910A1 (en) * 2010-07-27 2013-07-11 Idemitsu Kosan Co., Ltd. Indenoperylene compound, material for organic thin-film photovotaic cell containing indenoperylene derivative and organic thin film photovotaic cell using same
JP6025243B2 (ja) 2012-05-10 2016-11-16 富士フイルム株式会社 光電変換素子及びそれを用いた撮像素子
KR101574704B1 (ko) * 2012-08-09 2015-12-07 희성소재 (주) 신규한 화합물, 이를 포함하는 유기전계발광소자 및 유기태양전지
TWI613833B (zh) * 2012-11-09 2018-02-01 Sony Corp 光電變換元件、固體攝像裝置及電子機器

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009049278A (ja) * 2007-08-22 2009-03-05 Fujifilm Corp 光電変換素子、光電変換素子の製造方法、固体撮像素子
WO2011093067A1 (ja) * 2010-01-29 2011-08-04 出光興産株式会社 ジベンゾフルオランテン化合物及びそれを用いた有機薄膜太陽電池
JP2013041995A (ja) * 2011-08-16 2013-02-28 Fujifilm Corp 光電変換素子およびその使用方法、撮像素子、光センサ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KUNG, YUN-HUA ET AL.: "ynthesis, Structures, and Physical Properties of Benzo[k] fluoranthene-Based Linear Acenes", CHEMISTRY - A EUROPEAN JOURNAL, vol. 16, no. 20, 2010, pages 5909 - 5919, XP002715769, DOI: doi:10.1002/chem.200902695 *

Also Published As

Publication number Publication date
JP2017143133A (ja) 2017-08-17
US11121182B2 (en) 2021-09-14
JP6700825B2 (ja) 2020-05-27
US20180342559A1 (en) 2018-11-29

Similar Documents

Publication Publication Date Title
WO2017138363A1 (ja) 有機光電変換素子、光エリアセンサ、撮像素子及び撮像装置
JP6645700B2 (ja) 有機光電変換素子、二次元センサ、画像センサ及び撮像装置
US11128791B2 (en) Photoelectric conversion element
Strassel et al. Squaraine dye for a visibly transparent all-organic optical upconversion device with sensitivity at 1000 nm
JP7102114B2 (ja) 光電変換素子、撮像素子および撮像装置
US20190267545A1 (en) Photoelectric conversion element, and imaging element and imaging apparatus including the same
TWI683463B (zh) 光電轉換元件及使用其的影像感測器
CN103238221A (zh) 在低驱动电压下具有高探测灵敏度的ir光探测器
CN106663686A (zh) 光电转换膜、固态图像传感器和电子设备
JP2019099570A (ja) フラーレン誘導体及びそれを含む薄膜、光電素子並びにイメージセンサ及び電子装置
WO2018147202A1 (ja) 光電変換素子、及びこれを用いた光エリアセンサ、撮像素子、撮像装置
JP2018129505A (ja) 光電変換素子、及びこれを用いた光エリアセンサ、撮像素子、撮像装置
JP6675005B2 (ja) 光電変換素子、撮像素子、光センサ、化合物
JP2018020976A (ja) 有機化合物及びこれを用いた光電変換素子、光エリアセンサ、光電変換装置、撮像素子、撮像装置
JP7086573B2 (ja) 光電変換素子、及びこれを用いた光エリアセンサ、撮像素子、撮像装置
WO2018088325A1 (ja) 光電変換素子、撮像素子および撮像装置
CN112830938A (zh) 近红外吸收剂、近红外吸收/阻挡膜、光电器件、有机传感器、和电子装置
JP7016662B2 (ja) 有機化合物、それを用いた光電変換素子および撮像装置
JP2017174921A (ja) 有機光電変換素子、二次元センサ、画像センサ及び撮像装置
JP2016063084A (ja) 有機光電変換素子及びこれを備える撮像装置
JP6971561B2 (ja) 光電変換素子、撮像素子および撮像装置
JP2018078240A (ja) 光電変換素子、それを有する撮像素子及び撮像装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17750088

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17750088

Country of ref document: EP

Kind code of ref document: A1