WO2017169241A1 - Dispositif de capture d'image à semi-conducteurs - Google Patents

Dispositif de capture d'image à semi-conducteurs Download PDF

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WO2017169241A1
WO2017169241A1 PCT/JP2017/005645 JP2017005645W WO2017169241A1 WO 2017169241 A1 WO2017169241 A1 WO 2017169241A1 JP 2017005645 W JP2017005645 W JP 2017005645W WO 2017169241 A1 WO2017169241 A1 WO 2017169241A1
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photoelectric conversion
layers
layer
pixel
solid
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PCT/JP2017/005645
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Japanese (ja)
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森川隆史
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ソニー株式会社
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    • 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
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N25/00—Circuitry of solid-state image sensors [SSIS]; Control thereof
    • H04N25/70—SSIS architectures; Circuits associated therewith
    • H04N25/79—Arrangements of circuitry being divided between different or multiple substrates, chips or circuit boards, e.g. stacked image sensors
    • 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 at least one potential-jump barrier or surface barrier, 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
    • H04N23/10—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths
    • H04N23/12—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths with one sensor only
    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N25/00—Circuitry of solid-state image sensors [SSIS]; Control thereof
    • H04N25/70—SSIS architectures; Circuits associated therewith
    • H04N25/76—Addressed sensors, e.g. MOS or CMOS sensors

Definitions

  • This technology relates to a solid-state imaging device and an electronic device.
  • an imaging apparatus it is desired that clear imaging can be performed even in a dark place, and for this purpose, there are approaches for realizing higher sensitivity of photoelectric conversion elements and longer storage time of photoelectrically converted charges.
  • these approaches when these approaches are employed, if the storable amount of the photoelectrically converted charge cannot be sufficiently increased, the charge may be saturated during imaging in a bright place and whiteout or color saturation may occur.
  • a technique for preventing overexposure and color saturation a technique for realizing a wide dynamic range by overlapping images having different accumulation times is widely used in commercially available digital cameras.
  • Patent Documents 1 and 2 disclose a technique capable of obtaining a composite image having a wide dynamic range even when a moving subject is imaged by forming photodiodes of different sizes in the same imaging device.
  • the light receiving area of the photodiode can be switched by a switch, the light receiving area is reduced for a bright subject to reduce the sensitivity, and the light receiving area is increased for a dark subject.
  • a technique for increasing the sensitivity is disclosed.
  • Patent Documents 5 to 8 disclose technologies for realizing pixels having different sensitivities by arranging a plurality of pixels in parallel and varying the on-chip light collection rate between the pixels arranged in parallel.
  • Patent Documents 9 to 13 disclose a technique for realizing pixels having different sensitivities by arranging a plurality of pixels in parallel and changing the light attenuation layer and the filter film thickness between the pixels arranged in parallel.
  • JP 2000-059687 A Japanese Patent Application Laid-Open No. 2014-17592 JP-A-5-207376 JP 2006-86425 A JP 2003-198952 A JP 2010-080648 A JP 2005-86082 A JP 2005-86083 A JP 2012-048814 A JP 2003-198952 A JP 2006-86425 A JP 2014-075757 A JP 2014-175553 A
  • the above-described images having different accumulation times are images having different information in time, and image quality degradation such as afterimages occurs when a moving object is photographed.
  • image quality degradation such as afterimages occurs when a moving object is photographed.
  • signal processing after imaging becomes complicated, and processing time and power consumption increase, which causes problems such as an increase in imaging interval and battery consumption.
  • the present technology has been made in view of the above problems, and aims to prevent a spatial or temporal shift at the pixel level while realizing a wide dynamic range in a solid-state imaging device.
  • One aspect of the present technology includes a photoelectric conversion unit formed by stacking four or more photoelectric conversion layers in a direction along the thickness direction of the semiconductor, and the four or more photoelectric conversion layers include at least two layers.
  • the four or more photoelectric conversion layers include at least two layers.
  • the solid-state imaging device has a third spectral characteristic different from the characteristic.
  • the solid-state imaging device described above includes various modes such as being implemented in another device or implemented together with another method. Moreover, this technique is realizable also as an imaging system provided with the said solid-state imaging device.
  • FIG. 1 is a diagram illustrating a photoelectric conversion unit 10 included in the solid-state imaging device according to the present embodiment.
  • the solid-state imaging device according to the present embodiment constitutes one pixel in a solid-state imaging device such as a CMOS image sensor used in an electronic apparatus such as a digital still camera or a digital video camera.
  • the solid-state imaging device includes a so-called vertical spectroscopic photoelectric conversion unit 10 formed by stacking photoelectric conversion layers 11 to 14 in a direction along the thickness direction.
  • a microlens array may be further formed on the upper layer of the photoelectric conversion unit 10 to improve the light collection rate.
  • the side close to the light incident side may be called the upper layer, and the side far from the light incident side may be called the lower layer.
  • the photoelectric conversion unit 10 is disposed on a substrate (not shown).
  • a substrate not shown.
  • the photoelectric conversion layer 11 side it is assumed that light is incident from the photoelectric conversion layer 11 side, and the case where the photoelectric conversion layers 11, 12, 13, and 14 are provided in this order from the upper layer to the lower layer will be described as an example.
  • the arrangement order of the photoelectric conversion layers 11 to 14 can be variously changed.
  • the above-described substrate is preferably formed using a material such as highly transparent glass, polyethylene, polyethylene terephthalate, polyethersulfone, or polypropylene when light is incident from the substrate side.
  • a material such as highly transparent glass, polyethylene, polyethylene terephthalate, polyethersulfone, or polypropylene when light is incident from the substrate side.
  • other materials such as Si, Ge, and GaAs can be used in addition to the above materials.
  • the photoelectric conversion layer 11 has a spectral characteristic (first spectral characteristic) that mainly absorbs blue light, and the main photoelectric conversion wavelength region is the wavelength region of blue light.
  • the photoelectric conversion layers 12 and 13 have spectral characteristics (second spectral characteristics) that mainly absorb green light, and the main photoelectric conversion wavelength region is the wavelength region of green light.
  • the photoelectric conversion layer 14 has spectral characteristics (third spectral characteristics) that mainly absorb red light, and the main photoelectric conversion wavelength range is the wavelength range of red light.
  • the photoelectric conversion layers 12 and 13 having the same second spectral characteristics may be formed of the same material, or may be formed of different types of materials having substantially the same spectral characteristics.
  • the photoelectric conversion layer 11 can absorb light of at least 400 nm or more and 500 nm or less, and preferably has a peak wavelength absorptance of 50% or more in that wavelength region.
  • the photoelectric conversion layers 12 and 13 can absorb light having a wavelength of at least 500 nm and not more than 600 nm, and preferably have a peak wavelength absorptance of 50% or more in that wavelength region.
  • the photoelectric conversion layer 14 can absorb light having a wavelength of at least 600 nm and not more than 700 nm, and preferably has a peak wavelength absorptance of 50% or more in that wavelength region.
  • the photoelectric conversion layers 11 to 14 have the above-described spectral characteristics
  • various materials can be used without any particular limitation.
  • Si-based material, GaAs-based material, Ge-based material, InAs-based material, organic-based material, or the like can be used.
  • a structure in which the above-described dye having a light absorption function is added to an appropriately selected material may be employed.
  • the number of photoelectric conversion layers is not limited to four.
  • the layer having the first spectral characteristic has at least one layer, the layer having the second spectral characteristic has at least two layers, and has the third spectral characteristic.
  • Various changes are possible as long as at least one layer is included.
  • the upper photoelectric conversion layer functions as an optical filter for the lower photoelectric conversion layer. Therefore, especially between the photoelectric conversion layers 12 and 13 having the same second spectral characteristic, the lower photoelectric conversion layer 13 similarly uses the second photoelectric conversion layer 13 to absorb the remaining light absorbed by the second photoelectric characteristic. If these two photoelectric conversion layers have substantially the same spectral characteristics, the photoelectric conversion layer 13 has a lower sensitivity than the photoelectric conversion layer 12. That is, it is possible to realize a state of different sensitivity between the upper photoelectric conversion layer 12 and the lower photoelectric conversion layer 13.
  • FIG. 2 is a diagram showing a structure around the photoelectric conversion layer when an organic photoelectric conversion film is used.
  • a pair of upper and lower electrodes are disposed on the upper and lower surfaces of each of the photoelectric conversion layers 11 to 14. Specifically, an upper electrode 11a and a lower electrode 11b are disposed on the upper and lower surfaces of the photoelectric conversion layer 11, and an upper electrode 12a and a lower electrode 12b are disposed on the upper and lower surfaces of the photoelectric conversion layer 12, respectively. An upper electrode 13 a and a lower electrode 13 b are disposed on the upper and lower surfaces of the conversion layer 13, and an upper electrode 14 a and a lower electrode 14 b are disposed on the upper and lower surfaces of the photoelectric conversion layer 14.
  • a constant voltage Vb is applied to the upper electrodes 11a to 14a, and the lower electrodes 11b to 14b are high-concentration impurities formed on the substrate 20 by through electrodes that penetrate the photoelectric conversion layers 11 to 14 and connect to the substrate 20.
  • the region 21 is connected to a circuit element such as a transfer transistor.
  • the upper electrodes 11a to 14a and the lower electrodes 11b to 14b are preferably transparent electrodes.
  • materials for such electrodes include indium tin oxide, indium oxide, and tin oxide.
  • metals such as aluminum, vanadium, gold, silver, platinum, iron, cobalt, carbon, nickel, tungsten, palladium, magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese and their alloys
  • a semi-transparent electrode having a film thickness of about 20 to 80 nm may be used.
  • the electrode may be formed using a conductive polymer typified by polyacetylene, polyaniline, polypyrrole, or polythiophene.
  • An insulating film is provided between the electrodes of the photoelectric conversion layers adjacent to each other. That is, the lower electrode 11b of the photoelectric conversion layer 11 and the upper electrode 12a of the photoelectric conversion layer 12 are insulated by the insulating film 15, and the lower electrode 12b of the photoelectric conversion layer 12 and the upper electrode 13a of the photoelectric conversion layer 13 are insulated.
  • the film 16 is insulated, and the lower electrode 13 b of the photoelectric conversion layer 13 and the upper electrode 14 a of the photoelectric conversion layer 14 are insulated by the insulating film 17.
  • the insulating films 15, 16, and 17 can be formed using a transparent insulating material such as glass, polyethylene, polyethylene terephthalate, polyethersulfone, and polypropylene. Silicon nitride, silicon oxide, or the like may be used. Alternatively, silicon nitride formed by plasma CVD and having high density and good transparency may be used.
  • the photoelectric conversion unit 10 configured as described above, the light that the photoelectric conversion layers 11 to 14 absorb according to the spectral characteristics in a state where a voltage is applied between the upper and lower electrodes of each photoelectric conversion layer 11 to 14. A charge is generated by this, and thereby a photocurrent is generated.
  • the photoelectric conversion layer 11 generates an electric charge according to the amount of light absorbed by the first spectral characteristic of the incident light to the photoelectric conversion unit 10, and the photoelectric conversion layer 12 receives the incident light attenuated by the absorption amount of the photoelectric conversion layer 11.
  • the photoelectric conversion layer 13 generates a charge corresponding to the amount of light absorbed by the second spectral characteristic after the incident light attenuated by the absorption amount of the photoelectric conversion layers 11 and 12 is generated.
  • the photoelectric conversion layer 14 generates and generates charges corresponding to the amount of light absorbed by the third spectral characteristic of the incident light attenuated by the absorption amount of the photoelectric conversion layers 11, 12, 13, and 14.
  • the light receiving sensitivity of the photoelectric conversion layers 12 and 13 varies depending on the layer thickness of the photoelectric conversion layers 12 and 13.
  • the photoelectric conversion layers 12 and 13 are formed with the same thickness. The thinner the photoelectric conversion layers 12 and 13, the lower the sensitivity of the photoelectric conversion layers 12 and 13, and the smaller the sensitivity difference between the photoelectric conversion layers 12 and 13.
  • the sensitivity of the photoelectric conversion layer 12 increases and the sensitivity of the photoelectric conversion layer 13 decreases, and the sensitivity difference between the photoelectric conversion layers 12 and 13 increases.
  • the ratio of the sensitivity of the photoelectric conversion layers 12 and 13 formed with the same thickness can be adjusted by the layer thickness of the photoelectric conversion layers 12 and 13.
  • the output signals S11, S12, S13, and S14 from the photoelectric conversion layers 11 to 14 configured in this way are, for example, the output signal S12 of the photoelectric conversion layer 12 that is a high-sensitivity pixel and the low-sensitivity pixel as shown in FIG.
  • the output signal S13 of a certain photoelectric conversion layer 13 is switched and used.
  • Such switching control may be performed by providing a switching circuit in the pixel PXL, which will be described later.
  • the output signal S12 of the photoelectric conversion layer 12 that is a high-sensitivity pixel and another photoelectric conversion layer
  • the output signals S11 and S14 of the pixels 11 and 14 are used as RGB color signals of the pixel.
  • the amount of incident light is large as shown in FIG. 3B (such as shooting in a high illumination environment)
  • the low-sensitivity pixel The output signal S13 of the photoelectric conversion layer 13 and the output signals S11 and S14 of the other photoelectric conversion layers 11 and 14 are used as RGB signals of the pixel.
  • magnification information determined according to the sensitivity ratio between the photoelectric conversion layers 12 and 13 is measured and held in advance.
  • the combination of the output signal S12 of the photoelectric conversion layer 12 that is a high-sensitivity pixel and the output signals S11 and S14 of the other photoelectric conversion layers 11 and 14 is the RGB color signal of the pixel. Become.
  • the output signal S13 of the photoelectric conversion layer 13 which is a low-sensitivity pixel is amplified based on the magnification information (x times), and the output signal xS13 of the photoelectric conversion layer 13 after amplification and other photoelectric signals A combination of the output signals S11 and S14 of the conversion layers 11 and 14 becomes a signal of each color of RGB of the pixel.
  • the determination of the amount of incident light may be performed based on the output of a separately provided illuminance sensor or the like, but the saturation / output signal S12 of the photoelectric conversion layer 12 that is a high-sensitivity pixel. Determination can be based on desaturation. Specifically, the level (saturation level Smax) of the output signal S12 when the photoelectric conversion layer 12 is saturated is measured and held in advance. When the output signal S12 from the photoelectric conversion layer 12 does not reach the saturation level Smax, the output signal S12 from the photoelectric conversion layer 12 is used as the RGB color signal of the pixel, and the output signal from the photoelectric conversion layer 12 is output.
  • the output signal S13 of the photoelectric conversion layer 13 is amplified to be a signal for each color of RGB of the pixel. Note that it is possible to appropriately select whether the saturation level is determined based on the output signal S12 of the photoelectric conversion layer 12 in the plurality of pixels constituting the imaging device, and the output signal of the photoelectric conversion layer 12 of the specific pixel. The determination may be made based on S12, or may be made based on the average of the output signals S12 of the photoelectric conversion layers 12 of all the pixels or a plurality of pixels selected according to an appropriate selection criterion.
  • a wide dynamic range can be realized by providing two or more photoelectric conversion layers having sensitivity differences in the same first spectral characteristic in the stacked state. That is, if the photocurrent output from the photoelectric conversion layer 12 is used, a high-sensitivity pixel is realized, and if the photocurrent output from the photoelectric conversion layer 13 is used, a low-sensitivity pixel is realized.
  • the photoelectric conversion layers 12 and 13 generate charges based on the same incident light in a state where the photoelectric conversion layers 12 and 13 are stacked on the top and bottom, and therefore, between the signal based on the output from the high sensitivity pixel and the signal based on the output from the low sensitivity pixel. There will be no spatial or temporal misalignment.
  • the organic photoelectric conversion film for realizing the photoelectric conversion layers 11 to 14 is formed by stacking an electromagnetic wave absorption site, a photoelectric conversion site, an electron transport site, a hole transport site, an electron blocking site, a hole blocking site, a crystallization preventing site, or the like. Formed from mixing.
  • the organic photoelectric conversion film preferably contains an organic p-type semiconductor (compound) or an organic n-type semiconductor (compound). Any organic p-type semiconductor and organic n-type semiconductor may be contained in the organic photoelectric conversion film. Further, it may or may not have absorption in the visible and infrared regions, but preferably at least one compound (organic dye) having absorption in the visible region is used. Furthermore, a colorless p-type semiconductor and an n-type semiconductor may be used, and an organic dye may be added thereto. When a three-layer structure of p-type layer / bulk heterojunction layer / n-type layer is used, the p-type or n-type semiconductor on the incident light side is preferably colorless.
  • Organic p-type semiconductors are donor organic semiconductors (compounds), which are typically represented by hole-transporting organic compounds and refer to organic compounds that have the property of easily donating electrons. More specifically, an organic compound having a smaller ionization potential when two organic materials are used in contact with each other. Therefore, any organic compound can be used as the donor organic compound as long as it is an electron-donating organic compound.
  • the metal complex etc. which it has as can be used.
  • any organic compound having an ionization potential smaller than that of the organic compound used as the n-type (acceptor property) compound may be used as the donor organic semiconductor.
  • Organic n-type semiconductors are acceptor organic semiconductors (compounds), which are mainly represented by electron-transporting organic compounds and refer to organic compounds that have a property of easily accepting electrons. More specifically, the organic compound having the higher electron affinity when two organic compounds are used in contact with each other. Therefore, as the acceptor organic compound, any organic compound can be used as long as it is an electron-accepting organic compound.
  • condensed aromatic carbocyclic compounds naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, fluoranthene derivatives
  • 5- to 7-membered heterocyclic compounds containing nitrogen atoms, oxygen atoms, and sulfur atoms E.g.
  • pyridine pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, Benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, o Metal complexes having as ligands such as saziazole, imidazopyridine, pyralidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, tribenzazepine), polyarylene compounds, fluorene compounds, cyclopentadiene compounds,
  • Any p-type organic dye or n-type organic dye may be used, but preferably a cyanine dye, styryl dye, hemicyanine dye, merocyanine dye (including zero methine merocyanine (simple merocyanine)), three nucleus Merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenyl Methane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo
  • the metal complex compound is a metal complex having a ligand having at least one nitrogen atom or oxygen atom or sulfur atom coordinated to the metal, and the metal ion in the metal complex is not particularly limited, but preferably beryllium ion, magnesium Ion, aluminum ion, gallium ion, zinc ion, indium ion, or tin ion, more preferably beryllium ion, aluminum ion, gallium ion, or zinc ion, and still more preferably aluminum ion or zinc ion.
  • ligands contained in the metal complex For example, “Photochemistry and Photo physics of Coordination Compounds” Springer Verlag H. Examples include ligands described in Yersin's 1987 issue, “Organometallic Chemistry-Fundamentals and Applications”, ⁇ ⁇ ⁇ ⁇ Akio Yamamoto's issue in 1982, and the like.
  • the ligand is preferably a nitrogen-containing heterocyclic ligand (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms).
  • a bidentate or higher ligand preferably a bidentate ligand such as a pyridine ligand, a bipyridyl ligand, a quinolinol ligand, a hydroxyphenylazole ligand (hydroxyphenyl) Benzimidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon 1 to 10, for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc.), aryloxy coordination (Preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms,
  • Phenyloxy, 4-biphenyloxy, etc. heteroaryloxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms,
  • heteroaryloxy ligands preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms
  • alkylthio ligands preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
  • arylthio ligands preferably having 6 to 30 carbon atoms, more preferably Or having 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.
  • a heterocyclic substituted thio ligand preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom.
  • a nitrogen-containing heterocyclic ligand, an aryloxy ligand, a heteroaryloxy group, or a siloxy ligand is used.
  • a nitrogen-containing heterocyclic ligand, an aryloxy ligand, or a siloxy ligand is used.
  • Methine dyes such as cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squalium dyes, croconium dyes and azamethine dyes can be preferably used. More preferred are merocyanine dyes, trinuclear merocyanine dyes, and tetranuclear merocyanine dyes, and more preferred are merocyanine dyes.
  • 5,340,694 (particularly, 21 to 58, provided that the number of n12, n15, n17 and n18 is not limited in the dyes shown in (XI), (XII) and (XIII), and is an integer of 0 or more (preferably 4 or less) And a dye having a partial structure or structure shown in the general formula and specific examples described in (1)) can be preferably used.
  • the blending ratio of the p-type organic semiconductor and the n-type organic semiconductor in the intermediate layer of the photoelectric conversion film can be appropriately set within a range of 0.1: 99.9 to 99.9: 0.1 by mass ratio. .
  • the organic material (n-type compound) having an electron transporting property preferably has an ionization potential larger than 6.0 eV, and more preferably represented by the following general formula (X).
  • Formula (X) L- (A) m (In the formula, A represents a heterocyclic group in which two or more aromatic heterocycles are condensed, and the heterocyclic group represented by A may be the same or different. M represents an integer of 2 or more. L Represents a linking group.)
  • A represents a heterocyclic group in which two or more aromatic heterocycles are condensed, and the heterocyclic group represented by A may be the same or different.
  • M represents an integer of 2 or more.
  • the orientation control described below can be applied.
  • the orientation of the organic compound is ordered as compared with a random state. If it is not random, the degree of order may be low or high, but high order is preferable.
  • an organic photoelectric conversion film having a p-type semiconductor layer, an n-type semiconductor layer (preferably a mixed / dispersed (bulk heterojunction structure) layer) between a pair of electrodes, at least of the p-type semiconductor and the n-type semiconductor
  • An organic photoelectric conversion film characterized by containing an organic compound whose orientation is controlled in one direction is preferable, and more preferably, an (possible) organic compound whose orientation is controlled in both a p-type semiconductor and an n-type semiconductor. This is the case.
  • the organic compound used for the organic photoelectric conversion film of the photoelectric conversion element those having ⁇ -conjugated electrons are preferably used, but the ⁇ -electron plane is not perpendicular to the substrate (electrode substrate) but is an angle close to parallel. It is more preferable that it is oriented at.
  • the angle with respect to the substrate is preferably 0 ° or more and 80 ° or less, more preferably 0 ° or more and 60 ° or less, further preferably 0 ° or more and 40 ° or less, and further preferably 0 ° or more and 20 ° or less. Particularly preferably, it is 0 ° or more and 10 ° or less, and most preferably 0 ° (that is, parallel to the substrate).
  • the organic compound layer whose orientation is controlled may be partially included in the entire organic photoelectric conversion film.
  • the ratio of the portion whose orientation is controlled with respect to the entire organic photoelectric conversion film is 10% or more, more preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and particularly preferably 90% or more, most preferably 100%.
  • Such a state improves the photoelectric conversion efficiency by compensating for the short carrier diffusion length of the organic photoelectric conversion film by controlling the orientation of the organic compound in the organic photoelectric conversion film in the organic photoelectric conversion film. .
  • the orientation of the organic compound can be controlled by selecting the substrate and adjusting the deposition conditions. For example, the method of giving anisotropy to the organic compound which gives a rubbing process to the substrate surface and grows on it etc. is mentioned. However, the structure depending on the substrate crystal is observed only at a thickness of at most a dozen layers, and when the film thickness is increased, a bulk crystal structure is taken.
  • the film thickness is preferably 100 nm or more (100 layers or more as molecules). In such a case, the interaction between organic compounds in addition to the substrate is used. Therefore, it is necessary to control the orientation.
  • any interaction force between organic compounds may be used.
  • van der Waals force More precisely, an orientation force acting between a permanent dipole and a permanent dipole
  • It can be expressed in terms of induced force acting between permanent dipole and induced dipole, and dispersion force acting between temporary dipole and induced dipole.
  • Charge transfer force CT
  • Coulomb force electrostatic force
  • hydrophobic bond Force hydrogen bond strength, coordination bond strength and the like. Only one of these binding forces can be used, or a plurality of arbitrary binding forces can be used in combination.
  • van der Waals force charge transfer force, coulomb force, hydrophobic bond force and hydrogen bond force
  • van der Waals force charge transfer force
  • coulomb force hydrophobic bond force
  • hydrogen bond force hydrogen bond force
  • fan fan.
  • -Del Waals force and Coulomb force most preferably van der Waals force.
  • the covalent bond or the coordination bond may be formed in advance or may be formed in the process of forming the organic photoelectric conversion film.
  • intermolecular forces and covalent bonds the case where the orientation of the organic compound is controlled preferably using intermolecular forces.
  • the attractive energy of these intermolecular forces is preferably 15 kJ / mol or more, more preferably 20 kJ / mol or more, and particularly preferably 40 kJ / mol or more. Although there is no upper limit in particular, it is preferably 5000 kJ / mol or less, more preferably 1000 kJ / mol or less.
  • the heterojunction plane (for example, the pn junction plane) is not parallel to the substrate.
  • the heterojunction plane is oriented not at an angle close to the substrate (electrode substrate) but at an angle close to the vertical.
  • the angle with respect to the substrate is preferably 10 ° or more and 90 ° or less, more preferably 30 ° or more and 90 ° or less, further preferably 50 ° or more and 90 ° or less, and further preferably 70 ° or more and 90 ° or less. Particularly preferably, it is 80 ° or more and 90 ° or less, and most preferably 90 ° (that is, perpendicular to the substrate).
  • the organic compound layer having a heterojunction surface controlled as described above may be partially included in the entire organic photoelectric conversion film.
  • the ratio of the portion whose orientation is controlled with respect to the entire organic photoelectric conversion film is 10% or more, more preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and particularly preferably 90% or more, most preferably 100%.
  • the area of the heterojunction surface in the organic photoelectric conversion film is increased, the amount of carriers such as electrons, holes, and electron-hole pairs generated at the interface is increased, and the photoelectric conversion efficiency can be improved.
  • the layer containing these organic compounds is formed by a dry film formation method or a wet film formation method.
  • the dry film forming method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a physical vapor deposition method such as an MBE method, or a CVD method such as plasma polymerization.
  • a wet film forming method a casting method, a spin coating method, a dipping method, an LB method, or the like is used.
  • a polymer compound as at least one of the p-type semiconductor (compound) or the n-type semiconductor (compound)
  • a dry film formation method such as vapor deposition
  • an oligomer thereof can be preferably used instead.
  • a dry film forming method is preferably used, and a vacuum deposition method is particularly preferably used.
  • the vacuum deposition method is basically based on the method of heating compounds such as resistance heating deposition method and electron beam heating deposition method, shape of deposition source such as crucible and boat, vacuum degree, deposition temperature, substrate temperature, deposition rate, etc. It is a parameter. In order to make uniform deposition possible, it is preferable to perform deposition by rotating the substrate.
  • the degree of vacuum is preferably higher, and vacuum deposition is performed at 10 ⁇ 4 Torr or less, preferably 10 ⁇ 6 Torr or less, particularly preferably 10 ⁇ 8 Torr or less. It is preferable that all steps during the vapor deposition are performed in a vacuum, and basically the compound is not directly in contact with oxygen and moisture in the outside air.
  • the above-described conditions for vacuum deposition need to be strictly controlled because they affect the crystallinity, amorphousness, density, density, etc. of the organic film. It is preferable to perform PI or PID control of the deposition rate using a film thickness monitor such as a quartz crystal resonator or an interferometer.
  • a co-evaporation method, a flash vapor deposition method, or the like can be preferably used.
  • the photoelectric conversion layer is realized by a combination of an organic photoelectric conversion film and a photodiode made of a solid semiconductor material such as silicon, for example, a structure described in Japanese Patent Application Laid-Open No. 2015-38931 can be adopted. it can.
  • one or more layers on the upper layer side are constituted by an organic photoelectric conversion film, and the remaining layers on the lower layer side are constituted by photodiodes formed on a semiconductor substrate.
  • a wiring layer in which various transistors and wirings are formed is provided on the opposite side of the organic photoelectric conversion film across the semiconductor substrate on which the photodiode is provided.
  • the wiring layer and the organic photoelectric conversion film are connected by a through electrode penetrating the semiconductor substrate from the front and back, and the through electrode is provided according to the number of organic photoelectric conversion films.
  • JP-T-2004-510355 discloses a six-layer structure in which blue, green, and red photodiode sensors are formed at different depths below the surface of the semiconductor structure. As an eight-layer structure, blue, green, green and red photodiode sensors are formed at different depths below the surface of the semiconductor structure.
  • FIG. 4 is a diagram illustrating the photoelectric conversion unit 210 included in the solid-state imaging device according to the present embodiment.
  • the solid-state imaging device according to the present embodiment is the same as the solid-state imaging device according to the first embodiment described above except for the thickness of the photoelectric conversion layer constituting the photoelectric conversion unit.
  • the same reference numerals are given, and detailed description is omitted.
  • the photoelectric conversion unit 210 of this embodiment includes photoelectric conversion layers 211 to 214.
  • the spectral characteristics and materials of the photoelectric conversion layers 211 to 214 are the same as those of the photoelectric conversion layers 11 to 14 according to the first embodiment.
  • the arrangement order of the photoelectric conversion layers 211 to 214 can be variously changed. However, with respect to the photoelectric conversion layers 212 and 213, the photoelectric conversion layer 212 is provided in the upper layer and the photoelectric conversion layer 213 is provided in the lower layer. In the present embodiment, the case where the photoelectric conversion layers 211 to 214 are formed in this order from the upper layer to the lower layer will be described as an example.
  • the photoelectric conversion layers 212 and 213 have different layer thicknesses, and in particular, the upper photoelectric conversion layer 212 is formed thinner than the lower photoelectric conversion layer 213.
  • the photoelectric conversion layer 212 is formed with a thickness that absorbs and photoelectrically converts the incident light that passes through the layer at a ratio of half or less of the incident light included in the photoelectric conversion wavelength region of the photoelectric conversion layer 212. That is, more than half of the incident light included in the photoelectric conversion wavelength region of the photoelectric conversion layer 212 among the incident light passing through the photoelectric conversion layer 212 passes through the photoelectric conversion layer 212 and enters the photoelectric conversion layer 213.
  • the sensitivity difference between the photoelectric conversion layer 212 and the photoelectric conversion layer 213 can be increased by either reducing the thickness of the photoelectric conversion layer 212, increasing the thickness of the photoelectric conversion layer 213, or both.
  • the sensitivity difference between the photoelectric conversion layer 212 and the photoelectric conversion layer 213 becomes more prominent. That is, the sensitivity ratio of the photoelectric conversion layers 212 and 213 formed with different layer thicknesses can be adjusted by the thickness of the photoelectric conversion layer 212 and the thickness of the photoelectric conversion layer 213.
  • the solid-state imaging device can be downsized as a whole.
  • the photoelectric conversion layer 212 thin, a shift in wavelength characteristics between the photoelectric conversion layer 212 and the photoelectric conversion layer 213 can be suppressed. That is, when the absorption wavelength region of the photoelectric conversion layers 212 and 213 is broad, the photoelectric conversion layer 212 that absorbs light in the upper layer and the photoelectric conversion layer 213 that absorbs incident light after the photoelectric conversion layer 212 absorbs light actually There is a possibility that the wavelength characteristic of light absorption will change. This shift in wavelength characteristics is less likely to occur as the upper photoelectric conversion layer 212 is made thinner.
  • FIG. 5 is a diagram illustrating the photoelectric conversion unit 310 included in the solid-state imaging device according to the present embodiment.
  • the solid-state imaging device according to the present embodiment is the same as the solid-state imaging device according to the first embodiment described above except for the number of photoelectric conversion layers constituting the photoelectric conversion unit.
  • the same reference numerals are given, and detailed description is omitted.
  • the photoelectric conversion unit 310 of this embodiment includes photoelectric conversion layers 311 to 316.
  • the photoelectric conversion layers 311 and 312 have spectral characteristics (first spectral characteristics) that mainly absorb blue light, and the main photoelectric conversion wavelength region is the wavelength region of blue light.
  • the photoelectric conversion layers 313 and 314 have spectral characteristics (second spectral characteristics) that mainly absorb green light, and the main photoelectric conversion wavelength range is the wavelength range of green light.
  • the photoelectric conversion layers 315 and 316 have spectral characteristics (second spectral characteristics) that mainly absorb red light, and the main photoelectric conversion wavelength region is the wavelength region of red light.
  • the photoelectric conversion layers 311 and 312 having the first spectral characteristics may be formed of the same material, or may be formed of different types of materials having substantially the same spectral characteristics.
  • the photoelectric conversion layers 313 and 314 having the second spectral characteristics may be formed of the same material, or may be formed of different types of materials having substantially the same spectral characteristics.
  • the photoelectric conversion layers 315 and 316 having the third spectral characteristics may be formed of the same material, or may be formed of different types of materials having substantially the same spectral characteristics.
  • the spectral characteristics and materials of the photoelectric conversion layers 311 to 316 are the same as those of the photoelectric conversion layers 11 to 14 of the first embodiment having the same spectral characteristics.
  • the photoelectric conversion layers 311 to 316 are arranged such that the photoelectric conversion layer 311 is provided in the upper layer and the photoelectric conversion layer 312 is provided in the lower layer.
  • the photoelectric conversion layer 313 is provided in the upper layer
  • the photoelectric conversion layer 314 is provided in the lower layer
  • the photoelectric conversion layer 315 and 316 the photoelectric conversion layer 315 is provided in the upper layer and the photoelectric conversion layer 316 is provided in the lower layer.
  • the photoelectric conversion layers 311 to 316 are formed in this order from the upper layer to the lower layer will be described as an example.
  • the photoelectric conversion layers 311 and 312 are formed with the same thickness, the photoelectric conversion layers 313 and 314 are formed with the same thickness, and the photoelectric conversion layers 315 and 316 are formed with the same thickness.
  • the light receiving sensitivity of the photoelectric conversion layers 311 to 316 varies depending on the layer thickness of the photoelectric conversion layers 311 to 316. The thinner the photoelectric conversion layers 311 to 316, the higher the sensitivity of the photoelectric conversion layers 311 to 316, the difference in sensitivity between the photoelectric conversion layers 311 and 312, the difference in sensitivity between the photoelectric conversion layers 313 and 314, and the photoelectric conversion layer. The difference in sensitivity between 315 and 316 is reduced.
  • the ratio of the sensitivity of the photoelectric conversion layers 311 and 312, the photoelectric conversion layers 313 and 314, and the photoelectric conversion layers 315 and 316 formed with the same thickness can be adjusted by the layer thickness of the photoelectric conversion layer. it can.
  • the number of photoelectric conversion layers is not limited to six.
  • the layer having the first spectral characteristic has at least two layers, the layer having the second spectral characteristic has at least two layers, and has the third spectral characteristic.
  • Various changes can be made as long as at least two layers are included.
  • the light receiving sensitivity of the photoelectric conversion layers 311 and 312 varies depending on the layer thickness of the photoelectric conversion layers 311 and 312, and the light receiving sensitivity of the photoelectric conversion layers 313 and 314 varies depending on the layer thickness of the photoelectric conversion layers 313 and 314.
  • the light receiving sensitivity of the layers 315 and 316 varies depending on the layer thickness of the photoelectric conversion layers 315 and 316. This is the same as in the case of the photoelectric conversion layers 12 and 13 according to the first embodiment. Note that the photoelectric conversion layers 311 and 312, the photoelectric conversion layers 313 and 314, and the photoelectric conversion layers 315 and 316 may have different thicknesses in the upper layer and the lower layer as in the second embodiment.
  • a wide dynamic range can be realized for three different colors. That is, a high-sensitivity pixel is realized by using the photocurrent output from the photoelectric conversion layers 311, 313, and 315, and a low-sensitivity pixel is realized by using the photocurrent output from the photoelectric conversion layers 312, 314, and 316.
  • the photoelectric conversion layers 311 and 312, the photoelectric conversion layers 313 and 314, and the photoelectric conversion layers 315 and 316 generate charges based on the same incident light in a state where they are stacked one above the other, so that the output from the high-sensitivity pixels There is no spatial or temporal deviation between the base signal and the signal based on the output from the low sensitivity pixel.
  • FIG. 6 is a diagram illustrating the photoelectric conversion unit 410 included in the solid-state imaging device according to the present embodiment.
  • the solid-state imaging device according to the present embodiment is the same as the solid-state imaging device according to the first embodiment described above except for the stacking order and materials of the photoelectric conversion layers that constitute the photoelectric conversion unit. Are given the same reference numerals, and detailed description thereof is omitted.
  • the photoelectric conversion unit 410 includes photoelectric conversion layers 411 to 414.
  • light is incident from the photoelectric conversion layer 411 side, and the photoelectric conversion layers 411, 412, 413, and 414 are provided in this order from the upper layer to the lower layer.
  • the photoelectric conversion layers 411 to 414 are arranged in such a manner that the photoelectric conversion layers 411 and 412 are provided in the upper layer and the photoelectric conversion layers 413 and 414 are provided in the lower layer. Note that the arrangement order of the photoelectric conversion layers 413 and 414 may be changed.
  • the photoelectric conversion layers 411 and 412 have spectral characteristics (second spectral characteristics) that mainly absorb green light, and the main photoelectric conversion wavelength range is the wavelength range of green light.
  • the photoelectric conversion layer 413 has a spectral characteristic (first spectral characteristic) that mainly absorbs blue light, and the main photoelectric conversion wavelength range is the wavelength range of blue light.
  • the photoelectric conversion layer 414 has a spectral characteristic (third spectral characteristic) that mainly absorbs red light, and the main photoelectric conversion wavelength range is the wavelength range of red light.
  • the photoelectric conversion layers 411 and 412 having the second spectral characteristics may be formed of the same material, or may be formed of different types of materials having substantially the same spectral characteristics.
  • the photoelectric conversion layers 411 to 414 are composed of organic photoelectric conversion films, and the photoelectric conversion layer 413 that mainly absorbs blue light and the red light are mainly absorbed.
  • the photoelectric conversion layer 414 is composed of a photodiode made of a solid semiconductor material such as silicon. At present, organic photoelectric conversion materials having high photoelectric conversion quantum efficiency are widely known for green light, but organic photoelectric conversion materials having sufficient photoelectric conversion quantum efficiency for blue and red are not common.
  • an organic photoelectric conversion film is used for a green light photoelectric conversion layer provided with two layers of a high sensitivity layer and a low sensitivity layer, and a solid semiconductor material such as silicon is used for a photoelectric conversion layer that absorbs blue light or red light.
  • a configuration using the manufactured photodiode is realistic.
  • a wide dynamic range can be realized for three different colors. That is, a high-sensitivity pixel is realized by using the photocurrent output from the photoelectric conversion layer 411, and a low-sensitivity pixel is realized by using the photocurrent output from the photoelectric conversion layer 412.
  • the photoelectric conversion layers 411 and 412 generate charges based on the same incident light in a state where they are stacked one above the other. There will be no spatial or temporal misalignment.
  • FIG. 7 is a diagram illustrating the photoelectric conversion unit 510 included in the solid-state imaging device according to the present embodiment.
  • the solid-state imaging device according to the present embodiment is the same as the solid-state imaging device according to the first embodiment described above except for the arrangement of the photoelectric conversion layer that constitutes the photoelectric conversion unit, and thus has the same configuration. Reference numerals are attached and detailed description is omitted.
  • the photoelectric conversion unit 510 of this embodiment includes photoelectric conversion layers 511 to 516.
  • the photoelectric conversion layers 511 to 513 and the photoelectric conversion layers 514 to 516 are adjacently disposed in a positional relationship offset in a direction (plane direction) substantially perpendicular to the thickness direction.
  • light is incident from the photoelectric conversion layers 511 and 514, and the photoelectric conversion layers 511 to 513 are provided in the order of the photoelectric conversion layers 511, 512, and 513 from the upper layer to the lower layer,
  • the photoelectric conversion layers 514 to 516 are also provided in the order of the photoelectric conversion layers 514, 515, and 516 from the upper layer to the lower layer. Note that the arrangement order of the photoelectric conversion layers 511 to 513 and the arrangement order of the photoelectric conversion layers 514 to 516 can be variously changed.
  • the photoelectric conversion layers 511 and 514 have a spectral characteristic (second spectral characteristic) that mainly absorbs green light, and the main photoelectric conversion wavelength range is the wavelength range of green light.
  • the photoelectric conversion layers 512 and 515 have a spectral characteristic (first spectral characteristic) that mainly absorbs blue light, and the main photoelectric conversion wavelength region is the wavelength region of blue light.
  • the photoelectric conversion layers 513 and 516 have spectral characteristics (third spectral characteristics) that mainly absorb red light, and the main photoelectric conversion wavelength range is the wavelength range of red light.
  • the photoelectric conversion layers 411 and 412, the photoelectric conversion layers 512 and 515, and the photoelectric conversion layers 513 and 516 having the same spectral characteristics may be formed of the same material or different types of materials having substantially the same spectral characteristics. May be.
  • the photoelectric conversion layers 511 to 516 are composed of organic photoelectric conversion films.
  • the photoelectric conversion layers 511, 514, the photoelectric conversion layers 512, 515 and the photoelectric conversion layers 513, 516 having the same spectral characteristics are formed in the same size on the surfaces extending in the direction substantially perpendicular to the thickness direction. Further, the photoelectric conversion layers 511 and 514 have different layer thicknesses. Even when the photoelectric conversion unit 510 configured as described above is used, a spatial shift occurs between the photoelectric conversion layers 511 and 514, between the photoelectric conversion layers 512 and 515, and between the photoelectric conversion layers 513 and 516. However, a high-sensitivity pixel and a low-sensitivity pixel can be realized with a two-dimensional array of pixels of the same size.
  • the other photoelectric conversion layers 512 and 515 and / or the photoelectric conversion layers 513 and 516 may have different layer thicknesses.
  • FIG. 8 is a block diagram illustrating a configuration of an imaging apparatus 600 including a solid-state imaging element.
  • An imaging apparatus 600 illustrated in FIG. 1 is an example of an electronic device.
  • an imaging device refers to a solid-state imaging in an image capturing unit (photoelectric conversion unit) such as an imaging device such as a digital still camera or a digital video camera, or a mobile terminal device such as a mobile phone having an imaging function. It refers to all electronic devices that use equipment.
  • an electronic apparatus using a solid-state imaging device for an image capturing unit also includes a copying machine using a solid-state imaging device for an image reading unit.
  • the imaging device may be a module including a solid-state imaging device to be mounted on the electronic device described above.
  • an imaging device 600 includes an optical system 611 including a lens group, a solid-state imaging device 612, a DSP 613 (Digital Signal Processor), a frame memory 614, a display device 615, a recording device 616, an operation system 617, a power supply system 618, and a control. Part 619 is provided.
  • an optical system 611 including a lens group, a solid-state imaging device 612, a DSP 613 (Digital Signal Processor), a frame memory 614, a display device 615, a recording device 616, an operation system 617, a power supply system 618, and a control. Part 619 is provided.
  • the DSP 613, the frame memory 614, the display device 615, the recording device 616, the operation system 617, the power supply system 618, and the control unit 619 are connected to each other via a communication bus so that data and signals can be transmitted and received.
  • the optical system 611 takes in incident light (image light) from a subject and forms an image on the imaging surface of the solid-state imaging device 612.
  • the solid-state image sensor 612 generates an electrical signal corresponding to the amount of incident light received on the imaging surface by the optical system 611 for each pixel and outputs it as a pixel signal.
  • the pixel signal is input to the DSP 613 and appropriately subjected to various image processing, and then stored in the frame memory 614, recorded on a recording medium of the recording device 616, or output to the display device 615.
  • the display device 615 includes a panel type display device such as a liquid crystal display device or an organic EL (electroluminescence) display device, and displays a moving image, a still image, and other information captured by the solid-state image sensor 612.
  • the recording device 616 records a moving image or a still image captured by the solid-state imaging device 612 on a recording medium such as a DVD (Digital Versatile Disk), HD (Hard Disk), or semiconductor memory.
  • the operation system 617 receives various operations from the user, and transmits an operation command according to the user's operation to each unit 613, 614, 615, 616, 618, 619 via the communication bus.
  • the power supply system 618 generates various power supply voltages serving as drive power supplies and appropriately supplies them to the supply target (each unit 612, 613, 614, 615, 616, 617, 619).
  • the control unit 619 includes a CPU that performs arithmetic processing, a ROM that stores a control program for the imaging apparatus 600, a RAM that functions as a work area for the CPU, and the like.
  • the control unit 619 controls the units 613, 614, 615, 616, 617, and 618 via the communication bus by the CPU executing a control program stored in the ROM while using the RAM as a work area.
  • the control unit 619 controls a timing generator (not shown) to generate various timing signals and performs control to supply the timing signals to each unit.
  • FIG. 9 is a block diagram showing the configuration of the solid-state image sensor 612. As shown in FIG. In the present embodiment, a CMOS image sensor, which is a kind of XY address type solid-state image sensor, will be described as an example of the solid-state image sensor.
  • the solid-state imaging device 612 includes a pixel unit 721, a vertical drive unit 722, an analog / digital conversion unit 723 (AD conversion unit 723), a reference signal generation unit 724, a horizontal drive unit 725, a communication / timing control unit 726, and a signal.
  • a processing unit 727 is provided.
  • a plurality of pixels PXL including photodiodes as photoelectric conversion elements are arranged in a two-dimensional matrix (in this embodiment, a matrix of m columns ⁇ n rows).
  • a color filter array is not provided on the light receiving surface side of each pixel.
  • the pixel drive lines HSLy are wired along the horizontal direction (pixel arrangement direction / horizontal direction of the pixel row) in the figure, and are arranged at equal intervals in the vertical direction in the figure.
  • the pixel drive lines HSLi are wired in each row by four, which is the number of photoelectric conversion layers of one pixel.
  • the vertical signal lines VSLx are wired along the vertical direction (pixel arrangement direction / vertical direction of the pixel column) in the drawing, and are arranged at equal intervals in the horizontal direction in the drawing.
  • One vertical signal line VSLx is wired in each column.
  • the pixel drive line HSLy is connected to each pixel PXL arranged in the corresponding row, and one end thereof is connected to an output terminal corresponding to each row of the vertical drive unit 722.
  • the vertical signal lines VSLx are respectively connected to the pixels PXL arranged in the corresponding column, and one end thereof is connected to the AD conversion unit 723.
  • the vertical driving unit 722 and the horizontal driving unit 725 perform control of sequentially reading analog signals from the pixels PXL constituting the pixel unit 721 under the control of the communication / timing control unit 726. Note that specific connection of the pixel drive line HSLi and the vertical signal line VSLx to each pixel PXL will be described later together with the description of the pixel PXL.
  • the communication / timing control unit 726 includes, for example, a timing generator and a communication interface.
  • the timing generator generates various clock signals based on an externally input clock (master clock).
  • the communication interface receives data for instructing an operation mode given from the outside of the solid-state image sensor 612 and outputs data including internal information of the solid-state image sensor 612 to the outside.
  • the communication / timing control unit 726 Based on the master clock, the communication / timing control unit 726 generates a clock having the same frequency as the master clock, a clock obtained by dividing the clock by two, a low-speed clock obtained by dividing the clock, and the like (vertical drive). 722, horizontal drive unit 725, AD conversion unit 723, reference signal generation unit 724, signal processing unit 727, etc.).
  • the vertical drive unit 722 includes, for example, a shift register, an address decoder, and the like.
  • the vertical drive unit 722 includes a vertical address setting unit for controlling a row address and a row scanning control unit for controlling row scanning based on a signal obtained by decoding an externally input video signal.
  • the vertical drive unit 722 can perform readout scanning and sweep-out scanning.
  • the readout scanning is scanning that sequentially selects unit pixels from which signals are read out.
  • the reading scan is basically performed in order in units of rows.
  • the sweep-out scan is a scan that resets the unit pixels belonging to the row or pixel combination to be read before the row or pixel combination to be read by the read scan, by a time corresponding to the shutter speed before the read scan. is there.
  • the horizontal drive unit 725 sequentially selects each ADC circuit constituting the AD conversion unit 723 in synchronization with the clock output from the communication / timing control unit 726.
  • the horizontal drive unit 725 includes, for example, a horizontal address setting unit and a horizontal scanning unit, and selects individual ADC circuits of the AD conversion unit 723 corresponding to the horizontal readout column defined by the horizontal address setting unit.
  • the digital signal generated in the selected ADC circuit is guided to the horizontal signal line Ltrf.
  • the digital signal output from the AD conversion unit 723 is input to the signal processing unit 727 via the horizontal signal line Ltrf.
  • the signal processing unit 727 performs processing for converting a signal output from the pixel unit 721 via the AD conversion unit 723 into an image signal corresponding to the pixel array by arithmetic processing.
  • the signal processing unit 727 performs a process of thinning out the pixel signals in the horizontal direction and the vertical direction by addition, addition averaging, or the like as necessary.
  • the image signal generated in this way is output to the outside of the solid-state imaging device 612.
  • the reference signal generation unit 724 includes a DAC (Digital Analog Converter), and generates a reference signal Vramp (see FIG. 16 and the like described later) in synchronization with the count clock supplied from the communication / timing control unit 726.
  • the reference signal Vramp is a sawtooth wave (ramp waveform) that changes in time stepwise from the initial value supplied from the communication / timing control unit 726. This reference signal Vramp is supplied to each ADC circuit of the AD conversion unit 723.
  • the AD conversion unit 723 includes a plurality of ADC circuits.
  • the ADC circuit compares the analog signal output from each pixel PXL with a reference signal Vramp and the voltage of the vertical signal line VSLx in a predetermined AD conversion period (P-phase period and D-phase period described later). And the counter counts the time either before or after the magnitude relationship between the reference signal Vramp and the voltage of the vertical signal line VSLx (pixel voltage) is inverted. Thereby, a digital signal corresponding to an analog pixel voltage can be generated.
  • a specific example of the AD conversion unit 723 will be described later.
  • FIG. 10 is a diagram illustrating an example of an equivalent circuit of the pixel PXL
  • FIG. 11 is a diagram illustrating an example of an arrangement of elements in the pixel.
  • the equivalent circuit of the pixel PXL has a configuration in which the photoelectric conversion layers 11 to 14 are connected to the charge holding units FD1 to FD4 via the transfer transistors TG1 to TG4, respectively.
  • the pixel PXL has a photoelectric conversion unit and a transfer transistor for each color light, and other components are shared by each color light.
  • the pixel PXL includes photoelectric conversion layers 11 to 14, transfer transistors TG1 to TG4, charge holding units FD1 to FD4, reset transistors RST1 to RST4, amplification transistors AMP1 to AMP4, and selection transistors SEL1 to SEL4. .
  • the transfer transistor TG1 When the transfer transistor TG1 is turned on by the transfer signal supplied to the gate from the vertical drive unit 722, the transfer transistor TG1 transfers the signal charge generated in the photoelectric conversion layer 11 to the charge holding unit FD1.
  • the transfer transistor TG2 When the transfer transistor TG2 is turned on by the transfer signal supplied from the vertical drive unit 722 to the gate, the transfer transistor TG2 transfers the signal charge generated in the photoelectric conversion layer 12 to the charge holding unit FD2.
  • the transfer transistor TG3 When the transfer transistor TG3 is turned on by the transfer signal supplied to the gate from the vertical drive unit 722, the transfer transistor TG3 transfers the signal charge generated in the photoelectric conversion layer 13 to the charge holding unit FD3.
  • the transfer transistor TG4 When the transfer transistor TG4 is turned on by the transfer signal supplied from the vertical driving unit 722 to the gate, the transfer transistor TG4 transfers the signal charge generated in the photoelectric conversion layer 14 to the charge holding unit FD4.
  • the charge holding units FD1 to FD4 have the same function as so-called floating diffusion, the charge holding unit FD1 holds the signal charge transferred from the photoelectric conversion layer 11, and the charge holding unit FD2 is transferred from the photoelectric conversion layer 11.
  • the signal holding unit FD3 holds the signal charge transferred from the photoelectric conversion layer 11, and the charge holding unit FD4 holds the signal charge transferred from the photoelectric conversion layer 11.
  • the reset transistors RST1 to RST4 are turned on by a reset signal supplied to the gate from the vertical drive unit 722.
  • the reset transistor RST1 When the reset transistor RST1 is turned on, the charge holding unit FD1 is connected to the constant voltage source Vdd, and the potential of the charge holding unit FD1 is reset.
  • the reset transistor RST2 When the reset transistor RST2 is turned on, the charge holding unit FD2 is connected to the constant voltage source Vdd, and the potential of the charge holding unit FD2 is reset.
  • the reset transistor RST3 is turned on, the charge holding unit FD3 is connected to the constant voltage source Vdd, and the potential of the charge holding unit FD3 is reset.
  • the reset transistor RST4 When the reset transistor RST4 is turned on, the charge holding unit FD4 is connected to the constant voltage source Vdd, and the potential of the charge holding unit FD4 is reset.
  • the amplification transistor AMP1 has a gate connected to the charge holding unit FD1, a drain connected to the constant voltage source Vdd, and a source connected to the drain of the selection transistor SEL1.
  • the amplification transistor AMP2 has a gate connected to the charge holding unit FD2, a drain connected to the constant voltage source Vdd, and a source connected to the drain of the selection transistor SEL2.
  • the amplification transistor AMP3 has a gate connected to the charge holding unit FD3, a drain connected to the constant voltage source Vdd, and a source connected to the drain of the selection transistor SEL3.
  • the amplification transistor AMP4 has a gate connected to the charge holding unit FD4, a drain connected to the constant voltage source Vdd, and a source connected to the drain of the selection transistor SEL4.
  • the amplification transistor AMP1 generates at the source a potential obtained by amplifying the potential of the charge holding unit FD1.
  • the amplification transistor AMP2 generates at the source a potential obtained by amplifying the potential of the charge holding unit FD2.
  • the amplification transistor AMP3 generates a potential obtained by amplifying the potential of the charge holding unit FD3 at the source.
  • the amplification transistor AMP4 generates a potential obtained by amplifying the potential of the charge holding unit FD4 at the source.
  • the selection transistor SEL1 has a drain connected to the source of the amplification transistor AMP1, and a source connected to the vertical signal line VSL.
  • the selection transistor SEL1 is turned on by a selection signal supplied to the gate from the vertical drive unit 722, and outputs a potential generated at the source of the amplification transistor AMP1 to the AD conversion unit 723 as a pixel signal via the vertical signal line VSL.
  • the selection transistor SEL2 has a drain connected to the source of the amplification transistor AMP2, and a source connected to the vertical signal line VSL.
  • the selection transistor SEL2 is turned on by a selection signal supplied to the gate from the vertical drive unit 722, and outputs a potential generated at the source of the amplification transistor AMP2 to the AD conversion unit 723 as a pixel signal via the vertical signal line VSL.
  • the selection transistor SEL3 has a drain connected to the source of the amplification transistor AMP3 and a source connected to the vertical signal line VSL.
  • the selection transistor SEL3 is turned on by a selection signal supplied to the gate from the vertical drive unit 722, and outputs a potential generated at the source of the amplification transistor AMP3 to the AD conversion unit 723 as a pixel signal via the vertical signal line VSL.
  • the selection transistor SEL4 has a drain connected to the source of the amplification transistor AMP4 and a source connected to the vertical signal line VSL.
  • the selection transistor SEL4 is turned on by a selection signal supplied to the gate from the vertical drive unit 722, and outputs a potential generated at the source of the amplification transistor AMP4 to the AD conversion unit 723 as a pixel signal via the vertical signal line VSL.
  • the elements in the pixel may share the charge holding unit FD, the reset transistor RST, the amplification transistor AMP, and the selection transistor SEL.
  • the pixel PXL has a configuration in which the outputs of the photoelectric conversion layers 11 to 13 are connected to the charge holding unit FD via the FD transfer transistor FDG, and each transfer of the photoelectric conversion layers 11 to 13 is performed.
  • the capacitor C is connected between the transistors TG1 to TG3 and the FD transfer transistor FDG, and any of the transfer transistors TG1 to TG3 is turned on while the FD transfer transistor FDG is turned off.
  • the transfer transistor that has been turned on after being stored in the capacitor C for a certain period of time may be turned off and the FD transfer transistor FDG may be turned on to transfer the charge stored in the capacitor C to the charge holding unit FD.
  • the gain can be switched for the outputs of the photoelectric conversion layers 11 to 14.
  • FIG. 15 is a diagram illustrating a configuration of the AD conversion unit 723.
  • each ADC circuit constituting the AD conversion unit 723 includes a comparator 723a and a counter 723b provided for each vertical signal line VSLx, and a latch 723c.
  • the comparator 723a includes two input terminals T1 and T2 and one output terminal T3.
  • One input terminal T1 receives the reference signal Vramp from the reference signal generation unit 724, and the other input terminal T2 outputs an analog pixel signal (hereinafter referred to as a pixel signal Vvsl) output from the pixel through the vertical signal line VSL. .) Has been entered.
  • the comparator 723a compares the reference signal Vramp and the pixel signal Vvsl.
  • the comparator 723a outputs a high-level or low-level signal according to the magnitude relationship between the reference signal Vramp and the pixel signal Vvsl.
  • the comparator 723a outputs The output of the terminal T3 is inverted between the high level and the low level.
  • the counter 723b is supplied with a clock from the communication / timing control unit 726, and counts the time from the start to the end of AD conversion using the clock.
  • the timing for starting and ending AD conversion is specified based on a control signal output from the communication / timing control unit 726 (for example, whether or not the clock signal CLK is input) and output inversion of the comparator 723a.
  • the counter 723b performs A / D conversion on the pixel signal by so-called correlated double sampling (CDS). Specifically, the counter 723b counts down while the analog signal corresponding to the reset component is output from the vertical signal line VSLx (corresponding to a P-phase period described later) according to the control of the communication / timing control unit 726. Do. The count value obtained by this down-counting is used as an initial value, and up-counting is performed while an analog signal corresponding to a pixel signal is output from the vertical signal line VSLx (corresponding to a D-phase period described later).
  • CDS correlated double sampling
  • the count value generated in this way is a digital value corresponding to the difference between the signal component and the reset component. That is, a digital value corresponding to an analog pixel signal input from the pixel to the AD conversion unit 723 through the vertical signal line VSLx is a value calibrated with the reset component.
  • the digital value generated by the counter 723b is stored in the latch 723c, sequentially output from the latch 723c in accordance with the control of the horizontal scanning unit, and output to the signal processing unit 727 via the horizontal signal line Ltrf.
  • the AD conversion operation shown in the figure is repeatedly executed while sequentially reading out pixel signals of a plurality of pixels.
  • the pixel readout operation shown in the figure mainly includes a reset operation, an AZ operation, a reset level acquisition operation, and a pixel signal level acquisition operation.
  • the reset operation is executed in the reset period (t0 to t1) shown in FIG. 16, the reset level acquisition operation is executed in the P phase period (t3 to t4) shown in FIG. 16, and the pixel signal level acquisition operation is shown in FIG. It is executed in the D phase period (t5 to t6) shown in FIG. Between the reset period and the P-phase period, an AZ period (t1 to t2) for eliminating a potential difference between the input terminals T1 and T2 of the comparator 723a is provided.
  • the P phase preparation period (t2 to t3) is provided immediately before the P phase period
  • the D phase preparation period (t4 to t5) is provided immediately before the D phase period.
  • preparation for AD conversion operation performed in the P-phase period and D-phase period such as returning the reference signal Vramp to the initial value is performed.
  • each period will be described in order.
  • the reference signal Vramp is shown to rise at an acute angle at t2 when the P-phase preparation period is started and at t4 when the D-phase preparation period is started. Since there is a wiring capacity, it gradually rises with a predetermined time constant according to the wiring capacity.
  • the AZ period and the P-phase preparation period pass, and then the P-phase period.
  • the P-phase period a reset level acquisition operation for converting an analog voltage corresponding to the amount of charge accumulated in the reset pixel into a digital value is executed.
  • a reset pulse corresponding to the above-described reset off voltage and a transfer pulse corresponding to the above-described transfer off voltage are applied to the reset transistors RST1 to RST4 and the transfer transistors TG1 to TG4 of the processing target pixel, respectively.
  • a selection pulse corresponding to the above-described selection ON voltage is applied to the selection transistors SEL1 to SEL4.
  • the reset transistors RST1 to RST4 and the transfer transistors TG1 to TG4 of the pixel to be processed are turned off, and the selection transistors SEL1 to SEL4 are turned on.
  • the pixel signal Vvsl becomes a voltage obtained by amplifying the voltages in the charge holding units FD1 to FD4 immediately after being reset by the amplification transistors AMP1 to AMP4.
  • the comparator 723a receives the reference signal Vramp and the pixel signal Vvsl, and outputs a comparison output Vco corresponding to the magnitude relationship between the reference signal Vramp and the pixel signal Vvsl.
  • the pixel signal Vvsl is the voltage of the vertical signal line VSL connected to the target pixel for AD conversion
  • the reference signal Vramp has a predetermined reference value as an initial value
  • the time is a predetermined period from the start to the end of AD conversion. The voltage gradually changes from the initial value as time passes.
  • the comparison output Vco changes between the high level and the low level when the reference signal Vramp and the pixel signal Vvsl intersect and the magnitude relationship is inverted.
  • the comparison output Vco is a high level voltage when the reference signal Vramp is larger than the pixel signal Vvsl, and is a low level voltage when the reference signal Vramp is smaller than the pixel signal Vvsl. .
  • the comparison output Vco generated in this way is input to the counter 723b.
  • the counter 723b counts during a period until the reference signal Vramp and the pixel signal Vvsl intersect and the magnitude relationship is inverted. In other words, in the present embodiment, the counter 723b performs counting during a period in which the comparison output Vco is at a high level during the P-phase period, and does not perform counting when the comparison output Vco is at a low level.
  • the counter 723b can count the time from the start of AD conversion in the P-phase period to before the comparison output Vco and the reference signal Vramp intersect.
  • This count value is a digital value corresponding to the charge accumulated in the pixel in the reset state. As described above, in the P phase period, the counter 723b counts down.
  • the photoelectric conversion layers 11 to 14 When the P-phase period ends, after passing through the D-phase preparation period for returning the reference signal Vramp to the initial value, etc., in the D-phase period, the photoelectric conversion layers 11 to 14 according to the amount of charge generated according to the amount of received light
  • the pixel signal level acquisition operation for converting the obtained voltage (analog voltage) into a digital value is executed.
  • a reset pulse corresponding to the above-described reset-off voltage is applied to the reset transistors RST1 to RST4 of the pixel to be processed. Further, a transfer pulse corresponding to the above-described transfer on voltage is applied to the transfer transistors TG1 to TG4, and a selection pulse corresponding to the above-described selection on voltage is applied to the selection transistors SEL1 to SEL4.
  • the reset transistors RST1 to RST4 of the pixel to be processed are turned off, and the transfer transistors TG1 to TG4 and the selection transistors SEL1 to SEL4 are sequentially turned on.
  • the transfer transistors TG1 to TG4 and the selection transistors SEL1 to SEL4 are sequentially turned on.
  • charges generated by the photoelectric conversion layers 11 to 14 according to the amount of received light are transferred to the charge holding units FD1 to FD4, and the voltages of the charge holding units FD1 to FD4 are amplified as the pixel signals Vvsl.
  • the voltages amplified by AMP4 are sequentially output.
  • the comparator 723a receives the reference signal Vramp and the pixel signal Vvsl as in the P-phase period described above.
  • the comparator 723a outputs a voltage corresponding to the magnitude relationship between the reference signal Vramp and the pixel signal Vvsl.
  • the comparison output Vco changes between a high level and a low level when the reference signal Vramp and the pixel signal Vvsl cross and the magnitude relationship is inverted.
  • the counter 723b performs counting in a period until the reference signal Vramp and the pixel signal Vvsl intersect and the magnitude relationship is inverted. That is, in the present embodiment, the counter 723b performs counting during a period in which the comparison output Vco is at a high level during the D phase period, and does not perform counting when the comparison output Vco is at a low level.
  • the counter 723b can count the time from the start of AD conversion in the D phase period to the time before the comparison output Vco and the reference signal Vramp intersect.
  • the count value at this time is a digital value corresponding to the amount of charge generated by the photoelectric conversion layers 11 to 14 according to the amount of received light. Note that, as described above, in the D-phase period, the counter 723b performs up-counting opposite to that in the P-phase period.
  • the counter 723b performs counting using the count result in the P phase period as an initial value.
  • the count value held by the counter 723b at the end of the D-phase period is accumulated in the reset pixel from the count value corresponding to the voltage corresponding to the charge generated by the photoelectric conversion layers 11 to 14 according to the amount of received light.
  • the digital value is obtained by subtracting the count value corresponding to the voltage corresponding to the generated charge. That is, the value held by the counter 723b is a value from which the fixed noise component is removed by so-called correlated double sampling.
  • the digital value thus generated in the counter 723b is transferred to the latch 723c under the control of the communication / timing control unit 726, and the horizontal value is converted while the next pixel value is AD-converted in the comparator 723a and the counter 723b.
  • the signals are sequentially output to the signal processing unit 727 by the driving unit 725 via the horizontal signal line Ltrf.
  • the transfer instruction St is input from the horizontal driving unit 725 in the reset period of the AD conversion period of the next pixel value, and data transfer is performed while the P-phase period and the D-phase period are being executed. Done.
  • present technology is not limited to the above-described embodiments, and includes configurations in which the configurations disclosed in the above-described embodiments are mutually replaced or combinations are changed, known technologies, and the above-described embodiments. Also included are configurations in which the configurations disclosed in 1 are replaced with each other or combinations are changed.
  • the technical scope of the present technology is not limited to the above-described embodiment, but extends to the matters described in the claims and equivalents thereof.
  • a photoelectric conversion part formed by laminating four or more photoelectric conversion layers in a direction along the thickness direction of the semiconductor; Among the four or more photoelectric conversion layers, at least one layer has a first spectral characteristic, at least two layers have a second spectral characteristic different from the first spectral characteristic, and at least one layer has the above-mentioned A solid-state imaging device having a first spectral characteristic and a third spectral characteristic different from the second spectral characteristic.
  • the material having the second spectral characteristic is the same material.
  • the solid-state imaging device according to (1) The solid-state imaging device according to (1).
  • the photoelectric conversion layers of at least two layers formed of the material having the second spectral characteristics have substantially the same layer thickness.
  • the photoelectric conversion layers of at least two layers formed of the material having the second spectral characteristic have different layer thicknesses.
  • the photoelectric conversion layer formed of the material having the first spectral characteristic has a main photoelectric conversion wavelength range of blue light
  • the photoelectric conversion layer formed of the material having the second spectral characteristic has a main photoelectric conversion wavelength range of green light
  • the photoelectric conversion layer formed of the material having the third spectral characteristic has a main photoelectric conversion wavelength range of red light.
  • the photoelectric conversion part is configured by laminating at least six photoelectric conversion layers, Six or more photoelectric conversion layers have at least two layers having the first spectral characteristic, at least two layers having the second spectral characteristic, and at least two layers having the third spectral characteristic.
  • the solid-state imaging device according to any one of (1) to (5).
  • At least one layer of the photoelectric conversion layer is composed of an organic photoelectric conversion film, The solid-state imaging device according to any one of (1) to (6).
  • the at least two layers having the second spectral characteristics when the output signal of the high-sensitivity photoelectric conversion layer has reached a saturation level, the at least two layers having the second spectral characteristics are
  • the output signal of the low-sensitivity photoelectric conversion layer among the photoelectric conversion layers is a pixel signal.
  • Display device 616 ... Recording device, 617 ... Operation system, 618 ... Power supply system, 619 ... Control part, 721 ... Pixel part, 722 ... Vertical drive part, 723 ... Analog-digital conversion part (AD conversion part), 723a ... Comparator, 723b ... Counter, 723c ... Latch, 724 ... Reference signal generation part, 25 ... horizontal drive unit, 726 ... timing control section, 727 ... signal processing unit, AMP, AMP1 ⁇ AMP4 ... amplifying transistor, FD, FD1 ⁇ FD4 ... charge holding portion, PXL ... pixel, RST, RST1 ⁇ RST4 ... reset transistor, St ...
  • Transfer instruction SEL, SEL1 to SEL4 ... Selection transistor, T1 ... Input terminal, T2 ... Input terminal, T3 ... Output terminal, TG1-TG4 ... Transfer transistor, Vdd ... Constant voltage source, VSL, VSLx ... Vertical signal line

Abstract

L'invention a pour but de fournir un dispositif de capture d'image qui ne génère pas de décalages spatiaux et temporels au niveau des pixels, tout en obtenant une large gamme dynamique. L'invention concerne un dispositif de capture d'image à semi-conducteurs qui est pourvu d'une unité de conversion photoélectrique formée par stratification, dans la direction de l'épaisseur d'un semi-conducteur, de quatre ou plus de quatre couches de conversion photoélectrique, et, parmi les quatre ou plus de quatre couches de conversion photoélectrique, au moins une couche possède des premières caractéristiques spectroscopiques, au moins deux couches possèdent des deuxièmes caractéristiques spectroscopiques qui sont différentes des premières caractéristiques spectroscopiques, et au moins une couche possède des troisièmes caractéristiques spectroscopiques qui sont différentes des premières caractéristiques spectroscopiques et des deuxièmes caractéristiques spectroscopiques.
PCT/JP2017/005645 2016-03-31 2017-02-16 Dispositif de capture d'image à semi-conducteurs WO2017169241A1 (fr)

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