WO2016129298A1 - 光電変換膜、固体撮像素子、および電子機器 - Google Patents
光電変換膜、固体撮像素子、および電子機器 Download PDFInfo
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- WO2016129298A1 WO2016129298A1 PCT/JP2016/050156 JP2016050156W WO2016129298A1 WO 2016129298 A1 WO2016129298 A1 WO 2016129298A1 JP 2016050156 W JP2016050156 W JP 2016050156W WO 2016129298 A1 WO2016129298 A1 WO 2016129298A1
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- 239000007769 metal material Substances 0.000 description 1
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- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
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- 150000002964 pentacenes Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
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- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 150000003220 pyrenes Chemical class 0.000 description 1
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- 150000003233 pyrroles Chemical class 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical class [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical class C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003967 siloles Chemical class 0.000 description 1
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- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical class S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical class C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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Images
Classifications
-
- 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
- C09B47/00—Porphines; Azaporphines
-
- 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
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—Semiconductor devices 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; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/80—Camera processing pipelines; Components thereof
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N25/00—Circuitry of solid-state image sensors [SSIS]; Control thereof
- H04N25/10—Circuitry of solid-state image sensors [SSIS]; Control thereof for transforming different wavelengths into image signals
- H04N25/17—Colour separation based on photon absorption depth, e.g. full colour resolution obtained simultaneously at each pixel location
-
- 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
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
-
- 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
- H01L27/14643—Photodiode arrays; MOS imagers
- H01L27/14645—Colour imagers
-
- 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
- H01L27/14643—Photodiode arrays; MOS imagers
- H01L27/14645—Colour imagers
- H01L27/14647—Multicolour imagers having a stacked pixel-element structure, e.g. npn, npnpn or MQW elements
-
- 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
- H01L27/14665—Imagers using a photoconductor layer
- H01L27/14667—Colour imagers
-
- 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
-
- 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 disclosure relates to a photoelectric conversion film, a solid-state imaging device, and an electronic device.
- a solid-state imaging device in which organic photoelectric conversion films that absorb blue light, green light, and red light are stacked, or a solid-state imaging device in which organic photoelectric conversion films that absorb green light and a plurality of silicon photodiodes are stacked Proposed.
- the organic photoelectric conversion film in the solid-state imaging device as described above is required to selectively absorb light in a specific wavelength region in order to improve imaging characteristics.
- an organic photoelectric conversion film that absorbs green light is required to selectively absorb light in a wavelength region of 450 nm to 600 nm.
- Patent Document 1 As an organic dye compound that absorbs green light, a subphthalocyanine derivative disclosed in the following Patent Document 1 is known.
- a novel and improved photoelectric conversion film capable of improving the imaging characteristics of a solid-state imaging device with small absorption in a wavelength region exceeding 600 nm, a solid-state imaging device including the photoelectric conversion film, and the solid An electronic apparatus including an image sensor is proposed.
- a photoelectric conversion film including a subphthalocyanine derivative represented by the following general formula (1) is provided.
- X 1 to X 6 are independently of each other hydrogen, halogen, hydroxy group, thiol group, alkoxy group, cyano group, nitro group, silylalkyl group, silylalkoxy group, arylsilyl group, thioalkyl group, thioaryl group, sulfonyl Group, arylsulfonyl group, alkylsulfonyl group, amino group, alkylamino group, arylamino group, acyl group, acylamino group, acyloxy group, carboxy group, carboxamide group, carboalkoxy group, substituted or unsubstituted alkyl group, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or un
- R 1 to R 3 are independently of each other hydrogen, halogen, hydroxy group, alkoxy group, cyano group, nitro group, sulfonyl group, amino group, acyl group, carboxy group, substituted or unsubstituted alkyl group, At least two of R 1 to R 3 are fluorine.
- a solid-state imaging device including a photoelectric conversion film including the subphthalocyanine derivative represented by the general formula (1) is provided.
- a solid-state imaging device including a photoelectric conversion film including the subphthalocyanine derivative represented by the general formula (1), an optical system that guides incident light to the solid-state imaging device, and the solid-state imaging device And an arithmetic processing circuit that performs arithmetic processing on an output signal from the electronic device.
- a subphthalocyanine derivative that can absorb light in a wavelength region of 450 nm or more and 600 nm or less with little absorption of light in a wavelength region of more than 600 nm. Therefore, the photoelectric conversion film using the subphthalocyanine derivative according to the present disclosure can selectively absorb green light of 450 nm or more and 600 nm or less, and thus can be suitably used for a solid-state imaging device.
- FIG. 5 is a cross-sectional view illustrating a configuration of one pixel near a boundary between the pixel portion of FIG. 4 and a peripheral portion of the pixel portion in a cross section cut in a thickness direction of a substrate. It is the schematic explaining the structure of the electronic device which concerns on one Embodiment of this invention.
- the photoelectric conversion film according to the present embodiment has a light absorption characteristic in which absorption of light in a wavelength region exceeding 600 nm is small.
- the light absorption characteristics of the organic thin film are determined depending on the characteristics of the molecules constituting the organic thin film and the molecular orientation at the time of forming the organic thin film.
- the maximum absorption wavelength of the subphthalocyanine derivative is shifted to the short wavelength side, and the wavelength region exceeds 600 nm. Made it possible to reduce the absorption of light.
- Such a photoelectric conversion film according to this embodiment includes a subphthalocyanine derivative represented by the following general formula (1).
- X 1 to X 6 are independently of each other hydrogen, halogen, hydroxy group, thiol group, alkoxy group, cyano group, nitro group, silylalkyl group, silylalkoxy group, arylsilyl group, thioalkyl group, thioaryl group, sulfonyl Group, arylsulfonyl group, alkylsulfonyl group, amino group, alkylamino group, arylamino group, acyl group, acylamino group, acyloxy group, carboxy group, carboxamide group, carboalkoxy group, substituted or unsubstituted alkyl group, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, Z is hydrogen, halogen, hydroxy group, thiol group, im
- At least one of X 1 and X 2 , at least one of X 3 and X 4 , and at least one of X 5 and X 6 are substituents represented by the following general formula (2). is there.
- R 1 to R 3 are independently of each other hydrogen, halogen, hydroxy group, alkoxy group, cyano group, nitro group, sulfonyl group, amino group, acyl group, carboxy group, substituted or unsubstituted alkyl group, At least two of R 1 to R 3 are fluorine.
- substituent represented by the general formula (2) include a difluoromethyl group or a trifluoromethyl group.
- R 1 to R 3 When R 1 to R 3 have one or less fluorine, the maximum absorption wavelength of the subphthalocyanine derivative substituted with the substituent represented by the general formula (2) does not shift to the short wavelength side. Therefore, at least two of R 1 to R 3 need to be fluorine. In addition, as long as at least two of R 1 to R 3 are fluorine, the remaining one of R 1 to R 3 is not particularly limited and may be any atom or substituent.
- R 1 to R 3 are all fluorine. That is, the substituent represented by the general formula (2) is preferably a trifluoromethyl group. In such a case, as shown in the examples described later, since the maximum absorption wavelength of the subphthalocyanine derivative can be further moved to the short wavelength side, the absorption of light in the wavelength region exceeding 600 nm can be further reduced. .
- each terminal benzene ring is substituted with at least one or more substituents represented by the general formula (2), so that the maximum absorption wavelength is reduced to the short wavelength side. Can be moved to.
- the absorption of light in the wavelength region exceeding 600 nm becomes small, and thus light in the wavelength region of 450 nm or more and 600 nm or less can be selectively absorbed. Become.
- X 1 to X 6 are substituted with a substituent represented by the general formula (2) so that the subphthalocyanine derivative represented by the general formula (1) has symmetry. It may be substituted with a substituent represented by the general formula (2) so that the subphthalocyanine derivative represented by the general formula (1) does not have symmetry.
- X 1 , X 3 and X 5 are represented by the general formula (2) so that the subphthalocyanine derivative represented by the general formula (1) has symmetry.
- X 1 , X 3 and X 6 are represented by the general formula (2) so that the subphthalocyanine derivative represented by the general formula (1) does not have symmetry. It may be substituted with a substituent.
- X 1 to X 6 are all substituted with a substituent represented by the general formula (2).
- a substituent represented by the general formula (2) since the maximum absorption wavelength of the subphthalocyanine derivative can be further moved to the short wavelength side, the absorption of light in the wavelength region exceeding 600 nm can be further reduced. .
- Z may be any substituent as long as it is a substituent capable of binding to boron.
- Z is, for example, as described above, hydrogen, halogen, hydroxy group, thiol group, imide group, alkoxy group, cyano group, nitro group, silylalkyl group, silylalkoxy group, arylsilyl group, thioalkyl group, thioaryl group, Sulfonyl, arylsulfonyl, alkylsulfonyl, amino, alkylamino, arylamino, acyl, acylamino, acyloxy, carboxy, carboxamide, carboalkoxy, substituted or unsubstituted alkyl Linking via a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubsti
- Z may be a halogen, a hydroxy group, a substituted or unsubstituted alkoxy group.
- the subphthalocyanine derivative represented by the general formula (1) is a so-called ⁇ -oxo bridged subphthalocyanine dimer.
- each of the ⁇ -oxo-bridged subphthalocyanine derivatives may have the same structure or a different structure.
- subphthalocyanine derivative represented by the general formula (1) described above include compounds having the following structural formula.
- the subphthalocyanine derivative represented by the general formula (1) is not limited to the following compounds.
- the photoelectric conversion film according to this embodiment is preferably formed as a bulk hetero film.
- the bulk hetero film is a surface of crystal fine particles by disposing one of the different compounds forming the film (for example, p-type photoelectric conversion material and n-type photoelectric conversion material) into a crystalline fine particle state and the other into an amorphous state.
- the film for example, p-type photoelectric conversion material and n-type photoelectric conversion material
- the area of the pn junction that induces charge separation is increased by the fine structure, so that charge separation can be induced more efficiently and the photoelectric conversion efficiency can be improved.
- the photoelectric conversion film according to the present embodiment is formed as a bulk hetero film of the subphthalocyanine derivative represented by the general formula (1) and an arbitrary photoelectric conversion material, thereby obtaining better photoelectric conversion characteristics. be able to.
- the photoelectric conversion film according to the present embodiment may be formed as a bulk hetero film of the subphthalocyanine derivative represented by the general formula (1) described above and a p-type photoelectric conversion material such as a quinacridone derivative.
- the photoelectric conversion film according to this embodiment is represented by the general formula (1) in which the maximum absorption wavelength moves to the short wavelength side and the absorption of light in the wavelength region exceeding 600 nm is reduced.
- Subphthalocyanine derivatives are included in the photoelectric conversion film according to the present embodiment.
- the photoelectric conversion film according to the present embodiment can selectively absorb light in a wavelength region of 450 nm or more and 600 nm or less, and therefore is preferably used as an organic photoelectric conversion film for green light in a solid-state imaging device. it can. Therefore, according to the present embodiment, it is possible to improve the imaging characteristics of the solid-state imaging device.
- FIG. 1 is a schematic diagram illustrating an example of a photoelectric conversion element using the photoelectric conversion film according to the present embodiment.
- the photoelectric conversion element 100 is disposed on a substrate 101, a lower electrode 102 disposed on the substrate 101, a p buffer layer 103 disposed on the lower electrode 102, and a p buffer layer 103.
- the photoelectric conversion film 104, the n buffer layer 105 disposed on the photoelectric conversion film 104, and the upper electrode 106 disposed on the n buffer layer 105 are provided.
- the structure of the photoelectric conversion element 100 illustrated in FIG. 1 is merely an example, and the structure of the photoelectric conversion element 100 using the photoelectric conversion film according to the present embodiment is not limited to the structure illustrated in FIG. Absent.
- any one or more of the p buffer layer 103 and the n buffer layer 105 may be omitted.
- An electron blocking layer containing an electron donating material may be provided between the lower electrode 102 and the p buffer layer 103, and an electron accepting material is included between the n buffer layer 105 and the upper electrode 106.
- a hole blocking layer may be provided. Note that known materials can be used as the electron-donating material and the electron-accepting material.
- the substrate 101 is a support on which the layers constituting the photoelectric conversion element 100 are stacked.
- a substrate used in a general photoelectric conversion element can be used.
- the substrate 101 is a glass substrate such as a high strain point glass substrate, a soda glass substrate, and a borosilicate glass substrate, a quartz substrate, a semiconductor substrate, a plastic substrate such as polymethyl methacrylate, polyvinyl alcohol, polyimide, and polycarbonate. It may be.
- the substrate 101 when the incident light is transmitted to the opposite side of the element, the substrate 101 is preferably made of a transparent material.
- the lower electrode 102 and the upper electrode 106 are made of a conductive material such as metal or metal oxide.
- the lower electrode 102 is disposed on the substrate 101, and the upper electrode 106 is disposed on the n buffer layer 105.
- at least one of the lower electrode 102 and the upper electrode 106 is made of a transparent conductive material such as indium tin oxide (ITO).
- ITO indium tin oxide
- the lower electrode 102 and the upper electrode 106 are preferably made of a transparent conductive material such as ITO.
- tin oxide (SnO 2 ) or a tin oxide-based material to which a dopant is added, zinc oxide (ZnO) or a zinc oxide-based material to which a dopant is added can be used.
- zinc oxide-based material include aluminum zinc oxide to which aluminum (Al) is added as a dopant, gallium zinc oxide to which gallium (Ga) is added, and indium zinc oxide to which indium (In) is added.
- CuI, InSbO 4 , ZnMgO, CuInO 2 , MgIn 2 O 4 , ZnSnO 3 or the like can be used as the transparent conductive material.
- indium gallium zinc oxide, indium gallium oxide, aluminum gallium zinc oxide, graphene, a metal thin film, and PEDOT (polyethylenedioxythiophene) may be used as the transparent conductive material.
- a bias voltage is applied to the lower electrode 102 and the upper electrode 106.
- the polarity of the bias voltage is set so that, for example, among the charges generated in the photoelectric conversion film 104, electrons move to the upper electrode 106 and holes move to the lower electrode 102.
- the polarity of the bias voltage may be set so that holes move to the upper electrode 106 and electrons move to the lower electrode 102 among the charges generated in the photoelectric conversion film 104. In such a case, in the photoelectric conversion element 100 illustrated in FIG. 2, the positions of the p buffer layer 103 and the n buffer layer 105 are switched.
- the p buffer layer 103 is a layer that is disposed on the lower electrode 102 and functions to efficiently extract holes from the photoelectric conversion film 104.
- the p buffer layer 103 is composed of a p-type photoelectric conversion material, and includes arylamine, oxazole, oxadiazole, triazole, imidazole, stilbene, polyarylalkane, porphyrin, anthracene, fluorenone, hydrazone, quinacridone, or these Or a derivative thereof.
- the p buffer layer 103 includes N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (TPD), 4,4′-bis [N- ( Naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD), 4,4 ′, 4 ′′ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (m-MTDATA), tetraphenyl You may comprise porphyrin copper, phthalocyanine, copper phthalocyanine, etc.
- the photoelectric conversion film 104 is disposed on the p buffer layer 103, and selectively absorbs green light (for example, light having a wavelength of 450 nm or more and 600 nm or less) and performs a function of photoelectrically converting the absorbed light.
- the photoelectric conversion film 104 includes a subphthalocyanine derivative represented by the general formula (1) described above.
- the photoelectric conversion film 104 may be a bulk hetero film including a subphthalocyanine derivative represented by the general formula (1) as an n-type photoelectric conversion material and a quinacridone derivative as a p-type photoelectric conversion material.
- the photoelectric conversion material included in the photoelectric conversion film 104 is not limited to the quinacridone derivative described above.
- the photoelectric conversion film 104 includes, for example, phthalocyanine derivatives, porphyrin derivatives, squarylium derivatives, naphthalene or perylene derivatives, cyanine derivatives, merocyanine derivatives, rhodamine derivatives, diphenylmethane or triphenylmethane derivatives, xanthene derivatives, acridine derivatives, phenoxazine derivatives, quinoline derivatives.
- the photoelectric conversion film 104 is preferably formed as a bulk hetero film, the photoelectric conversion film 104 is not limited to the bulk hetero mixed film as long as it includes the subphthalocyanine derivative represented by the general formula (1), and is a single layer film, a planar film It may be formed of a heterojunction film or the like.
- the n buffer layer 105 is a layer that is disposed on the photoelectric conversion film 104 and performs a function of efficiently extracting electrons from the photoelectric conversion film 104.
- the n buffer layer 105 is composed of an n-type photoelectric conversion material such as fullerene, carbon nanotube, oxadiazole, triazole compound, anthraquinodimethane, diphenylquinone, distyrylarylene, silole compound, or these. Or a derivative thereof.
- the n buffer layer 105 includes 1,3-bis (4-tert-butylphenyl-1,3,4-oxadiazolyl) phenylene (OXD-7), bathocuproine, bathophenanthroline, tris (8-hydroxyxyl).
- each layer of the photoelectric conversion element 100 described above can be formed by selecting an appropriate film formation method according to the material, such as vacuum deposition, sputtering, and various coating methods.
- the lower electrode 102 and the upper electrode 106 are, for example, an evaporation method including an electron beam evaporation method, a hot filament evaporation method, and a vacuum evaporation method, a sputtering method, and a chemical vapor deposition method.
- CVD method a combination of ion plating method and etching method, various printing methods such as screen printing method, ink jet printing method, and metal mask printing method, plating method (electroplating method and electroless plating method), etc. It is possible.
- each layer such as the p buffer layer 103, the photoelectric conversion film 104, and the n buffer layer 105 constituting the photoelectric conversion element 100 is formed by, for example, a vapor deposition method such as a vacuum vapor deposition method, a printing method such as a screen printing method, and an ink jet printing method, It can be formed by a laser transfer method or a coating method such as a spin coat method.
- a vapor deposition method such as a vacuum vapor deposition method
- a printing method such as a screen printing method
- an ink jet printing method It can be formed by a laser transfer method or a coating method such as a spin coat method.
- “Bay-6CF 3 -SubPc”, “Bay-3CF 3 -SubPc”, and “Bay-6CF 2 H-SubPc” are subphthalocyanine derivatives represented by the general formula (1), “SubPc”, “Bay-6CH 2 F-SubPc” and “6CF 3 -SubPc” are subphthalocyanine derivatives according to comparative examples.
- UV-VIS ultraviolet-visible absorption spectrum
- TD-DFT Time-Dependent Density Functional Theory
- Gaussian 09 is used as a calculation program
- a functional form “6-31 + G ** ” obtained by adding a polarization function and a dispersion function to a double basis function system is used as a basis function
- a structure optimization is performed using a B3LYP functional.
- the calculation was performed.
- UV-visible absorption spectrum calculation was performed using TD-DFT at the B3LYP / 6-31 + G ** level, and the maximum absorption wavelength ⁇ max was calculated.
- the maximum absorption wavelength ⁇ max of each subphthalocyanine derivative calculated by calculation is shown in Table 1 below.
- the energy of the HOMO (High Occupied Molecular Orbital) level and the LUMO (Lowest Unoccupied Molecular Orbital) level of each subphthalocyanine derivative calculated simultaneously when calculating the maximum absorption wavelength ⁇ max is also shown.
- the maximum absorption wavelength ⁇ max of each subphthalocyanine derivative shown in Table 1 is a simulation analysis result for one molecule, the absolute value of the maximum absorption wavelength in the absorption spectrum described later measured after forming on a thin film is one. I have not done it. However, as can be seen from the result of the absorption spectrum described later measured after forming the thin film, the tendency is consistent between the simulation analysis result and the actual measurement result, and a relative comparison is possible.
- the subphthalocyanine derivatives according to Examples 1 to 3 have a shorter maximum absorption wavelength ⁇ max than that of SubPc (Comparative Example 1), and light in a wavelength region exceeding 600 nm. It can be seen that the absorption can be reduced. In addition, it can be seen that in the subphthalocyanine derivatives according to Comparative Examples 2 and 3, the maximum absorption wavelength ⁇ max is not shortened as compared with SubPc (Comparative Example 1).
- Examples 1 to 3 and Comparative Example 3 are compared, Examples 1 to 3 have a substituent represented by the general formula (2) at the Bay position of the subphthalocyanine skeleton. It can be seen that the maximum absorption wavelength ⁇ max is shorter than that of SubPc. On the other hand, since Comparative Example 3 has the substituent represented by the general formula (2) at a position other than the Bay position of the subphthalocyanine skeleton, it can be seen that the maximum absorption wavelength ⁇ max is not shortened with respect to SubPc. .
- Examples 1 to 3 and Comparative Example 2 are compared, Examples 1 to 3 have a maximum with respect to SubPc because there are two or more fluorine atoms in the substituent represented by the general formula (2). It can be seen that the absorption wavelength ⁇ max is shortened. On the other hand, in Comparative Example 2, since the substituent represented by the general formula (2) has only one fluorine, it can be seen that the maximum absorption wavelength ⁇ max is not shortened with respect to SubPc.
- Example 1 when Example 1 is compared with Example 3, Example 1 has a larger absorption wavelength than Example 3 because the number of fluorine in the substituent represented by the general formula (2) is larger. It can be seen that ⁇ max is even shorter, which is preferable. Further, when Example 1 is compared with Example 2, Example 1 is such that all of X 1 to X 6 are substituted with the substituent represented by the general formula (2). It can be seen that the maximum absorption wavelength ⁇ max is further shorter than 2, which is preferable.
- the subphthalocyanine derivative represented by the general formula (1) can be synthesized by a generalized synthesis method represented by the following reaction formula 1.
- the synthesis method described below is merely an example, and the synthesis method of the subphthalocyanine derivative represented by the general formula (1) is not limited to the following example.
- a phthalonitrile derivative and boron trichloride are mixed in a solvent and heated to reflux to synthesize a subphthalocyanine derivative.
- Z may be Cl (chlorine)
- Y may be H (hydrogen)
- X may be CF 3 (trifluoromethyl group) or H (hydrogen).
- Example 4 UV / ozone treatment was performed on the quartz substrate.
- the treated quartz substrate is put into an organic vapor deposition apparatus, and the C 1 -CF 3 -SubPc synthesized above is deposited by a resistance heating method while rotating the substrate holder in a vacuum of 1 ⁇ 10 ⁇ 5 Pa or less, An evaluation sample was prepared.
- the film thickness of the deposited C 1 -CF 3 -SubPc was 50 nm.
- ITO indium tin oxide
- Example 5 An evaluation sample was prepared in the same manner as in Example 4 except that C 3 —CF 3 —SubPc was used instead of C 1 —CF 3 —SubPc used in Example 4, and ITO film formation and annealing were similarly performed. Processed.
- Example 4 An evaluation sample was prepared in the same manner as in Example 4 except that subphthalocyanine chloride (SubPc) shown below was used instead of C 1 -CF 3 -SubPc used in Example 4, and an ITO film was formed in the same manner. And annealing treatment was performed.
- Subphthalocyanine chloride was purchased from Sigma-Aldrich and used after sublimation purification.
- FIG. 2A is a graph showing the evaluation results of changes in spectral characteristics of Example 4 (C 1 -CF 3 -SubPc), and FIG. 2B shows the results of Example 5 (C 3 -CF 3 -SubPc). It is a graph which shows the evaluation result of a spectral characteristic change.
- FIG. 3 is a graph showing evaluation results of changes in spectral characteristics of Comparative Example 4 (SubPc).
- the maximum absorption wavelength ⁇ max in Examples 4 and 5 and Comparative Example 4 was calculated from the results of FIGS. 2A, 2B, and 3. Table 2 shows the results of the calculated maximum absorption wavelength ⁇ max in Examples 4 and 5 and Comparative Example 4.
- Example 4 and Example 5 have low absorption of light in the wavelength region exceeding 600 nn, and can selectively absorb green light in the wavelength region of 450 nm to 600 nm. Recognize. Referring to Table 2, it can also be seen that in Examples 4 and 5, the maximum absorption wavelength ⁇ max hardly changed before and after the ITO film formation and before and after the annealing, and had heat resistance. On the other hand, referring to FIG. 3, it can be seen that Comparative Example 4 has a large absorption of light in the wavelength region exceeding 600 nm and also absorbs red light in the wavelength region exceeding 600 nm.
- the subphthalocyanine derivative represented by the general formula (1) has small absorption of light in the wavelength region exceeding 600 nn, and can selectively absorb green light in the wavelength region of 450 nm to 600 nm. I understand.
- Example 6 UV / ozone treatment was performed on a quartz substrate with an ITO electrode.
- the film thickness of the ITO electrode (lower electrode) on the quartz substrate was 50 nm.
- the treated quartz substrate is put into an organic vapor deposition apparatus, and C 1 -CF 3 -SubPc and quinacridone are vapor-deposited by resistance heating while rotating the substrate holder in a vacuum of 1 ⁇ 10 ⁇ 5 Pa or less. did.
- the deposition rate was 0.1 nm / second for vapor deposition so that the volume ratio of C 1 -CF 3 -SubPc and quinacridone was 1: 1, and a total of 100 nm was formed to form a photoelectric conversion film. did.
- AlSiCu was deposited on the photoelectric conversion film by a vapor deposition method to a film thickness of 100 nm to form an upper electrode.
- a photoelectric conversion element having a 1 mm ⁇ 1 mm photoelectric conversion region was manufactured by the above manufacturing method.
- quinacridone is a compound having the following structural formula, and a sublimation-purified product purchased from Tokyo Chemical Industry Co., Ltd. was used.
- Example 7 A photoelectric conversion element was produced in the same manner as in Example 5 except that C 3 —CF 3 —SubPc was used instead of C 1 —CF 3 —SubPc used in Example 5.
- Evaluation of photoelectric conversion efficiency was performed by measuring external quantum efficiency using a semiconductor parameter analyzer. Specifically, a light current value of 1.62 ⁇ W / cm 2 from a light source through a filter is applied to the photoelectric conversion element, and a bias voltage applied between the electrodes is set to ⁇ 1 V, and a dark current value. The external quantum efficiency was calculated from the current value. The external quantum efficiency was measured before and after annealing at 160 ° C. for 5 minutes. In Table 3, “QD” represents quinacridone.
- the photoelectric conversion elements according to Examples 6 and 7 have good photoelectric conversion ability. Moreover, since the photoelectric conversion element which concerns on Example 6 and 7 has high external quantum efficiency after the annealing process for 160 degreeC for 5 minutes, it turns out that it has heat resistance. Therefore, it turns out that the subphthalocyanine derivative represented by General formula (1) can be used suitably as a photoelectric conversion material.
- the photoelectric conversion film according to the present embodiment includes a subphthalocyanine derivative represented by the general formula (1), thereby reducing the absorption of light in the wavelength region exceeding 600 nm, and thereby generating green light. It can be seen that can be selectively absorbed. Therefore, the photoelectric conversion film according to the present embodiment can be suitably used for a green light photoelectric conversion element in a solid-state imaging device, and can improve imaging characteristics of the solid-state imaging device.
- the photoelectric conversion element 100 using the photoelectric conversion film according to the present embodiment can be suitably used, for example, as the organic photoelectric conversion unit 11G in the solid-state imaging element.
- FIG. 4 is a schematic diagram illustrating the entire configuration of the solid-state imaging device 1 to which the photoelectric conversion device 100 according to the present embodiment is applied.
- the solid-state image sensor 1 is, for example, a CMOS (Complementary Metal Oxide Semiconductor) image sensor.
- the solid-state imaging device 1 has a pixel unit 10a as an imaging area on a semiconductor substrate 11, and, for example, a row scanning unit 131, a horizontal selection unit 133, a column scanning unit 134, and a system in a peripheral region of the pixel unit 10a.
- the peripheral circuit unit 130 including the control unit 132 is included.
- the pixel unit 10a includes, for example, a plurality of unit pixels C that are two-dimensionally arranged in a matrix.
- a pixel drive line Lread (specifically, a row selection line and a reset control line) is wired for each pixel row, and a vertical signal line Lsig is wired for each pixel column.
- the pixel drive line Lread transmits a drive signal for reading a signal from the pixel. Note that one end of the pixel drive line Lread is connected to an output end corresponding to each row of the row scanning unit 131, for example.
- the row scanning unit 131 includes a shift register, an address decoder, and the like, and is a pixel driving unit that drives each unit pixel C of the pixel unit 10a, for example, in units of rows.
- a signal output from each unit pixel C in the pixel row selectively scanned by the row scanning unit 131 is supplied to the horizontal selection unit 133 through each of the vertical signal lines Lsig.
- the horizontal selection unit 133 is configured by an amplifier, a horizontal selection switch, and the like provided for each vertical signal line Lsig.
- the column scanning unit 134 includes a shift register, an address decoder, and the like, scans each horizontal selection switch of the horizontal selection unit 133, and drives the horizontal selection unit 133 in order.
- the signal of each pixel transmitted through each of the vertical signal lines Lsig is sequentially output to a horizontal signal line (not shown), and is output to the outside of the semiconductor substrate 11 through the horizontal signal line. Is transmitted.
- circuit portion including the row scanning unit 131, the horizontal selection unit 133, the column scanning unit 134, and the horizontal signal line may be formed directly on the semiconductor substrate 11 or provided in the external control IC. May be.
- the circuit portion may be formed on another substrate connected by a cable or the like.
- the system control unit 132 receives a clock given from the outside of the semiconductor substrate 11, data instructing an operation mode, and the like. In addition, the system control unit 132 outputs data such as internal information of the solid-state imaging device 1. Further, the system control unit 132 includes a timing generator that generates various timing signals, and the peripherals such as the row scanning unit 131, the horizontal selection unit 133, and the column scanning unit 134 based on the timing signals generated by the timing generator. Performs drive control of the circuit.
- FIG. 5 is a cross-sectional view showing the configuration of one pixel 10a1 in the vicinity of the boundary between the pixel portion 10a and the peripheral portion 10b of the pixel portion 10a in a cross section cut in the thickness direction of the substrate.
- the solid-state imaging device 1 has pixel transistors (including transfer transistors Tr1 to Tr3 described later) on the surface (surface S2 opposite to the light receiving surface) side of the semiconductor substrate 11, and includes a multilayer wiring.
- This is an imaging device having a structure having a layer 51 (so-called back-illuminated structure).
- the pixel 10a1 has a structure in which an organic photoelectric conversion unit that selectively detects light in different wavelength ranges and performs photoelectric conversion and an inorganic photoelectric conversion unit are stacked in the vertical direction. Thereby, the solid-state imaging device 1 can acquire a plurality of types of color signals for each pixel without using a color filter.
- the pixel 10a1 has a stacked structure of one organic photoelectric conversion unit 11G and two inorganic photoelectric conversion units 11B and 11R, whereby red (R), green (G), and blue (B ) Shows a structure for acquiring each color signal.
- the organic photoelectric conversion unit 11 ⁇ / b> G is formed on the back surface (surface S ⁇ b> 1) of the semiconductor substrate 11, and the inorganic photoelectric conversion units 11 ⁇ / b> B and 11 ⁇ / b> R are embedded in the semiconductor substrate 11. Yes.
- the configuration of each unit will be described.
- the semiconductor substrate 11 includes, for example, an n-type silicon (Si) layer 110.
- Si n-type silicon
- inorganic photoelectric conversion portions 11B and 11R and a green power storage layer 110G are embedded.
- conductive plugs 120a1 and 120b1 serving as a transmission path for charges (electrons or holes) from the organic photoelectric conversion unit 11G are embedded in the semiconductor substrate 11.
- the back surface (surface S1) of the semiconductor substrate 11 is a light receiving surface.
- a plurality of pixel transistors (including transfer transistors Tr1 to Tr3) corresponding to each of the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R are formed on the surface (surface S2) side of the semiconductor substrate 11, and further, logic A peripheral circuit composed of a circuit or the like is formed.
- the pixel transistor includes, for example, transfer transistors Tr1 to Tr3, a reset transistor, an amplification transistor, and a selection transistor. These pixel transistors are constituted by, for example, MOS transistors or the like, and are formed in the p-type semiconductor well region on the surface S2. A circuit including such a pixel transistor is formed for each of the red, green, and blue photoelectric conversion units. Each of these circuits may have a three-transistor configuration including, for example, a transfer transistor, a reset transistor, and an amplifying transistor, or may further have a four-transistor configuration including a selection transistor.
- FIG. 5 shows and describes only the transfer transistors Tr1 to Tr3 among these pixel transistors.
- Other pixel transistors other than the transfer transistors Tr1 to Tr3 can be shared between the photoelectric conversion units or between the pixels. It is also possible to use a structure sharing a floating diffusion (a so-called pixel sharing structure).
- the transfer transistors Tr1 to Tr3 include a gate electrode (gate electrodes TG1 to TG3) and a floating diffusion (not shown). Among these, the gate electrodes TG 1 to TG 3 are formed in the multilayer wiring layer 51, and the floating diffusion is formed in the semiconductor substrate 11.
- the transfer transistor Tr1 transfers the signal charge (charge corresponding to green) generated in the organic photoelectric conversion unit 11G and accumulated in the green power storage layer 110G to a vertical signal line Lsig described later.
- the transfer transistor Tr2 transfers the signal charge (charge corresponding to blue) generated and accumulated in the inorganic photoelectric conversion unit 11B to a vertical signal line Lsig described later.
- the transfer transistor Tr3 transfers the accumulated signal charge (charge corresponding to red) generated in the inorganic photoelectric conversion unit 11R to a vertical signal line Lsig described later.
- the inorganic photoelectric conversion units 11B and 11R are photodiodes each having a pn junction.
- the inorganic photoelectric conversion units 11B and 11R are formed on the optical path in the semiconductor substrate 11 in the order of the inorganic photoelectric conversion unit 11B and the inorganic photoelectric conversion unit 11R from the surface S1 side.
- the inorganic photoelectric conversion unit 11B selectively detects blue light and accumulates signal charges corresponding to blue.
- the inorganic photoelectric conversion unit 11 ⁇ / b> B extends from a selective region along the surface S ⁇ b> 1 of the semiconductor substrate 11 to a region near the interface with the multilayer wiring layer 51.
- the inorganic photoelectric conversion unit 11R selectively detects red light and accumulates signal charges corresponding to red.
- the inorganic photoelectric conversion unit 11R is formed over a lower layer (surface S2 side) region than the inorganic photoelectric conversion unit 11B.
- blue (B) is a color corresponding to a wavelength region of 400 nm or more and less than 450 nm, for example, and red (R) is a color corresponding to a wavelength region of 600 nm or more and less than 750 nm, for example.
- the inorganic photoelectric conversion units 11 ⁇ / b> B and 11 ⁇ / b> R are only required to be able to detect light in at least some of the wavelength regions in each wavelength region.
- the green power storage layer 110G includes, for example, an n-type region that serves as an electron storage layer. A part of the n-type region is connected to the conductive plug 120a1, and can store electrons transmitted from the lower electrode 13a side through the conductive plug 120a1.
- the conductive plug 120a1 is electrically connected to the lower electrode 13a of the organic photoelectric conversion unit 11G, and is connected to the green power storage layer 110G.
- the conductive plug 120b1 is electrically connected to the upper electrode 16 of the organic photoelectric conversion unit 11G and serves as a wiring for discharging holes.
- the conductive plugs 120a1 and 120b1 may be formed, for example, by burying a conductive film material such as tungsten in a through via.
- a conductive film material such as tungsten
- the via side surface is preferably covered with an insulating film such as silicon oxide (SiO 2 ) or silicon nitride (SiN).
- the conductive plugs 120a1 and 120b1 may be formed by embedding a conductive semiconductor layer.
- the conductive plug 120a1 is preferably n-type because it serves as an electron transmission path
- the conductive plug 120b1 is preferably p-type because it serves as a hole transmission path.
- a multilayer wiring layer 51 is formed on the surface S ⁇ b> 2 of the semiconductor substrate 11.
- a plurality of wirings 51 a are arranged via an interlayer insulating film 52.
- the multilayer wiring layer 51 is formed on the side opposite to the light receiving surface, which is a so-called back-illuminated solid-state imaging device.
- a support substrate 53 made of silicon may be bonded to the multilayer wiring layer 51.
- the organic photoelectric conversion unit 11G absorbs light in a selective wavelength region (here, green light corresponding to a wavelength region of 450 nm to 600 nm) by an organic compound, and generates an electron / hole pair. It is.
- the organic photoelectric conversion unit 11G has a configuration in which the organic photoelectric conversion film 15 is sandwiched between a pair of electrodes (lower electrode 13a and upper electrode 16) for extracting signal charges.
- the lower electrode 13a and the upper electrode 16 are electrically connected to conductive plugs 120a1 and 120b1 embedded in the semiconductor substrate 11 via a wiring layer and a contact metal layer.
- interlayer insulating films 12a and 12b are formed on the surface S1 of the semiconductor substrate 11 in the organic photoelectric conversion unit 11G.
- interlayer insulating film 12a through holes are provided in regions corresponding to the conductive plugs 120a1 and 120b1, and the conductive plugs 120a2 and 120b2 are embedded in the through holes.
- conductive plugs 120a3 and 120b3 are embedded in regions corresponding to the conductive plugs 120a2 and 120b2, respectively.
- a lower electrode 13a is provided on the interlayer insulating film 12b, and a wiring layer 13b that is electrically separated from the lower electrode 13a by the insulating film 14 is provided. Further, an organic photoelectric conversion film 15 is formed on the lower electrode 13a, and an upper electrode 16 and a sealing film 17 are formed so as to cover the organic photoelectric conversion film 15. The contact metal layer 18 is formed so as to be electrically connected to the upper electrode 16 and the conductive plug 120b3.
- the conductive plugs 120a2 and 120a3 function as a connector together with the conductive plug 120a1, and form a charge (electron) transmission path from the lower electrode 13a to the green storage layer 110G.
- the conductive plugs 120b2 and 120b3 function as a connector together with the conductive plug 120b1, and form a discharge path of charges (holes) from the upper electrode 16 through the wiring layer 13b and the contact metal layer 18.
- the conductive plugs 120a2 and 120b2 are preferably formed of a laminated film of a metal material such as titanium (Ti), titanium nitride (TiN), and tungsten so as to function as a light shielding film. Further, by using such a laminated film, contact with silicon can be ensured even when the conductive plugs 120a1 and 120b1 are formed as n-type or p-type semiconductor layers.
- a metal material such as titanium (Ti), titanium nitride (TiN), and tungsten
- the lower electrode 13a is provided in a region that faces the light receiving surfaces of the inorganic photoelectric conversion portions 11B and 11R formed in the semiconductor substrate 11 and covers these light receiving surfaces.
- the upper electrode 16 may be provided in common for each pixel.
- a planarizing film 21 is formed on the sealing film 17 and the contact metal layer 18 so as to cover the entire surface.
- An on-chip lens 22 (for example, a microlens) is provided on the planarizing film 21.
- the on-chip lens 22 condenses light incident from above onto the light receiving surfaces of the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R.
- the multilayer wiring layer 51 is formed on the surface S2 side of the semiconductor substrate 11, the light receiving surfaces of the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R can be arranged close to each other. As a result, it is possible to reduce the variation in sensitivity between the colors depending on the F value of the on-chip lens 22.
- a light reception signal is acquired as follows.
- the green light L g is selectively detected in the organic photoelectric conversion section 11G (absorption), it is photoelectrically converted.
- the generated electron / hole pairs electrons are taken out from the lower electrode 13a side and accumulated in the green power storage layer 110G via the conductive plugs 120a1 to 120a3.
- the accumulated electrons are read out to the vertical signal line Lsig via a pixel transistor (not shown) during a read operation. Holes are discharged from the upper electrode 16 side through the contact metal layer 18, the wiring layer 13b, and the conductive plugs 120b1 to 120b3.
- the red light L r at the inorganic photoelectric conversion unit 11R are sequentially absorbed respectively, it is photoelectrically converted .
- the inorganic photoelectric conversion part 11B electrons corresponding to the incident blue light L b are accumulated in the n-type region (not shown). The accumulated electrons are read out to the vertical signal line Lsig via a pixel transistor (not shown) during a read operation. Holes are accumulated in a p-type region (not shown).
- the inorganic photoelectric conversion part 11R the electrons corresponding to the incident red light L r is accumulated in the n-type region (not shown).
- the accumulated electrons are read out to the vertical signal line Lsig via a pixel transistor (not shown) during a read operation. Holes are accumulated in a p-type region (not shown).
- the solid-state imaging device 1 described above can be applied to all types of electronic devices having an imaging function, such as a camera system such as a digital still camera or a video camera, or a mobile phone having an imaging function.
- FIG. 6 shows a schematic configuration of such an electronic device.
- FIG. 6 is a schematic diagram illustrating the configuration of the electronic device according to the present embodiment.
- the electronic device 2 is, for example, a video camera capable of shooting a still image or a moving image, and includes a solid-state image sensor 1, an optical system 310, a shutter device 311, the solid-state image sensor 1, and a shutter device.
- a driving unit 313 for driving 311 and a signal processing unit 312 are provided.
- the optical system 310 is, for example, an optical lens, and guides image light (incident light) from a subject to the pixel unit 10 a of the solid-state imaging device 1.
- the optical system 310 may be composed of a plurality of optical lenses.
- the shutter device 311 controls the light irradiation period and the light shielding period to the solid-state imaging device 1.
- the drive unit 313 controls the transfer operation of the solid-state imaging device 1 and the shutter operation of the shutter device 311.
- the signal processing unit 312 performs various types of signal processing on the signal output from the solid-state imaging device 1.
- the video signal Dout after the signal processing may be stored in a storage medium such as a memory, or may be output to a monitor or the like.
- the solid-state imaging device 1 has a configuration in which an organic photoelectric conversion unit 11G that detects green light and inorganic photoelectric conversion units 11B and 11R that detect blue light and red light, respectively, are stacked.
- an organic photoelectric conversion unit 11G that detects green light and inorganic photoelectric conversion units 11B and 11R that detect blue light and red light, respectively are stacked.
- the present technology is not limited to the above example.
- an organic photoelectric conversion unit including an organic photoelectric conversion film that detects blue light and red light may be provided instead of the inorganic photoelectric conversion units 11B and 11R that respectively detect blue light and red light.
- an organic photoelectric conversion unit including an organic photoelectric conversion film that detects blue light and red light may be provided.
- it may replace with the structure which laminates
- the configuration of the back-illuminated solid-state image sensor is illustrated, but the technology according to the present disclosure can also be applied to the front-illuminated solid-state image sensor.
- the photoelectric conversion film according to this embodiment can reduce the absorption of light in the wavelength region exceeding 600 nm by including the subphthalocyanine derivative represented by the general formula (1). Therefore, the photoelectric conversion film according to this embodiment can selectively absorb green light in a wavelength region of 450 nm to 600 nm. Therefore, the photoelectric conversion film according to the present embodiment can be suitably used for the green light photoelectric conversion element in the solid-state imaging device, and the imaging characteristics of the solid-state imaging device can be improved.
- a photoelectric conversion film comprising a subphthalocyanine derivative represented by the following general formula (1).
- X 1 to X 6 are independently of each other hydrogen, halogen, hydroxy group, thiol group, alkoxy group, cyano group, nitro group, silylalkyl group, silylalkoxy group, arylsilyl group, thioalkyl group, thioaryl group, sulfonyl Group, arylsulfonyl group, alkylsulfonyl group, amino group, alkylamino group, arylamino group, acyl group, acylamino group, acyloxy group, carboxy group, carboxamide group, carboalkoxy group, substituted or unsubstituted alkyl group, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group
- R 1 to R 3 are independently of each other hydrogen, halogen, hydroxy group, alkoxy group, cyano group, nitro group, sulfonyl group, amino group, acyl group, carboxy group, substituted or unsubstituted alkyl group, At least two of R 1 to R 3 are fluorine.
- the substituent represented by the general formula (2) is the photoelectric conversion film according to (1) or (2), wherein the substituent is a difluoromethyl group or a trifluoromethyl group.
- X 1 to X 6 are independently of each other hydrogen, halogen, hydroxy group, thiol group, alkoxy group, cyano group, nitro group, silylalkyl group, silylalkoxy group, arylsilyl group, thioalkyl group, thioaryl group, sulfonyl Group, arylsulfonyl group, alkylsulfonyl group, amino group, alkylamino group, arylamino group, acyl group, acylamino group, acyloxy group, carboxy group, carboxamide group, carboalkoxy group, substituted or unsubstituted alkyl group, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, Z is hydrogen, halogen, hydroxy group, thiol group, imide group
- R 1 to R 3 are independently of each other hydrogen, halogen, hydroxy group, alkoxy group, cyano group, nitro group, sulfonyl group, amino group, acyl group, carboxy group, substituted or unsubstituted alkyl group, At least two of R 1 to R 3 are fluorine.
- a solid-state imaging device comprising a photoelectric conversion film containing a subphthalocyanine derivative represented by the following general formula (1); An optical system for guiding incident light to the solid-state imaging device; An electronic device comprising: an arithmetic processing circuit that performs arithmetic processing on an output signal from the solid-state imaging device.
- X 1 to X 6 are independently of each other hydrogen, halogen, hydroxy group, thiol group, alkoxy group, cyano group, nitro group, silylalkyl group, silylalkoxy group, arylsilyl group, thioalkyl group, thioaryl group, sulfonyl Group, arylsulfonyl group, alkylsulfonyl group, amino group, alkylamino group, arylamino group, acyl group, acylamino group, acyloxy group, carboxy group, carboxamide group, carboalkoxy group, substituted or unsubstituted alkyl group, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, Z is hydrogen, halogen, hydroxy group, thiol group, imide group
- R 1 to R 3 are independently of each other hydrogen, halogen, hydroxy group, alkoxy group, cyano group, nitro group, sulfonyl group, amino group, acyl group, carboxy group, substituted or unsubstituted alkyl group, At least two of R 1 to R 3 are fluorine.
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Abstract
Description
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。
1.本開示の一実施形態
1.1.本実施形態に係る光電変換膜
1.2.本実施形態に係る光電変換膜を用いた光電変換素子
1.3.実施例
2.本実施形態に係る光電変換膜の適用例
2.1.固体撮像素子
2.2.電子機器
3.まとめ
[1.1.本実施形態に係る光電変換膜]
まず、本開示の一実施形態に係る光電変換膜について説明する。本実施形態に係る光電変換膜は、600nmを超える波長領域の光の吸収が小さい光吸収特性を有する。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
R1~R3のうち少なくとも2つ以上は、フッ素である。
続いて、図1を参照して、本実施形態に係る光電変換膜を用いた光電変換素子100について説明する。図1は、本実施形態に係る光電変換膜を用いた光電変換素子の一例を示す概略図である。
以下では、実施例および比較例を参照しながら、本実施形態に係るサブフタロシアニン誘導体、光電変換膜、および光電変換素子について具体的に説明する。なお、以下に示す実施例は、あくまでも一例であって、本実施形態に係るサブフタロシアニン誘導体、光電変換膜、および光電変換素子が下記の例に限定されるものではない。
まず、一般式(1)で表されるサブフタロシアニン誘導体の光吸収特性をシミュレーション解析にて評価した。具体的には、以下で構造式を示すサブフタロシアニン誘導体に対してシミュレーション解析を行い、極大吸収波長λmaxを計算した。
次に、一般式(1)で表されるサブフタロシアニン誘導体の合成方法について説明する。一般式(1)で表されるサブフタロシアニン誘導体は、下記の反応式1で表される一般化された合成方法により合成することができる。なお、以下に述べる合成方法はあくまでも一例であって、一般式(1)で表されるサブフタロシアニン誘導体の合成方法が下記の例に限定されるものではない。
続いて、上記で合成したC1-CF3-SubPcおよびC3-CF3-SubPcの分光特性を評価した。具体的には、C1-CF3-SubPcおよびC3-CF3-SubPcを薄膜形成した評価サンプルを作製し、分光特性を評価した。
まず、石英基板に対してUV/オゾン処理を行った。処理後の石英基板を有機蒸着装置に投入し、1×10-5Pa以下の真空中で基板ホルダを回転させながら、上記で合成したC1-CF3-SubPcを抵抗加熱法によって蒸着し、評価サンプルを作製した。蒸着したC1-CF3-SubPcの膜厚は50nmであった。
実施例4で用いたC1-CF3-SubPcの代わりに、C3-CF3-SubPcを用いた以外は実施例4と同様にして評価サンプルを作製し、同様にITO成膜、およびアニール処理を行った。
実施例4で用いたC1-CF3-SubPcの代わりに、下記で示すサブフタロシアニンクロライド(SubPc)を用いた以外は実施例4と同様にして評価サンプルを作製し、同様にITO成膜、およびアニール処理を行った。なお、サブフタロシアニンクロライドは、Sigma-Aldrich社から購入したものを昇華精製して使用した。
作製した実施例4および5、比較例4の評価サンプルに対して、紫外可視分光光度計を用いて、ITO成膜前(ITO無/アニール無)、ITO成膜後(ITO有/アニール無)、アニール処理後(ITO有/アニール有)の分光特性の変化を評価した。各評価サンプルの分光特性変化の評価結果を図2A、図2Bおよび図3に示す。
さらに、上記で合成したC1-CF3-SubPcおよびC3-CF3-SubPcを用いて、以下の作製方法で光電変換素子を作製し、光電変換効率を評価した。なお、以下に述べる光電変換素子の構造および作製方法はあくまでも一例であって、本実施形態に係る光電変換膜を用いた光電変換素子の構造および作製方法が下記の例に限定されるものではない。
まず、ITO電極付石英基板に対してUV/オゾン処理を行った。なお、該石英基板におけるITO電極(下部電極)の膜厚は、50nmであった。次に、処理後の石英基板を有機蒸着装置に投入し、1×10-5Pa以下の真空中で、基板ホルダを回転させながら、C1-CF3-SubPcおよびキナクリドンを抵抗加熱法によって蒸着した。なお、蒸着速度は、C1-CF3-SubPcとキナクリドンとの体積比が1:1となるように、それぞれ0.1nm/秒にて蒸着し、合計100nm成膜して光電変換膜を形成した。続いて、該光電変換膜上にAlSiCuを蒸着法にて膜厚100nmで成膜し、上部電極を形成した。以上の作製方法により1mm×1mmの光電変換領域を有する光電変換素子を作製した。
実施例5で用いたC1-CF3-SubPcの代わりに、C3-CF3-SubPcを用いた以外は実施例5と同様にして光電変換素子を作製した。
作製した実施例6および7に係る光電変換素子に対して、アニール処理前後での光電変換効率を評価した。光電変換効率の評価結果を表3に示す。
以下では、図4~6を参照して、本実施形態に係る光電変換膜を用いた光電変換素子100の適用例について説明する。本実施形態に係る光電変換素子100は、例えば、固体撮像素子における有機光電変換部11Gとして好適に用いることができる。
図4は、本実施形態に係る光電変換素子100を適用した固体撮像素子1の全体構成を表した概略図である。固体撮像素子1は、例えば、CMOS(Complementary Metal Oxide Semiconductor)イメージセンサである。固体撮像素子1は、半導体基板11上に、撮像エリアとしての画素部10aを有し、画素部10aの周辺領域に、例えば、行走査部131、水平選択部133、列走査部134、およびシステム制御部132からなる周辺回路部130を有する。
半導体基板11は、例えば、n型のシリコン(Si)層110を含み、シリコン層110の所定の領域には、無機光電変換部11B、11R、および緑用蓄電層110Gが埋め込み形成されている。また、半導体基板11には、有機光電変換部11Gからの電荷(電子または正孔)の伝送経路となる導電性プラグ120a1、120b1が埋設されている。
半導体基板11の面S2上には、多層配線層51が形成される。多層配線層51には、複数の配線51aが、層間絶縁膜52を介して配設されている。このように、画素10a1では、多層配線層51が受光面とは反対側に形成されており、いわゆる裏面照射型の固体撮像素子となっている。多層配線層51には、例えば、シリコンよりなる支持基板53が貼り合わせられていてもよい。
有機光電変換部11Gは、有機化合物により選択的な波長領域の光(ここでは、450nm以上600nm以下の波長領域に対応する緑色光)を吸収し、電子・正孔対を発生させる有機光電変換素子である。有機光電変換部11Gは、信号電荷を取り出すための一対の電極(下部電極13a、上部電極16)によって有機光電変換膜15が挟持された構成を有する。下部電極13aおよび上部電極16は、配線層やコンタクトメタル層を介して、半導体基板11内に埋設された導電性プラグ120a1、120b1に電気的に接続されている。
上述した固体撮像素子1は、例えば、デジタルスチルカメラまたはビデオカメラ等のカメラシステムや、撮像機能を有する携帯電話など、撮像機能を備えたあらゆるタイプの電子機器に適用することができる。図6にて、このような電子機器の概略構成を示す。図6は、本実施形態に係る電子機器の構成を説明する概略図である。
以上説明したように、本実施形態に係る光電変換膜は、一般式(1)で表されるサブフタロシアニン誘導体を含むことにより、600nmを超える波長領域の光の吸収を小さくすることができる。したがって、本実施形態に係る光電変換膜は、450nm以上600nm以下の波長領域の緑色光を選択的に吸収することができる。よって、本実施形態に係る光電変換膜は、固体撮像素子における緑色光の光電変換素子に対して好適に用いることができ、固体撮像素子の撮像特性を向上させることができる。
(1)
下記一般式(1)で表されるサブフタロシアニン誘導体を含む、光電変換膜。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。
(2)
前記X1~X6は、互いに独立して、前記一般式(2)で表される置換基である、前記(1)に記載の光電変換膜。
(3)
前記一般式(2)で表される置換基は、ジフルオロメチル基またはトリフルオロメチル基である、前記(1)または(2)に記載の光電変換膜。
(4)
前記Zは、ハロゲン、ヒドロキシ基、または置換もしくは未置換のアルコキシ基である、前記(1)~(3)のいずれか一項に記載の光電変換膜。
(5)
前記光電変換膜は、バルクヘテロ膜として形成される、前記(1)~(4)のいずれか一項に記載の光電変換膜。
(6)
下記一般式(1)で表されるサブフタロシアニン誘導体を含む光電変換膜を備える、固体撮像素子。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。
(7)
前記光電変換膜は、450nm以上600nm以下の波長の緑色光を吸収し、吸収した緑色光を光電変換する、前記(6)に記載の固体撮像素子。
(8)
前記光電変換膜を含む複数の光電変換膜が積層され、積層型固体撮像素子として構成された、前記(6)または(7)に記載の固体撮像素子。
(9)
下記一般式(1)で表されるサブフタロシアニン誘導体を含む光電変換膜を備える固体撮像素子と、
前記固体撮像素子に入射光を導く光学系と、
前記固体撮像素子からの出力信号を演算処理する演算処理回路と、を備える電子機器。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。
101 基板
102 下部電極
103 pバッファ層
104 光電変換膜
105 nバッファ層
106 上部電極
Claims (9)
- 下記一般式(1)で表されるサブフタロシアニン誘導体を含む、光電変換膜。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。 - 前記X1~X6は、互いに独立して、前記一般式(2)で表される置換基である、請求項1に記載の光電変換膜。
- 前記一般式(2)で表される置換基は、ジフルオロメチル基またはトリフルオロメチル基である、請求項1に記載の光電変換膜。
- 前記Zは、ハロゲン、ヒドロキシ基、または置換もしくは未置換のアルコキシ基である、請求項1に記載の光電変換膜。
- 前記光電変換膜は、バルクヘテロ膜として形成される、請求項1に記載の光電変換膜。
- 下記一般式(1)で表されるサブフタロシアニン誘導体を含む光電変換膜を備える、固体撮像素子。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。 - 前記光電変換膜は、450nm以上600nm以下の波長の緑色光を吸収し、吸収した緑色光を光電変換する、請求項6に記載の固体撮像素子。
- 前記光電変換膜を含む複数の光電変換膜が積層され、積層型固体撮像素子として構成された、請求項7に記載の固体撮像素子。
- 下記一般式(1)で表されるサブフタロシアニン誘導体を含む光電変換膜を備える固体撮像素子と、
前記固体撮像素子に入射光を導く光学系と、
前記固体撮像素子からの出力信号を演算処理する演算処理回路と、を備える電子機器。
X1~X6は、互いに独立して、水素、ハロゲン、ヒドロキシ基、チオール基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、または置換もしくは未置換のヘテロアリール基であり、
Zは、水素、ハロゲン、ヒドロキシ基、チオール基、イミド基、アルコキシ基、シアノ基、ニトロ基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、チオアルキル基、チオアリール基、スルホニル基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、アシル基、アシルアミノ基、アシルオキシ基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のシクロアルキル基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、または酸素原子を介して連結されたサブフタロシアニン誘導体であり、
前記X1およびX2の少なくとも1つ以上、前記X3およびX4の少なくとも1つ以上、ならびに前記X5およびX6の少なくとも1つ以上は、下記一般式(2)で表される置換基である。
R1~R3は、互いに独立して、水素、ハロゲン、ヒドロキシ基、アルコキシ基、シアノ基、ニトロ基、スルホニル基、アミノ基、アシル基、カルボキシ基、置換もしくは未置換のアルキル基であり、
前記R1~R3のうち少なくとも2つ以上は、フッ素である。
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