WO2018105269A1 - 光電変換素子、光センサ、及び、撮像素子 - Google Patents
光電変換素子、光センサ、及び、撮像素子 Download PDFInfo
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- WO2018105269A1 WO2018105269A1 PCT/JP2017/039027 JP2017039027W WO2018105269A1 WO 2018105269 A1 WO2018105269 A1 WO 2018105269A1 JP 2017039027 W JP2017039027 W JP 2017039027W WO 2018105269 A1 WO2018105269 A1 WO 2018105269A1
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- photoelectric conversion
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Images
Classifications
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- 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
- C09B57/008—Triarylamine dyes containing no other chromophores
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K19/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
- H10K19/20—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00 comprising components having an active region that includes an inorganic semiconductor
-
- 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
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] 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
- H10K85/60—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
-
- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
- H10K30/211—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions comprising multiple junctions, e.g. double heterojunctions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- 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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a photoelectric conversion element, an optical sensor, and an imaging element.
- a planar solid-state imaging device in which photodiodes (PD) are two-dimensionally arranged and signal charges generated in each PD are read by a circuit has been widely used.
- a structure in which a color filter that transmits light of a specific wavelength is arranged on the light incident surface side of the flat solid-state imaging device is generally used.
- a single-plate type solid-state imaging device in which color filters that transmit blue (B) light, green (G) light, and red (R) light are regularly arranged on each PD arranged two-dimensionally is often used.
- B blue
- G green
- R red
- Patent Document 1 describes a photovoltaic element in which an electron-accepting organic material layer is formed using a squarylium compound.
- this invention makes it a subject to provide the photoelectric conversion element which shows the outstanding responsiveness and the outstanding manufacturing aptitude. Moreover, this invention makes it a subject to provide the optical sensor and imaging device provided with the said photoelectric conversion element.
- the present inventor has obtained a photoelectric conversion film containing a compound represented by the formula (1) (preferably a compound represented by the formula (2)) as a photoelectric conversion material. It has been found that the above-described problems can be solved by the photoelectric conversion element provided, and the present invention has been completed. That is, it has been found that the above object can be achieved by the following configuration.
- Photoelectric conversion element. (2) The photoelectric conversion device according to (1), wherein the absorption maximum wavelength of the compound represented by the formula (1) is in the range of 500 to 600 nm. (3) The photoelectric conversion element according to (1) or (2), wherein the compound represented by the above formula (1) is a compound represented by the following formula (2).
- R 3 is an alkyl group having 1 to 3 carbon atoms.
- the present invention it is possible to provide a photoelectric conversion element that exhibits excellent responsiveness and excellent manufacturing aptitude. Moreover, according to this invention, the optical sensor and imaging device provided with the said photoelectric conversion element can be provided.
- the characteristic point compared with the prior art of the present invention is that a squarylium compound having a predetermined structure (hereinafter, also simply referred to as “specific squarylium compound”) is used.
- a specific squarylium compound a specific organic group is introduced at a specific position.
- the characteristics (responsiveness and manufacturing suitability) of the photoelectric conversion element having the photoelectric conversion film containing the specific squarylium compound are improved. ing.
- FIG. 1A the cross-sectional schematic diagram of one Embodiment of the photoelectric conversion element of this invention is shown.
- a photoelectric conversion element 10a shown in FIG. 1A includes a conductive film (hereinafter also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking film 16A, and a photoelectric conversion that includes a compound represented by formula (1) described later.
- the film 12 and a transparent conductive film (hereinafter also referred to as an upper electrode) 15 functioning as an upper electrode are stacked in this order.
- FIG. 1B shows a configuration example of another photoelectric conversion element.
- FIGS. 1A and 1B has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are stacked on the lower electrode 11 in this order. Note that 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 appropriately changed according to the use and characteristics.
- the photoelectric conversion element 10 a it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15. Moreover, when using the photoelectric conversion element 10a (or 10b), a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 7 V / cm is applied between the pair of electrodes. From the viewpoint of performance and power consumption, a voltage of 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 7 V / cm is more preferable, and a voltage of 1 ⁇ 10 ⁇ 3 to 5 ⁇ 10 6 V / cm is more preferable.
- the photoelectric conversion element 10a (or 10b) is used as an optical sensor, or when it is incorporated in an imaging element, a voltage can be applied by the same method.
- the photoelectric conversion element 10a (or 10b) can be suitably applied to an imaging element application and an optical sensor application.
- FIG. 2 the cross-sectional schematic diagram of another embodiment of the photoelectric conversion element of this invention is shown.
- the photoelectric conversion element 200 shown in FIG. 2 is a hybrid photoelectric conversion element including an organic photoelectric conversion film 209 and an inorganic photoelectric conversion film 201.
- the organic photoelectric conversion film 209 includes a compound represented by the formula (1) described later.
- the inorganic photoelectric conversion film 201 has an n-type well 202, a p-type well 203, and an n-type well 204 on a p-type silicon substrate 205.
- Blue light is photoelectrically converted at the pn junction formed between the p-type well 203 and the n-type well 204 (B pixel), and the pn junction formed between the p-type well 203 and the n-type well 202 is converted into a pn junction.
- the red light is photoelectrically converted (R pixel). Note that the conductivity types of the n-type well 202, the p-type well 203, and the n-type well 204 are not limited to these.
- a transparent insulating layer 207 is disposed on the inorganic photoelectric conversion film 201.
- a transparent pixel electrode 208 divided for each pixel is disposed on the insulating layer 207, and an organic photoelectric conversion film 209 that absorbs green light and performs photoelectric conversion is disposed on the insulating layer 207 in a single pixel configuration.
- an electron blocking film 212 is arranged in a single sheet common to each pixel, on which a transparent common electrode 210 of a single sheet is arranged, and a transparent protective film 211 is arranged on the uppermost layer.
- the stacking order of the electron blocking film 212 and the organic photoelectric conversion film 209 may be opposite to that shown in FIG. 2, and the common electrode 210 may be divided for each pixel.
- the organic photoelectric conversion film 209 constitutes a G pixel that detects green light.
- the pixel electrode 208 is the same as the lower electrode 11 of the photoelectric conversion element 10a shown in FIG. 1A.
- the common electrode 210 is the same as the upper electrode 15 of the photoelectric conversion element 10a illustrated in FIG. 1A.
- Blue light having a short wavelength is photoelectrically converted mainly in the shallow part of the semiconductor substrate (inorganic photoelectric conversion film) 201 (near the pn junction formed between the p-type well 203 and the n-type well 204) to generate photocharges.
- the signal is output to the outside.
- Red light having a long wavelength is photoelectrically converted mainly in the deep part of the semiconductor substrate (inorganic photoelectric conversion film) 201 (near the pn junction formed between the p-type well 203 and the n-type well 202), and photocharge is generated.
- a signal is output to the outside.
- a signal readout circuit (a charge transfer path in the case of a CCD (Charge-Coupled Device) type, CMOS (Complementary-Metal-Oxide-Semiconductor) is provided on the surface of the p-type silicon substrate 205. If it is a type, a MOS (Metal-Oxide-Semiconductor) transistor circuit) or a green signal charge accumulation region is formed. In addition, the pixel electrode 208 is connected to a corresponding green signal charge accumulation region by a vertical wiring.
- CCD Charge-Coupled Device
- CMOS Complementary-Metal-Oxide-Semiconductor
- the photoelectric conversion film 12 (or the organic photoelectric conversion film 209) is a film containing a compound represented by the formula (1) as a photoelectric conversion material. By using this compound, a photoelectric conversion element having excellent responsiveness and production suitability can be obtained.
- the compound represented by Formula (1) will be described in detail.
- R 1 and R 2 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Among them, R 1 and R 2 are preferably aryl groups in that the responsiveness and / or production suitability of the photoelectric conversion element is more excellent (hereinafter also referred to simply as “the effect of the present invention is more excellent”). R 1 and R 2 may be connected to each other to form a ring.
- the kind of ring formed is not particularly limited, and may be an aromatic ring or a non-aromatic ring, and is preferably an aromatic ring.
- the ring may be a single ring or a condensed ring composed of two or more rings.
- the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
- the ring formed by connecting R 1 and R 2 to each other may be substituted with a substituent (preferably a substituent W described later).
- a substituent preferably a substituent W described later.
- R 1 and R 2 are aryl groups and are not connected to each other to form a ring.
- the number of carbon atoms in the alkyl group represented by R 1 and R 2 is not particularly limited, and is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3 in terms of more excellent effects of the present invention.
- the alkyl group may be linear, branched, or cyclic. Further, the alkyl group may be substituted with a substituent (preferably a substituent W (other than an alkyl group) described later). Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, and a cyclohexyl group.
- the number of carbon atoms in the aryl group represented by R 1 and R 2 is not particularly limited, and is preferably 6 to 30, and more preferably 6 to 18 in terms of more excellent effects of the present invention.
- the aryl group may be a monocyclic structure or a condensed ring structure in which two or more rings are condensed (fused ring structure).
- the aryl group may be substituted with a substituent (preferably, a substituent W described later).
- aryl group examples include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthrenyl group, a methylphenyl group, a dimethylphenyl group, a biphenyl group, and a fluorenyl group.
- a phenyl group, a naphthyl group, or Anthryl group is preferable, and a phenyl group is more preferable.
- the number of carbon atoms in the heteroaryl group (monovalent aromatic heterocyclic group) represented by R 1 and R 2 is not particularly limited, and is preferably 3 to 30 in terms of more excellent effects of the present invention. 18 is more preferred.
- the heteroaryl group may be substituted with a substituent (preferably, a substituent W described later).
- a heteroaryl group includes heteroatoms in addition to carbon and hydrogen atoms. Examples of the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and a nitrogen atom, a sulfur atom, or an oxygen atom is preferable.
- the number of heteroatoms contained in the heteroaryl group is not particularly limited, and is usually about 1 to 10, preferably 1 to 4, and more preferably 1 to 2.
- the number of ring members of the heteroaryl group is not particularly limited, preferably a 3- to 8-membered ring, more preferably a 5- to 7-membered ring, still more preferably a 5- to 6-membered ring.
- the heteroaryl group may be a monocyclic structure or a condensed ring structure in which two or more rings are condensed. In the case of a condensed ring structure, an aromatic hydrocarbon ring not containing a hetero atom (for example, a benzene ring) may be contained.
- heteroaryl group examples include pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, pteridinyl group, pyrazinyl group, quinoxalinyl group, pyrimidinyl group, quinazolyl group, pyridazinyl group, cinnolinyl group, and phthalazinyl group.
- R 3 represents an alkyl group, an aryl group, or a heteroaryl group.
- Examples of the alkyl group, aryl group or heteroaryl group represented by R 3 include those exemplified for R 1 and R 2 , and the preferred embodiments thereof are also the same.
- R 3 is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, from the viewpoint that the effects of the present invention are more excellent.
- A represents a ring containing at least one carbon atom and one cationic nitrogen atom.
- the one carbon atom and one cationic nitrogen atom are intended to be a carbon atom and a cationic nitrogen atom contained in a group represented by C ⁇ N + in the formula (1).
- the type of ring is not particularly limited, and may be an aromatic ring or a non-aromatic ring, and is preferably an aromatic ring.
- the ring may be a single ring or a condensed ring composed of two or more rings.
- the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Further, the ring may be substituted with a substituent (preferably, a substituent W described later).
- R 1 and R 2 each independently represents an aryl group or a heteroaryl group. Among these, R 1 and R 2 are preferably aryl groups in that the effects of the present invention are more excellent.
- R 1 and R 2 may be connected to each other to form a ring.
- the kind of ring formed is not particularly limited, and may be an aromatic ring or a non-aromatic ring, and is preferably an aromatic ring.
- the ring may be a single ring or a condensed ring composed of two or more rings.
- the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
- the ring formed by connecting R 1 and R 2 to each other may be substituted with a substituent (preferably a substituent W described later).
- R 1 and R 2 are aryl groups and are not connected to each other to form a ring.
- Aryl radicals represented by R 1, and R 2 and, definitions and the preferred embodiments of the heteroaryl group represented by R 1, and R 2 are similar to those shown by the above formula (1), respectively.
- R 3 are as defined for R 3 in the formula (1) and its preferred embodiments are also the same.
- R 4 to R 7 each independently represents a hydrogen atom or a substituent.
- the definition of the said substituent is synonymous with the substituent W mentioned later.
- adjacent groups (R 4 and R 5 , R 5 and R 6 , or R 6 and R 7 ) among R 4 to R 7 may be connected to each other to form a ring.
- the kind of ring formed is not particularly limited, and may be an aromatic ring or a non-aromatic ring, and is preferably an aromatic ring.
- the ring may be a single ring or a condensed ring composed of two or more rings.
- the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
- the ring formed by connecting adjacent groups among R 4 to R 7 may be substituted with a substituent (preferably a substituent W described later).
- R 4 to R 7 are preferably hydrogen atoms from the viewpoint of more excellent effects of the present invention.
- R A1 to R A5 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
- R A1 and R A2 are each independently preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group having 1 to 3 carbon atoms, from the viewpoint that the effects of the present invention are more excellent.
- R A3 and R A4 are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further a hydrogen atom. preferable.
- substituent W it describes about the substituent W in this specification.
- substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), and an alkynyl group.
- Aryl group, heterocyclic group may be referred to as heterocyclic group), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy Group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, Alkyl or ant Rusulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group
- substituent W may be further substituted with the substituent W.
- a halogen atom may be substituted on the alkyl group. The details of the substituent W are described in paragraph [0023] of JP-A-2007-234651.
- the molecular weight of the compound represented by the formula (1) is not particularly limited, but is preferably 300 to 900. When the molecular weight is 900 or less, the deposition temperature does not increase and the compound is hardly decomposed. When the molecular weight is 300 or more, the glass transition point of the deposited film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
- the compound represented by the formula (1) has an ionization potential of ⁇ 5.0 to ⁇ 6 in terms of the stability when used as a p-type organic semiconductor and the energy level of the n-type organic semiconductor.
- a compound that is 0.0 eV is preferred.
- the absorption maximum wavelength of the compound represented by the formula (1) is preferably in the range of 450 to 650 nm in order to be applicable to the organic photoelectric conversion film 209 that absorbs green light and performs photoelectric conversion as described above. More preferably, it is in the range of 600 nm.
- the absorption maximum wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the compound represented by the formula (1) to a concentration at which the absorbance is 0.5 to 1. .
- the compound represented by the formula (1) is particularly useful as a material for a photoelectric conversion film used for an image sensor, a photosensor, or a photovoltaic cell.
- the compound represented by the formula (1) often functions as a p-type organic compound (p-type organic semiconductor) in the photoelectric conversion film.
- the compound represented by Formula (1) can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescent diagnostic material.
- the photoelectric conversion film may contain components other than the compound represented by the formula (1) described above.
- the photoelectric conversion film may contain an n-type organic semiconductor.
- the n-type organic semiconductor is an acceptor organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting electrons. More specifically, an n-type organic semiconductor refers to an organic compound having a larger electron affinity when two organic compounds are used in contact with each other.
- n-type organic semiconductor examples include condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives), nitrogen atoms, oxygen atoms, and 5- to 7-membered heterocyclic compounds containing at least one sulfur atom (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, Tetrazole, pyrazole, imidazole, thiazole, etc.), polyarylene compounds, fluorene compounds, cyclopentadiene compounds, silyl compounds, and nitrogen-containing heterocyclic compounds as lig
- An organic dye may be used as the n-type organic semiconductor.
- the n-type organic semiconductor is colorless or has an absorption maximum wavelength and / or an absorption waveform close to those of the compound represented by the formula (1).
- the absorption maximum wavelength is 400 nm or less, or 500 nm or more and 600 nm or less.
- the photoelectric conversion film preferably has a bulk heterostructure formed by mixing the compound represented by the above formula (1) and the n-type organic semiconductor.
- the bulk heterostructure is a layer in which an n-type organic semiconductor and a p-type organic semiconductor are mixed and dispersed in a photoelectric conversion film.
- the photoelectric conversion film having a bulk heterostructure can be formed by either a wet method or a dry method.
- the bulk heterostructure is described in detail in ⁇ 0013> to ⁇ 0014> of JP-A-2005-303266.
- the film thickness in terms of a single layer of the compound represented / (the film thickness in terms of a single layer of the compound represented by the formula (1) + the film thickness in terms of a single layer of an n-type organic semiconductor) ⁇ 100) is 20 It is preferably ⁇ 80 volume%, more preferably 30 to 70 volume%, further preferably 35 to 65 volume%.
- the photoelectric conversion film containing the compound represented by the formula (1) is a non-light-emitting film and has characteristics different from those of an organic electroluminescent element (OLED).
- the non-light-emitting film is intended for a film having an emission quantum efficiency of 1% or less, and the emission quantum efficiency is preferably 0.5% or less, and more preferably 0.1% or less.
- the photoelectric conversion film can be formed mainly by a dry film forming method.
- the dry film forming method include vapor deposition (particularly, vacuum deposition), sputtering, ion plating, physical vapor deposition such as MBE (Molecular Beam Epitaxy), or plasma polymerization.
- CVD Chemical Vapor Deposition
- vacuum deposition is preferred.
- manufacturing conditions such as a degree of vacuum and a vapor deposition temperature can be set according to a conventional method.
- the thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, and still more preferably 50 to 500 nm.
- the electrodes are made of a conductive material.
- the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, the upper electrode 15 is preferably transparent to the light to be detected.
- the material constituting the upper electrode 15 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO).
- Conductive metal oxides metal thin films such as gold, silver, chromium and nickel, mixtures or laminates of these metals and conductive metal oxides, and polyaniline, polythiophene, polypyrrole, etc. Examples thereof include organic conductive materials. Among these, conductive metal oxides are preferable from the viewpoints of high conductivity and transparency.
- the sheet resistance is preferably 100 to 10,000 ⁇ / ⁇ .
- the degree of freedom in the range of film thickness that can be made thin is great.
- the thickness of the upper electrode (transparent conductive film) 15 decreases, the amount of light absorbed decreases, and the light transmittance generally increases.
- An increase in light transmittance is preferable because it increases light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
- the thickness of the upper electrode 15 is preferably 5 to 100 nm, and more preferably 5 to 20 nm.
- the lower electrode 11 may have transparency, or conversely, may have no transparency and reflect light.
- the material constituting the lower electrode 11 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO).
- Conductive metal oxides such as gold, silver, chromium, nickel, titanium, tungsten, and aluminum, and conductive compounds such as oxides or nitrides of these metals (for example, titanium nitride (TiN)) And mixtures or laminates of these metals and conductive metal oxides, and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.
- the method for forming the electrode is not particularly limited, and can be appropriately selected depending on the electrode material. Specific examples include wet methods such as a printing method and a coating method, physical methods such as a vacuum deposition method, a sputtering method, and an ion plating method, and chemical methods such as a CVD method and a plasma CVD method. .
- wet methods such as a printing method and a coating method
- physical methods such as a vacuum deposition method, a sputtering method, and an ion plating method
- chemical methods such as a CVD method and a plasma CVD method.
- methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method or the like), and a coating of a dispersion of indium tin oxide can be given.
- the photoelectric conversion element of the present invention may have a charge blocking film. By having this 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
- the electron blocking film contains an electron donating compound.
- polymer material examples include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, and diacetylene, or derivatives thereof.
- the electron blocking film may be composed of a plurality of films.
- the electron blocking film may be made of an inorganic material.
- an inorganic material has a dielectric constant larger than that of an organic material, when the inorganic material is used for an electron blocking film, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency is increased.
- inorganic materials that can serve as an electron blocking film include calcium oxide, chromium oxide, chromium oxide copper, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium copper oxide, niobium oxide, molybdenum oxide, and indium oxide. Examples thereof include copper, silver indium oxide, and iridium oxide.
- the hole blocking film contains an electron accepting compound.
- the electron accepting compound include oxadiazole derivatives such as 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7), anthraquinodimethane derivatives, and diphenylquinone derivatives.
- Bathocuproine, bathophenanthroline, and derivatives thereof triazole compounds, tris (8-hydroxyquinolinato) aluminum complexes, bis (4-methyl-8-quinolinato) aluminum complexes, distyrylarylene derivatives, triazine compounds, phenazine compounds
- examples include silole compounds.
- other examples include compounds described in paragraphs 0056 to 0057 of JP-A-2006-10077.
- the method for producing the charge blocking film is not particularly limited, and examples thereof include a dry film forming method and a wet film forming method.
- the dry film forming method include a vapor deposition method and a sputtering method.
- the vapor deposition may be either physical vapor deposition (PVD) or chemical vapor deposition (CVD), but physical vapor deposition such as vacuum vapor deposition is preferred.
- the wet film forming method include an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and a gravure coating method. From the viewpoint of precision patterning, the inkjet method is preferred.
- the thickness of the charge blocking film is preferably 10 to 200 nm, more preferably 30 to 150 nm, and still more preferably 30 to 100 nm.
- the photoelectric conversion element may further include a substrate.
- substrate used in particular is not restrict
- substrate is not restrict
- the photoelectric conversion element may further include a sealing layer.
- the performance of a photoelectric conversion material may be significantly degraded due to the presence of degradation factors such as water molecules. Accordingly, the entire photoelectric conversion film is covered with a sealing layer made of a dense metal oxide, metal nitride, metal nitride oxide, or other ceramic that does not allow water molecules to permeate, or diamond-like carbon (DLC), and sealed. By stopping, the above deterioration can be prevented.
- the material may be selected and manufactured according to paragraphs ⁇ 0210> to ⁇ 0215> of JP2011-082508A.
- the photoelectric conversion element examples include a photovoltaic cell and an optical sensor, and the photoelectric conversion element of the present invention is preferably used as an optical sensor.
- the photoelectric conversion element may be used alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged linearly or a two-dimensional sensor arranged on a plane.
- the photoelectric conversion element of the present invention converts optical image information into an electrical signal using an optical system and a drive unit like a scanner in a line sensor, and optically converts optical image information like an imaging module in a two-dimensional sensor.
- the system functions as an image sensor by forming an image on a sensor and converting it into an electrical signal.
- An image sensor is an element that converts optical information of an image into an electric signal.
- a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and an optical signal is converted into an electric signal in each photoelectric conversion element (pixel). That can be output to the outside of the imaging device for each pixel sequentially. Therefore, one pixel is composed of one photoelectric conversion element and one or more transistors.
- FIG. 3 is a schematic cross-sectional view showing a schematic configuration of an image sensor for explaining an embodiment of the present invention.
- This image pickup device is mounted on an image pickup apparatus such as a digital camera and a digital video camera, and an image pickup module such as an electronic endoscope and a mobile phone.
- This imaging element has a plurality of photoelectric conversion elements having the configuration as shown in FIG. 1A and a circuit board on which a readout circuit for reading a signal corresponding to the charge generated in the photoelectric conversion film of each photoelectric conversion element is formed.
- a plurality of photoelectric conversion elements are arranged one-dimensionally or two-dimensionally on the same surface above the circuit board.
- connection electrode 103 includes a connection electrode 103, a pixel electrode (lower electrode) 104, a connection portion 105, a connection portion 106, a photoelectric conversion film 107, and a counter electrode.
- the pixel electrode 104 has the same function as the lower electrode 11 of the photoelectric conversion element 10a shown in FIG. 1A.
- the counter electrode 108 has the same function as the upper electrode 15 of the photoelectric conversion element 10a illustrated in FIG. 1A.
- 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 10a illustrated in FIG. 1A.
- the substrate 101 is a glass substrate or a semiconductor substrate such as Si.
- An insulating layer 102 is formed on the substrate 101.
- a plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.
- the photoelectric conversion film 107 is a layer common to all the photoelectric conversion elements provided on the plurality of pixel electrodes 104 so as to cover them.
- the counter electrode 108 is one electrode provided on the photoelectric conversion film 107 and common to all the photoelectric conversion elements.
- the counter electrode 108 is formed up to the connection electrode 103 disposed outside the photoelectric conversion film 107, and is electrically connected to the connection electrode 103.
- connection unit 106 is a plug that is embedded in the insulating layer 102 and electrically connects the connection electrode 103 and the counter electrode voltage supply unit 115.
- the counter electrode voltage supply unit 115 is formed on the substrate 101 and applies a predetermined voltage to the counter electrode 108 via the connection unit 106 and the connection electrode 103.
- the power supply voltage is boosted by a booster circuit such as a charge pump to supply the predetermined voltage.
- the readout circuit 116 is provided on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the charge collected by the corresponding pixel electrode 104.
- the reading circuit 116 is constituted by, for example, a CCD, a CMOS circuit, or a TFT (Thin FilmTransistor) circuit, and is shielded by a light shielding layer (not shown) disposed in the insulating layer 102.
- the readout circuit 116 is electrically connected to the corresponding pixel electrode 104 via the connection unit 105.
- the buffer layer 109 is formed on the counter electrode 108 so as to cover the counter electrode 108.
- the sealing layer 110 is formed on the buffer layer 109 so as to cover the buffer layer 109.
- the color filter 111 is formed at a position facing each pixel electrode 104 on the sealing layer 110.
- the partition wall 112 is provided between the color filters 111 and is for improving the light transmission efficiency of the color filter 111.
- the light shielding layer 113 is formed in a region other than the region where the color filter 111 and the partition 112 are provided on the sealing layer 110, and prevents light from entering the photoelectric conversion film 107 formed outside the effective pixel region.
- the protective layer 114 is formed on the color filter 111, the partition 112, and the light shielding layer 113, and protects the entire image sensor 100.
- the imaging device 100 when light is incident, the light is incident on the photoelectric conversion film 107, and charges are generated here. Holes in the generated charges are collected by the pixel electrode 104, and a voltage signal corresponding to the amount is output to the outside of the image sensor 100 by the readout circuit 116.
- the manufacturing method of the image sensor 100 is as follows.
- 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 board on which the common 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 a square lattice pattern, for example.
- the photoelectric conversion film 107 is formed on the plurality of pixel electrodes 104 by, for example, a vacuum deposition method.
- the counter electrode 108 is formed on the photoelectric conversion film 107 under vacuum by, for example, sputtering.
- the buffer layer 109 and the sealing layer 110 are sequentially formed on the counter electrode 108 by, for example, a vacuum deposition method.
- the protective layer 114 is formed, and the imaging element 100 is completed.
- FIG. 5 shows the absorption spectrum of compound (D-1) in a chloroform solution.
- the absorption spectrum was measured using a UV-3600 manufactured by Shimadzu Corporation at a concentration of 10 ⁇ M (concentration where the absorbance is about 0.5 to 1).
- the ionization potential of compound (D-1) was ⁇ 5.13 eV.
- compounds (D-2) to (D-13) were also synthesized using the same reaction.
- the compound (R-1) corresponding to the comparative compound was purchased from Luminescence Technology.
- the compound (R-2) corresponding to the comparative compound corresponds to the squarylium compound described in Patent Document 1.
- a photoelectric conversion element having the configuration shown in FIG. 1A was produced using the obtained compound.
- the compound (D-1) is used as the case where the compound (D-1) is used.
- an amorphous ITO film is formed on a glass substrate by a sputtering method to form a lower electrode 11 (thickness: 30 nm), and molybdenum oxide (MoO x ) is further vacuum-deposited on the lower electrode 11.
- a molybdenum oxide layer was formed as the electron blocking film 16A.
- the compound (D-1) and the following compound (N-1) are vacuum heated and evaporated so as to be 40 nm and 40 nm, respectively, in terms of a single layer on the molybdenum oxide layer.
- the substrate temperature controlled at 25 ° C. the compound (D-1) and the following compound (N-1) are vacuum heated and evaporated so as to be 40 nm and 40 nm, respectively, in terms of a single layer on the molybdenum oxide layer.
- an amorphous ITO film was formed 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 is formed thereon by an ALCVD (Atomic Layer Chemical Vapor Deposition) method.
- ALCVD Atomic Layer Chemical Vapor Deposition
- the photoelectric conversion element produced here that is, the photoelectric conversion element provided with the photoelectric conversion film 12 having the compound (D-1) and the following compound (N-1) at 40 nm and 40 nm, respectively, in terms of a single layer, It is called a photoelectric conversion element A.
- Each Example was performed according to the same procedure as above except that the compound (D-1) was changed to each of the compounds (D-2) to (D-13) and the compounds (R-1) to (R-2).
- a photoelectric conversion element A was prepared.
- the following responsiveness was evaluated. Specifically, a voltage was applied to the photoelectric conversion element A so as to have an intensity of 2.0 ⁇ 10 5 V / cm. After that, the LED (light emitting diode) is turned on instantaneously, light is irradiated from the upper electrode (transparent conductive film) side, the photocurrent at that time is measured with an oscilloscope, and the signal intensity ranges from 0 to 97%. Rise time was measured. And the relative value when the rise time of the comparative example 1 was set to 10 was calculated
- the relative value of the rise time is “A” when the relative value of the rise time is less than 3, “B” when 3 or more and less than 5, and “C” when 5 or more and less than 10, and 10 or more.
- the results are shown in Table 4. Practically, it is preferably “A” or “B”, and more preferably “A”.
- the photoelectric conversion film 12 was prepared by the same method except that the compound (D-1) and the compound (N-1) were changed to 30 nm and 50 nm, respectively, in terms of a single layer. B was produced. Further, in the production of the photoelectric conversion element A described above, the photoelectric conversion film 12 was subjected to photoelectric conversion by a similar method except that the compound (D-1) and the compound (N-1) were changed to 50 nm and 30 nm in terms of a single layer, respectively. A conversion element C was produced.
- Photoelectric conversion elements (A, B, C) were prepared. Next, using the photoelectric conversion elements A to C, the following photoelectric conversion efficiency was evaluated. Specifically, a voltage was applied to each photoelectric conversion element so as to have an intensity of 2.0 ⁇ 10 5 V / cm to measure the photoelectric conversion efficiency at 550 nm, and a comparative evaluation was performed based on the relative value. .
- the photoelectric conversion element of the present invention containing the compound represented by the formula (1) as a photoelectric conversion material has excellent responsiveness and excellent manufacturing aptitude (composition ratio dependency of photoelectric conversion efficiency).
- the photoelectric conversion element of the present invention containing the compound represented by the formula (1) as a photoelectric conversion material has excellent responsiveness and excellent manufacturing aptitude (composition ratio dependency of photoelectric conversion efficiency).
- Examples 1, 4, 5, 7, 8, 11, and 12 when R 1 and R 2 are aryl groups or heteroaryl groups in the compound represented by formula (1) (in other words, photoelectric conversion) It was shown that when the material is a compound represented by the formula (2), responsiveness and manufacturability (characteristic in which the photoelectric conversion efficiency is less dependent on the composition ratio) can be well balanced.
- An image sensor similar to that shown in FIG. 3 was produced. That is, after depositing amorphous TiN 30 nm on the CMOS substrate by sputtering, patterning is performed by photolithography so that one pixel exists on each photodiode (PD) on the CMOS substrate to form the lower electrode. After the formation of the electron blocking material, it was produced in the same manner as in Examples 1 to 13. The responsiveness evaluation and the manufacturing suitability (composition ratio dependency of photoelectric conversion efficiency) of the obtained image sensor are also performed in the same manner, and the same results as in Table 4 are obtained, and the image sensor also exhibits excellent performance. I understood.
- Photoelectric conversion element 11 Conductive film (lower electrode) 12 Photoelectric conversion film 15 Transparent conductive film (upper electrode) 16A Electron blocking film 16B Hole blocking film 100 Pixel separation type imaging device 101 Substrate 102 Insulating layer 103 Connection electrode 104 Pixel electrode (lower electrode) 105 connecting portion 106 connecting portion 107 photoelectric conversion film 108 counter electrode (upper electrode) 109 Buffer layer 110 Sealing layer 111 Color filter (CF) DESCRIPTION OF SYMBOLS 112 Partition 113 Light shielding layer 114 Protective layer 115 Counter electrode voltage supply part 116 Read-out circuit 200 Photoelectric conversion element (hybrid type photoelectric conversion element) 201 Inorganic photoelectric conversion film 202 n-type well 203 p-type well 204 n-type well 205 p-type silicon substrate 207 insulating layer 208 pixel electrode 209 organic photoelectric conversion film 210 common electrode 211 protective film 212 electron blocking film
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Abstract
Description
カラー固体撮像素子を実現するには、平面型固体撮像素子の光入射面側に、特定の波長の光を透過するカラーフィルタを配した構造が一般的である。現在、2次元的に配列した各PD上に、青色(B)光、緑色(G)光、及び、赤色(R)光を透過するカラーフィルタを規則的に配した単板式固体撮像素子がよく知られている。しかし、この単板式固体撮像素子においては、カラーフィルタを透過しなかった光が利用されず光利用効率が悪い。
これらの欠点を解決するため、近年、有機光電変換膜を信号読み出し用基板上に配置した構造を有する光電変換素子の開発が進んでいる。
また、本発明は、上記光電変換素子を備えた光センサ及び撮像素子を提供することを課題とする。
すなわち、以下の構成により上記目的を達成することができることを見出した。
(2) 上記式(1)で表される化合物の吸収極大波長が500~600nmの範囲にある、(1)に記載の光電変換素子。
(3) 上記式(1)で表される化合物が、後述する式(2)で表される化合物である、(1)又は(2)に記載の光電変換素子。
(4) 上記R1及びR2はアリール基である、(1)~(3)のいずれかに記載の光電変換素子。
(5) 上記R3は炭素数1~3のアルキル基である、(1)~(4)のいずれかに記載の光電変換素子。
(6) 上記R4~R7は水素原子である、(3)に記載の光電変換素子。
(7) 上記光電変換膜が、更にn型有機半導体を含有する、(1)~(6)のいずれかに記載の光電変換素子。
(8) 更に、電荷ブロッキング膜を有する、(1)~(7)のいずれかに記載の光電変換素子。
(9) (1)~(8)のいずれかに記載の光電変換素子を含む光センサ。
(10) (1)~(8)のいずれかに記載の光電変換素子を含む撮像素子。
以下に、本発明の光電変換素子の好適実施形態について説明する。
なお、本明細書において置換又は無置換を明記していない置換基等については、目的とする効果を損なわない範囲で、その基に更に置換基(好ましくは、後述する置換基W)が置換していてもよい。例えば、「アルキル基」という表記は、置換基(好ましくは、置換基W)が置換していてもよいアルキル基に該当する。
また、本明細書において「~」を用いて表される数値範囲は、「~」前後に記載される数値を下限値及び上限値として含む範囲を意味する。
図1Aに示す光電変換素子10aは、下部電極として機能する導電性膜(以下、下部電極とも記す)11と、電子ブロッキング膜16Aと、後述する式(1)で表される化合物を含む光電変換膜12と、上部電極として機能する透明導電性膜(以下、上部電極とも記す)15とがこの順に積層された構成を有する。
図1Bに別の光電変換素子の構成例を示す。図1Bに示す光電変換素子10bは、下部電極11上に、電子ブロッキング膜16Aと、光電変換膜12と、正孔ブロッキング膜16Bと、上部電極15とがこの順に積層された構成を有する。なお、図1A及び図1B中の電子ブロッキング膜16A、光電変換膜12、及び、正孔ブロッキング膜16Bの積層順は、用途及び特性に応じて、適宜変更してもよい。
また、光電変換素子10a(又は、10b)を使用する場合には、電圧を印加することができる。この場合、下部電極11と上部電極15とが一対の電極をなし、この一対の電極間に、1×10-5~1×107V/cmの電圧を印加することが好ましい。性能及び消費電力の観点から、1×10-4~1×107V/cmの電圧がより好ましく、1×10-3~5×106V/cmの電圧が更に好ましい。
なお、電圧印加方法については、図1A及び図1Bにおいて、電子ブロッキング膜16A側が陰極となり、光電変換膜12側が陽極となるように印加することが好ましい。光電変換素子10a(又は、10b)を光センサとして使用した場合、また、撮像素子に組み込んだ場合も、同様の方法により電圧を印加できる。
後段で、詳述するように、光電変換素子10a(又は、10b)は撮像素子用途、及び、光センサ用途に好適に適用できる。
図2に示される光電変換素子200は、有機光電変換膜209と無機光電変換膜201とを備えるハイブリッド型の光電変換素子である。なお、有機光電変換膜209には、後述する式(1)で表される化合物が含まれる。
無機光電変換膜201は,p型シリコン基板205上に、n型ウェル202、p型ウェル203、及び、n型ウェル204を有する。
p型ウェル203とn型ウェル204との間に形成されるpn接合にて青色光が光電変換され(B画素)、p型ウェル203とn型ウェル202との間に形成されるpn接合にて赤色光が光電変換される(R画素)。なお、n型ウェル202、p型ウェル203、及びn型ウェル204の導電型は、これらに限らない。
絶縁層207の上には、画素毎に区分けした透明な画素電極208が配置され、その上に、緑色光を吸収して光電変換する有機光電変換膜209が各画素共通に一枚構成で配置され、その上に、電子ブロッキング膜212が各画素共通に一枚構成で配置され、その上に、一枚構成の透明な共通電極210が配置され、最上層に、透明な保護膜211が配置されている。電子ブロッキング膜212と有機光電変換膜209との積層順は図2とは逆であってもよく、共通電極210は、画素毎に区分けして配置されてもよい。
有機光電変換膜209は、緑色光を検出するG画素を構成する。
(式(1)で表される化合物)
光電変換膜12(又は、有機光電変換膜209)は、光電変換材料として式(1)で表される化合物を含む膜である。この化合物を使用することにより、優れた応答性及び製造適性を示す光電変換素子が得られる。
以下、式(1)で表される化合物について詳述する。
なお、R1とR2とは互いに連結して環を形成してもよい。形成される環の種類は特に制限されず、芳香環であっても、非芳香環であってもよく、芳香環であることが好ましい。また、環は、単環であっても、2つ以上の環からなる縮環であってもよい。また、芳香環は、芳香族炭化水素環であっても、芳香族複素環であってもよい。R1とR2とが互いに連結して形成される環には、置換基(好ましくは、後述する置換基W)が置換していてもよい。
本発明の効果がより優れる点では、R1及びR2は、アリール基であり、且つ、互いに連結して環を形成しないことがより好ましい。
上記アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、i-プロピル基、n―ブチル基、n-ヘキシル基、及び、シクロへキシル基等が挙げられる。
上記アリール基としては、例えば、フェニル基、ナフチル基、アントリル基、ピレニル基、フェナントレニル基、メチルフェニル基、ジメチルフェニル基、ビフェニル基、及び、フルオレニル基等が挙げられ、フェニル基、ナフチル基、又は、アントリル基が好ましく、フェニル基がより好ましい。
ヘテロアリール基には、炭素原子及び水素原子以外にヘテロ原子が含まれる。ヘテロ原子としては、例えば、窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、及び、ホウ素原子が挙げられ、窒素原子、硫黄原子、又は、酸素原子が好ましい。
ヘテロアリール基に含まれるヘテロ原子の数は特に制限されず、通常、1~10個程度であり、1~4個が好ましく、1~2個がより好ましい。
ヘテロアリール基の環員数は特に制限されず、3~8員環が好ましく、5~7員環がより好ましく、5~6員環が更に好ましい。なお、ヘテロアリール基は、単環構造であっても、2つ以上の環が縮環した縮環構造であってもよい。縮環構造の場合、ヘテロ原子を含まない芳香族炭化水素環(例えば、ベンゼン環)が含まれていてもよい。
上記ヘテロアリール基としては、例えば、ピリジル基、キノリル基、イソキノリル基、アクリジニル基、フェナントリジニル基、プテリジニル基、ピラジニル基、キノキサリニル基、ピリミジニル基、キナゾリル基、ピリダジニル基、シンノリニル基、フタラジニル基、トリアジニル基、オキサゾリル基、ベンゾオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、イミダゾリル基、ベンゾイミダゾリル基、ピラゾリル基、インダゾリル基、イソオキサゾリル基、ベンゾイソオキサゾリル基、イソチアゾリル基、ベンゾイソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、テトラゾリル基、フリル基、ベンゾフリル基、チエニル基、ベンゾチエニル基、ジベンゾフリル基、ジベンゾチエニル基、ピロリル基、インドリル基、イミダゾピリジニル基、及び、カルバゾリル基等が挙げられる。
Aは、1つの炭素原子と1つのカチオン性窒素原子とを少なくとも含む環を表す。なお、上記1つの炭素原子及び1つのカチオン性窒素原子は、式(1)中のC=N+で表される基に含まれる炭素原子及びカチオン性窒素原子を意図する。環の種類は特に制限されず、芳香環であっても、非芳香環であってもよく、芳香環であることが好ましい。また、環は、単環であっても、2つ以上の環からなる縮環であってもよい。また、芳香環は、芳香族炭化水素環であっても、芳香族複素環であってもよい。また、上記環には、置換基(好ましくは、後述する置換基W)が置換していてもよい。
上記式(1)で表される化合物のなかでも、下記式(2)で表される化合物がより好ましい。
なお、R1とR2とは互いに連結して環を形成してもよい。形成される環の種類は特に制限されず、芳香環であっても、非芳香環であってもよく、芳香環であることが好ましい。また、環は、単環であっても、2つ以上の環からなる縮環であってもよい。また、芳香環は、芳香族炭化水素環であっても、芳香族複素環であってもよい。R1とR2とが互いに連結して形成される環には、置換基(好ましくは、後述する置換基W)が置換していてもよい。
本発明の効果がより優れる点では、R1及びR2は、アリール基であり、且つ、互いに連結して環を形成しないことが好ましい。
R1及びR2で表されるアリール基、及び、R1及びR2で表されるヘテロアリール基の定義及びその好適態様は、それぞれ上記式(1)で示したものと同様である。
式(2)中、R4~R7は、それぞれ独立に、水素原子又は置換基を表す。上記置換基の定義は、後述する置換基Wと同義である。
なお、R4~R7のうち隣り合う基同士(R4とR5、R5とR6、又はR6とR7)は、それぞれ互いに連結して環を形成してもよい。形成される環の種類は特に制限されず、芳香環であっても、非芳香環であってもよく、芳香環であることが好ましい。また、環は、単環であっても、2つ以上の環からなる縮環であってもよい。また、芳香環は、芳香族炭化水素環であっても、芳香族複素環であってもよい。R4~R7のうち隣り合う基同士が互いに連結して形成される環には、置換基(好ましくは、後述する置換基W)が置換していてもよい。
なかでも、本発明の効果がより優れる点で、R4~R7は、水素原子が好ましい。
RA1~RA5は、それぞれ独立に、水素原子、アルキル基、アリール基、又はヘテロアリール基を表す。RA1~RA5で表されるアルキル基、アリール基、又はヘテロアリール基としては、R1及びR2で例示したものが挙げられ、またその好適態様も同じである。なかでも、本発明の効果がより優れる点で、RA1及びRA2は、それぞれ独立に、水素原子又はアルキル基が好ましく、炭素数1~3のアルキル基がより好ましい。また、本発明の効果がより優れる点で、RA3及びRA4は、それぞれ独立に、水素原子又はアルキル基が好ましく、水素原子又は炭素数1~3のアルキル基がより好ましく、水素原子が更に好ましい。
なお、下記表中、「Ph」はフェニル基を表し、「Me」はメチル基を表し、「Et」はエチル基を表し、「Pr」はプロピル基を表し、「Bu」はブチル基を表す。また、表中のX1欄において、「-C(CH3)2-」は「-C(CH3)2-」を意味し、「-CH2=CH2-」は「-CH2=CH2-」を意味する。
置換基Wとしては、例えば、ハロゲン原子、アルキル基(シクロアルキル基、ビシクロアルキル基、及び、トリシクロアルキル基を含む)、アルケニル基(シクロアルケニル基、及び、ビシクロアルケニル基を含む)、アルキニル基、アリール基、複素環基(ヘテロ環基といってもよい)、シアノ基、ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基(アニリノ基を含む)、アンモニオ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル又はアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキル又はアリールスルフィニル基、アルキル又はアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール又はヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ホスホノ基、シリル基、ヒドラジノ基、ウレイド基、ボロン酸基(-B(OH)2)、ホスファト基(-OPO(OH)2)、スルファト基(-OSO3H)、及び、その他の公知の置換基が挙げられる。
また、置換基Wは、更に置換基Wで置換されていてもよい。例えば、アルキル基にハロゲン原子が置換していてもよい。
なお、置換基Wの詳細については、特開2007-234651号公報の段落[0023]に記載される。
光電変換膜には、上述した式(1)で表される化合物以外の他の成分が含まれていてもよい。例えば、光電変換膜には、n型有機半導体が含まれていてもよい。
n型有機半導体とは、アクセプタ性有機半導体材料(化合物)であり、電子を受容しやすい性質がある有機化合物をいう。更に詳しくは、n型有機半導体とは、2つの有機化合物を接触させて用いたときに電子親和力の大きい方の有機化合物をいう。
n型有機半導体としては、例えば、縮合芳香族炭素環化合物(例えば、ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、テトラセン誘導体、ピレン誘導体、ペリレン誘導体、及び、フルオランテン誘導体)、窒素原子、酸素原子、及び、硫黄原子の少なくとも1つを含有する5~7員のヘテロ環化合物(例えば、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、キノリン、キノキサリン、キナゾリン、フタラジン、シンノリン、イソキノリン、プテリジン、アクリジン、フェナジン、フェナントロリン、テトラゾール、ピラゾール、イミダゾール、及び、チアゾール等)、ポリアリーレン化合物、フルオレン化合物、シクロペンタジエン化合物、シリル化合物、並びに、含窒素ヘテロ環化合物を配位子として有する金属錯体等が挙げられる。
光電変換膜は、主に、乾式成膜法により成膜できる。乾式成膜法の具体例としては、蒸着法(特に、真空蒸着法)、スパッタリング法、イオンプレーティング法、及び、MBE(Molecular Beam Epitaxy)法等の物理気相成長法、又は、プラズマ重合等のCVD(Chemical Vapor Deposition)法が挙げられる。なかでも、真空蒸着法が好ましい。真空蒸着法により光電変換膜を成膜する場合、真空度及び蒸着温度等の製造条件は常法に従って設定することができる。
電極(上部電極(透明導電性膜)15と下部電極(導電性膜)11)は、導電性材料から構成される。導電性材料としては、金属、合金、金属酸化物、電気伝導性化合物、及び、これらの混合物等が挙げられる。
上部電極15から光が入射されるため、上部電極15は検知したい光に対し透明であることが好ましい。上部電極15を構成する材料としては、例えば、アンチモン又はフッ素等をドープした酸化錫(ATO、FTO)、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫(ITO)、及び、酸化亜鉛インジウム(IZO)等の導電性金属酸化物、金、銀、クロム、及び、ニッケル等の金属薄膜、これらの金属と導電性金属酸化物との混合物又は積層物、並びに、ポリアニリン、ポリチオフェン、及び、ポリピロール等の有機導電性材料等が挙げられる。なかでも、高導電性及び透明性等の点から、導電性金属酸化物が好ましい。
電極の材料がITOの場合、電子ビーム法、スパッタリング法、抵抗加熱蒸着法、化学反応法(ゾル-ゲル法等)、及び、酸化インジウムスズの分散物の塗布等の方法が挙げられる。
本発明の光電変換素子は、電荷ブロッキング膜を有していてもよい。この膜を有することにより、得られる光電変換素子の特性(光電変換効率及び応答速度等)がより優れる。電荷ブロッキング膜としては、電子ブロッキング膜と正孔ブロッキング膜とが挙げられる。以下に、それぞれの膜について詳述する。
電子ブロッキング膜には、電子供与性化合物が含まれる。具体的には、低分子材料では、N,N’-ビス(3-メチルフェニル)-(1,1’-ビフェニル)-4,4’-ジアミン(TPD)、及び、4,4’-ビス[N-(ナフチル)-N-フェニル-アミノ]ビフェニル(α-NPD)等の芳香族ジアミン化合物、ポルフィリン、テトラフェニルポルフィリン銅、フタロシアニン、銅フタロシアニン、及び、チタニウムフタロシアニンオキサイド等のポルフィリン化合物、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、スチルベン誘導体、ピラゾリン誘導体、テトラヒドロイミダゾール、ポリアリールアルカン、ブタジエン、4,4’,4’’-トリス(N-(3-メチルフェニル)N-フェニルアミノ)トリフェニルアミン(m-MTDATA)、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、並びに、シラザン誘導体等が挙げられ、高分子材料では、フェニレンビニレン、フルオレン、カルバゾール、インドール、ピレン、ピロール、ピコリン、チオフェン、アセチレン、及び、ジアセチレン等の重合体、又は、その誘導体が挙げられる。
電子ブロッキング膜は、無機材料で構成されていてもよい。一般的に、無機材料は有機材料よりも誘電率が大きいため、無機材料を電子ブロッキング膜に用いた場合に、光電変換膜に電圧が多くかかるようになり、光電変換効率が高くなる。電子ブロッキング膜となりうる無機材料としては、例えば、酸化カルシウム、酸化クロム、酸化クロム銅、酸化マンガン、酸化コバルト、酸化ニッケル、酸化銅、酸化ガリウム銅、酸化ストロンチウム銅、酸化ニオブ、酸化モリブデン、酸化インジウム銅、酸化インジウム銀、及び、酸化イリジウム等が挙げられる。
正孔ブロッキング膜には、電子受容性化合物が含まれる。
電子受容性化合物としては、1,3-ビス(4-tert-ブチルフェニル-1,3,4-オキサジアゾリル)フェニレン(OXD-7)等のオキサジアゾール誘導体、アントラキノジメタン誘導体、ジフェニルキノン誘導体、バソクプロイン、バソフェナントロリン、及びこれらの誘導体、トリアゾール化合物、トリス(8-ヒドロキシキノリナート)アルミニウム錯体、ビス(4-メチル-8-キノリナート)アルミニウム錯体、ジスチリルアリーレン誘導体、トリアジン化合物、フェナジン化合物、並びに、シロール化合物等が挙げられる。また、その他にも特開2006-100767の段落0056~0057に記載の化合物などが挙げられる。
光電変換素子は、更に基板を含んでいてもよい。使用される基板の種類は特に制限されず、半導体基板、ガラス基板、及び、プラスチック基板が挙げられる。
なお、基板の位置は特に制限されず、通常、基板上に導電性膜、光電変換膜、及び透明導電性膜をこの順で積層する。
光電変換素子は、更に封止層を含んでいてもよい。光電変換材料は水分子等の劣化因子の存在で顕著にその性能が劣化することがある。そこで、水分子を浸透させない緻密な金属酸化物、金属窒化物、及び、金属窒化酸化物等のセラミックス、又は、ダイヤモンド状炭素(DLC)等の封止層で光電変換膜全体を被覆して封止することで、上記劣化を防止できる。
なお、封止層としては、特開2011-082508号公報の段落<0210>~<0215>に記載に従って、材料の選択及び製造を行ってもよい。
光電変換素子の用途として、例えば、光電池及び光センサが挙げられ、本発明の光電変換素子は光センサとして用いることが好ましい。光センサとしては、上記光電変換素子単独で用いてもよいし、上記光電変換素子を直線状に配したラインセンサ、又は、平面上に配した2次元センサとして用いてもよい。本発明の光電変換素子は、ラインセンサでは、スキャナー等の様に光学系及び駆動部を用いて光画像情報を電気信号に変換し、2次元センサでは、撮像モジュールのように光画像情報を光学系でセンサ上に結像させ電気信号に変換することで撮像素子として機能する。
次に、光電変換素子10aを備えた撮像素子の構成例を説明する。
なお、以下に説明する構成例において、すでに説明した部材等と同等な構成又は作用を有する部材等については、図中に同一符号又は相当符号を付すことにより、説明を簡略化又は省略する。
撮像素子とは画像の光情報を電気信号に変換する素子であり、複数の光電変換素子が同一平面状でマトリクス上に配置されており、各々の光電変換素子(画素)において光信号を電気信号に変換し、その電気信号を画素ごとに逐次撮像素子外に出力できるものをいう。そのために、画素ひとつあたり、一つの光電変換素子、一つ以上のトランジスタから構成される。
図3は、本発明の一実施形態を説明するための撮像素子の概略構成を示す断面模式図である。この撮像素子は、デジタルカメラ及びデジタルビデオカメラ等の撮像装置、並びに、電子内視鏡及び携帯電話機等の撮像モジュール等に搭載される。
この撮像素子は、図1Aに示したような構成の複数の光電変換素子と、各光電変換素子の光電変換膜で発生した電荷に応じた信号を読み出す読み出し回路が形成された回路基板とを有し、回路基板上方の同一面上に、複数の光電変換素子が一次元状又は二次元状に配列された構成となっている。
対向電極電圧供給部115と読み出し回路116が形成された回路基板上に、接続部105及び106、複数の接続電極103、複数の画素電極104、並びに、絶縁層102を形成する。複数の画素電極104は、絶縁層102の表面に例えば正方格子状に配置する。
化合物(D-1)は、以下のスキームに従って、合成した。
得られた化合物(D-1)は、NMR(Nuclear Magnetic Resonance)、及びMS(Mass Spectrometry)により同定した。
1H NMRスペクトル(400MHz、CDCl3)を図4に示す。
MS(ESI+)m/z:420.3([M+H]+)
なお、比較化合物に該当する化合物(R-1)は、Luminescence Technology社より購入した。また、比較化合物に該当する化合物(R-2)は、特許文献1に記載されたスクアリリウム化合物に相当する。
得られた化合物を用いて図1Aの形態の光電変換素子を作製した。以下では、化合物(D-1)を用いた場合について詳述する。
具体的には、ガラス基板上に、アモルファス性ITOをスパッタ法により成膜して、下部電極11(厚み:30nm)を形成し、更に下部電極11上に酸化モリブデン(MoOX)を真空加熱蒸着法により成膜して、電子ブロッキング膜16Aとして酸化モリブデン層(厚み:30nm)を形成した。
更に、基板の温度を25℃に制御した状態で、酸化モリブデン層上に化合物(D-1)と下記化合物(N-1)とをそれぞれ単層換算で40nm、40nmとなるように真空加熱蒸着により共蒸着して成膜し、80nmの光電変換膜12を形成した。
更に、光電変換膜12上に、アモルファス性ITOをスパッタ法により成膜して、上部電極15(透明導電性膜)(厚み:10nm)を形成した。上部電極15上に、加熱蒸着により封止層としてSiO膜を形成した後、その上にALCVD(Atomic Layer Chemical Vapor Deposition)法により酸化アルミニウム(Al2O3)層を形成し、光電変換素子を作製した。
なお、ここで作製した光電変換素子、つまり、化合物(D-1)と下記化合物(N-1)とをそれぞれ単層換算で40nm、40nmで有する光電変換膜12を備えた光電変換素子を、光電変換素子Aという。
(光電変換素子としての動作確認)
得られた光電変換素子Aを用いて、以下の動作確認の評価を実施した。
具体的には、光電変換素子Aに2.0×105V/cmの強度になるように電圧を印加し、550nmにおける光電変換の外部量子効率(入射光子が出力電子に変換された効率、以下「光電変換効率」ともいう。)を測定した。
この結果、得られた光電変換素子Aは、その550nmにおける光電変換効率がいずれも30%超であり、光電変換素子として機能することを確認した。
得られた光電変換素子Aを用いて、以下の応答性の評価を実施した。
具体的には、光電変換素子Aに2.0×105V/cmの強度となるように電圧を印加した。その後、LED(light emitting diode)を瞬間的に点灯させて上部電極(透明導電性膜)側から光を照射し、そのときの光電流をオシロスコープで測定して、0から97%信号強度までの立ち上がり時間を計った。そして比較例1の立ち上がり時間を10としたときの相対値を求めた。
なお、立ち上がり時間の相対値が比較例1に対して、3未満のものを「A」、3以上5未満のものを「B」、5以上10未満のものを「C」、10以上のものを「D」とした。結果を表4に示す。実用上、「A」又は「B」であることが好ましく、「A」であることがより好ましい。
上述した光電変換素子Aの作製において、光電変換膜12を、化合物(D-1)と化合物(N-1)とをそれぞれ単層換算で30nm、50nmとした以外は同様の方法により光電変換素子Bを作製した。また、上述した光電変換素子Aの作製において、光電変換膜12を、化合物(D-1)と化合物(N-1)とをそれぞれ単層換算で50nm、30nmとした以外は同様の方法により光電変換素子Cを作製した。
つまり、光電変換膜12中において化合物(D-1)とn型有機半導体との組成比が異なる(言い換えると、光電変換膜12中の化合物(D-1)の含有量が異なる)3種の光電変換素子(A、B、C)を準備した。
次に、光電変換素子A~Cを用いて、以下の光電変換効率の評価を実施した。
具体的には、各光電変換素子に2.0×105V/cmの強度になるように電圧を印加して550nmにおける光電変換効率を測定し、その相対値に基づいて比較評価を実施した。
なお、光電変換素子A~Cの光電変換効率の平均値を1とした場合に、相対値が最も離れている光電変換素子の光電変換効率の値が、0.9~1.1の場合には「A」、0.8以上0.9未満、又は、1.1超1.2以下の場合には「B」、0.8未満、又は、1.2超の場合には「C」として評価した。実用上、「A」又は「B」であることが好ましく、「A」であることがより好ましい。
なお、上記化合物(D-1)を、化合物(D-2)~(D-13)及び化合物(R-1)~(R-2)のそれぞれに変更した以外は上記と同様の手順に従って、各例の光電変換素子B及び光電変換素子Cを作製し、上記と同様の評価を実施した。
結果を表4に示す。
例1、4、5、7、8、11、12の対比から、式(1)で表される化合物中、R1及びR2がアリール基又はヘテロアリール基である場合(言い換えると、光電変換材料が式(2)で表される化合物である場合)、応答性と製造適性(光電変換効率の組成比依存性が小さい特性)とをよりバランスがよく両立できることが示された。
また、なかでも、例1、4、5、7、8、12の対比から、式(1)で表される化合物中、R1及びR2がアリール基である場合、応答性により優れることを確認した。特に、例1、4、5、7、8の対比から、R1及びR2がアリール基であり、且つ、互いに連結して環を形成しない場合、応答性と製造適性(光電変換効率の組成比依存性が小さい特性)をより優れたレベルで両立できることを確認した。
例1、6の対比から、式(2)で表される化合物中、R4~R7が水素原子の場合、応答性により優れることが確認された。
例1、9、10の対比から、式(2)で表される化合物中、R3が炭素数1~3のアルキル基の場合、応答性により優れることが確認された。
図3に示す形態と同様の撮像素子を作製した。すなわち、CMOS基板上に、アモルファス性TiN 30nmをスパッタ法により成膜後、フォトリソグラフィーによりCMOS基板上のフォトダイオード(PD)の上にそれぞれ1つずつ画素が存在するようにパターニングして下部電極とし、電子ブロッキング材料の成膜以降は例1~13と同様に作製した。得られた撮像素子での応答性評価及び製造適性(光電変換効率の組成比依存性)の評価も同様に行い、表4と同様な結果が得られ、撮像素子においても優れた性能を示すことが分かった。
11 導電性膜(下部電極)
12 光電変換膜
15 透明導電性膜(上部電極)
16A 電子ブロッキング膜
16B 正孔ブロッキング膜
100 画素分離型撮像素子
101 基板
102 絶縁層
103 接続電極
104 画素電極(下部電極)
105 接続部
106 接続部
107 光電変換膜
108 対向電極(上部電極)
109 緩衝層
110 封止層
111 カラーフィルタ(CF)
112 隔壁
113 遮光層
114 保護層
115 対向電極電圧供給部
116 読み出し回路
200 光電変換素子(ハイブリッド型の光電変換素子)
201 無機光電変換膜
202 n型ウェル
203 p型ウェル
204 n型ウェル
205 p型シリコン基板
207 絶縁層
208 画素電極
209 有機光電変換膜
210 共通電極
211 保護膜
212 電子ブロッキング膜
Claims (10)
- 前記式(1)で表される化合物の吸収極大波長が500~600nmの範囲にある、請求項1に記載の光電変換素子。
- 前記式(1)で表される化合物が、式(2)で表される化合物である、請求項1又は2に記載の光電変換素子。
式(2)中、R1及びR2は、それぞれ独立に、アリール基又はヘテロアリール基を表す。R1とR2とは互いに連結して環を形成してもよい。R3は、アルキル基、アリール基、又はヘテロアリール基を表す。R4~R7は、それぞれ独立に、水素原子又は置換基を表す。R4とR5、R5とR6、又はR6とR7は、それぞれ互いに連結して環を形成してもよい。X1は硫黄原子、酸素原子、セレン原子、CRA1RA2、CRA3=CRA4、及びNRA5から選ばれるいずれかを表す。RA1~RA5は、それぞれ独立に、水素原子、アルキル基、アリール基、又はヘテロアリール基を表す。 - 前記R1及びR2はアリール基である、請求項1~3のいずれか1項に記載の光電変換素子。
- 前記R3は炭素数1~3のアルキル基である、請求項1~4のいずれか1項に記載の光電変換素子。
- 前記R4~R7は水素原子である、請求項3に記載の光電変換素子。
- 前記光電変換膜が、更にn型有機半導体を含有する、請求項1~6のいずれか1項に記載の光電変換素子。
- 更に、電荷ブロッキング膜を有する、請求項1~7のいずれか1項に記載の光電変換素子。
- 請求項1~8のいずれか1項に記載の光電変換素子を含む光センサ。
- 請求項1~8のいずれか1項に記載の光電変換素子を含む撮像素子。
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WO2021221108A1 (ja) | 2020-04-30 | 2021-11-04 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、化合物 |
WO2022014721A1 (ja) | 2020-07-17 | 2022-01-20 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、及び化合物 |
WO2022138833A1 (ja) | 2020-12-24 | 2022-06-30 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、化合物 |
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WO2021221108A1 (ja) | 2020-04-30 | 2021-11-04 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、化合物 |
WO2022014721A1 (ja) | 2020-07-17 | 2022-01-20 | 富士フイルム株式会社 | 光電変換素子、撮像素子、光センサ、及び化合物 |
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