WO2017154444A1 - Élément de conversion photoélectrique et dispositif de capture d'image - Google Patents

Élément de conversion photoélectrique et dispositif de capture d'image Download PDF

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Publication number
WO2017154444A1
WO2017154444A1 PCT/JP2017/004428 JP2017004428W WO2017154444A1 WO 2017154444 A1 WO2017154444 A1 WO 2017154444A1 JP 2017004428 W JP2017004428 W JP 2017004428W WO 2017154444 A1 WO2017154444 A1 WO 2017154444A1
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Prior art keywords
photoelectric conversion
light
layer
conversion unit
image sensor
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PCT/JP2017/004428
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English (en)
Japanese (ja)
Inventor
戸田　淳
山口　哲司
望 瀧口
大介 保原
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ソニー株式会社
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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
    • H04N23/20—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from infrared radiation only
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/02—Details
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • 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

Definitions

  • the present disclosure relates to a photoelectric conversion element and an imaging device.
  • a detection device in which a light receiving element is sensitive to infrared rays having a wavelength of 1.0 ⁇ m or more is known from, for example, Japanese Patent Application Laid-Open No. 2011-096921.
  • the light receiving element has a light receiving layer such as GaAsSb / InGaAs formed on the InP substrate.
  • JP 2011-096921 A Japanese Patent Laid-Open No. 02-080928
  • the detection device disclosed in the above patent publication is manufactured using an InP substrate having a maximum size of 4 inches, the productivity of the detection device is low and the manufacturing cost is high. Further, the dark current value is about 10 ⁇ 9 amperes / cm 2, which is about three orders of magnitude higher than that of a CMOS image sensor formed on a silicon substrate.
  • the silicon semiconductor substrate has a large diameter, and the productivity of the photoelectric conversion element is high.
  • silicon cannot absorb infrared rays having a wavelength of 1.0 ⁇ m or more, infrared rays having a wavelength of 1.0 ⁇ m or more cannot be detected using a silicon semiconductor substrate.
  • An infrared image sensor including a polycrystalline film made of a nonlinear optical material (second harmonic material, SHG (Second Harmonic Generation) material) that converts infrared rays into second harmonics is well known from Japanese Patent Laid-Open No. 02-080928. It is. However, the second harmonic material basically only performs wavelength conversion of light having the same phase, that is, coherent light (for example, laser light). Therefore, natural light having a random phase cannot be detected. Therefore, the application and use environment of the infrared image sensor disclosed in Japanese Patent Laid-Open No. 02-080928 is limited.
  • an object of the present disclosure is to provide a photoelectric conversion element and an imaging apparatus that can be applied to a wide range of uses and usage environments.
  • the photoelectric conversion element of the present disclosure is: A photoelectric conversion unit, and A photon up-conversion layer that is arranged on the light incident side of the photoelectric conversion unit and converts infrared light into light having a wavelength shorter than that of the infrared light and having a sensitivity of the photoelectric conversion unit, It has.
  • an imaging apparatus includes: A plurality of image sensor units each including a first image sensor and a second image sensor juxtaposed with the first image sensor;
  • the first image sensor is A first photoelectric conversion unit; and Arranged on the light incident side of the first photoelectric conversion unit, the infrared light is light having a shorter wavelength than the infrared light, and converts the light into a wavelength region in which the first photoelectric conversion unit has sensitivity.
  • an imaging apparatus includes: A plurality of image sensor units each including a first image sensor and a second image sensor disposed above the first image sensor; Light is incident on the second image sensor, infrared light that has passed through the second image sensor is incident on the first image sensor,
  • the first image sensor is A first photoelectric conversion unit; and Arranged on the light incident side of the first photoelectric conversion unit, the infrared light is light having a shorter wavelength than the infrared light, and converts the light into a wavelength region in which the first photoelectric conversion unit has sensitivity.
  • the photon up-conversion layer for example, light having a wavelength that cannot be absorbed by a silicon material (specifically, For example, infrared light of 1.0 ⁇ m or more) is converted into light having a short wavelength that can be absorbed by the silicon material, and can be detected by the photoelectric conversion unit or the first photoelectric conversion unit. Therefore, it is possible to provide a photoelectric conversion element and an imaging device that can be applied to a wide range of applications and usage environments. Note that the effects described in the present specification are merely examples and are not limited, and may have additional effects.
  • FIG. 1 is a schematic partial cross-sectional view of the photoelectric conversion element (imaging element) and the imaging apparatus according to the first embodiment.
  • FIG. 2 is a schematic partial cross-sectional view of a modification of the photoelectric conversion element (imaging element) and the imaging apparatus according to the first embodiment.
  • FIG. 3 is a schematic partial cross-sectional view of the photoelectric conversion element (imaging element) and the imaging apparatus according to the second embodiment.
  • FIG. 4 is a schematic partial cross-sectional view of a modification of the photoelectric conversion element (imaging element) and the imaging apparatus according to the second embodiment.
  • FIG. 5 is a schematic partial cross-sectional view of another modification of the photoelectric conversion element (imaging element) and the imaging apparatus according to the second embodiment.
  • FIG. 1 is a schematic partial cross-sectional view of the photoelectric conversion element (imaging element) and the imaging apparatus according to the first embodiment.
  • FIG. 2 is a schematic partial cross-sectional view of a modification of the photoelectric conversion element (imaging element
  • FIG. 6 is a schematic partial cross-sectional view of still another modification example of the photoelectric conversion element (imaging element) and the imaging apparatus according to the second embodiment.
  • FIG. 7 is a schematic partial cross-sectional view of the photoelectric conversion element (imaging element) and the imaging apparatus according to the third embodiment.
  • FIG. 8 is a schematic partial cross-sectional view of a modification of the photoelectric conversion element (imaging element) and the imaging apparatus according to the third embodiment.
  • FIG. 9 is a schematic partial cross-sectional view of the photoelectric conversion element (imaging element) and the imaging apparatus according to the fourth embodiment.
  • 10A and 10B are a graph showing a light reflection spectrum of the optical interference film provided in the photoelectric conversion element of Example 1, and a graph showing a light transmission spectrum of the second type filter layer, respectively.
  • FIG. 11 is a graph showing a light absorption spectrum of the light absorption layer provided in the modification of the photoelectric conversion element of Example 1.
  • FIG. 12 is an equivalent circuit diagram of a control unit that controls the operation of the photoelectric conversion element (imaging element) according to the first embodiment.
  • FIG. 13 is a conceptual diagram of the imaging apparatus according to the first embodiment.
  • FIG. 14A is a graph showing the result of comparison of noise between a conventional InGaAs-based sensor that images short-wavelength infrared light and the photoelectric conversion element (imaging element) of Example 1 (band gap and intrinsic carrier at a room temperature of 300 K). a graph) showing a relationship between the concentration n i, FIG. 14B, the Macbeth chart No. 19-No.
  • FIG. 15 is a diagram schematically illustrating the arrangement of the second electrodes constituting the second imaging element in the imaging apparatus according to the third embodiment.
  • FIG. 16 is a diagram schematically illustrating the arrangement of the first electrodes constituting the second imaging element in the imaging apparatus according to the third embodiment.
  • FIG. 17A and FIG. 17B are diagrams schematically illustrating the arrangement of the second electrode and the first electrode constituting the second imaging element in the modification of the imaging apparatus according to the third embodiment.
  • FIG. 18 is a diagram schematically illustrating the arrangement of the first image sensor and the second image sensor in the image pickup apparatus according to the second embodiment.
  • FIG. 19 is a diagram schematically illustrating the arrangement of the first image sensor and the second image sensor in the image pickup apparatus according to the second embodiment.
  • FIG. 20 is a diagram schematically illustrating the arrangement of the first image sensor and the second image sensor in the image pickup apparatus according to the second embodiment.
  • FIG. 21 is a diagram schematically illustrating the arrangement of the first imaging element and the second imaging element in the imaging apparatus according to the second embodiment.
  • FIG. 22 is a diagram schematically illustrating the arrangement of the first imaging element and the second imaging element in the imaging apparatus according to the second embodiment.
  • FIG. 23 is a diagram schematically illustrating the arrangement of the first imaging element and the second imaging element in the imaging apparatus according to the second embodiment.
  • FIG. 24 is a diagram schematically illustrating the arrangement of the first image sensor and the second image sensor in the imaging apparatus according to the third embodiment.
  • FIG. 25 is a diagram schematically illustrating the arrangement of the first image sensor and the second image sensor in the imaging apparatus according to the third embodiment.
  • FIG. 26 is a schematic partial cross-sectional view of another modified example of the photoelectric conversion element (imaging element) and the imaging apparatus according to the first embodiment.
  • FIG. 27 is a conceptual diagram of an example in which the imaging apparatus of the present disclosure is used with an electronic device (camera).
  • FIG. 28 is a graph showing the spectrum of atmospheric light.
  • FIG. 29 is a graph of a light absorption spectrum showing a so-called biological window.
  • FIG. 30 is an energy level diagram for explaining triplet-triplet annihilation.
  • FIG. 31 is a schematic diagram for explaining a phenomenon in which after a nanoparticle absorbs input light, its energy is transferred to a dye and light of higher energy is emitted based on triplet-triplet annihilation.
  • FIG. 32 is a schematic diagram for explaining a phenomenon in which photon upconversion occurs in a cascade manner by combining a plurality of donor molecules (sensitizers) and acceptor molecules (luminescent agents).
  • Example 1 (photoelectric conversion element and imaging device of the present disclosure) 3.
  • Example 2 (an image pickup apparatus according to a modification of Example 1 and the first aspect of the present disclosure) 4).
  • Example 3 an imaging device according to a modification of Example 1 and the second aspect of the present disclosure) 5.
  • Example 4 (Modification of Example 3) 6).
  • the second imaging element is further provided with a color filter that is disposed closer to the light incident side than the second photoelectric conversion unit and transmits visible light.
  • the color filter is, for example, an on-chip color filter (OCCF) for color separation of red, green, and blue, or an on-chip color for color separation of cyan, magenta, and yellow. It consists of a filter (OCCF).
  • the color filter is composed of a resin to which a colorant composed of a desired pigment or dye is added. By selecting the pigment or dye, the light transmittance in the target wavelength range such as red, green, and blue is high. The light transmittance in other wavelength ranges is adjusted to be low.
  • the first imaging device can be configured to be larger than the second imaging device.
  • the first photoelectric conversion unit and the second photoelectric conversion unit are formed in a silicon layer. be able to.
  • the second imaging element is disposed on the light incident side with respect to the second photoelectric conversion unit, and visible light and infrared light to be incident on the first imaging element. It is possible to adopt a form further including a filter layer that allows the filter to pass through. Such a filter layer is referred to as a “first type filter layer” for convenience.
  • the first photoelectric conversion unit may be formed in a silicon layer.
  • the wavelength of infrared light incident on the photon upconversion layer can be 0.9 ⁇ m or more, preferably 1.0 ⁇ m or more.
  • the wavelength of the light emitted to the photoelectric conversion unit may be less than 0.9 ⁇ m, preferably less than 1.0 ⁇ m.
  • the wavelength of the infrared light incident on the photon upconversion layer is not limited to 0.9 ⁇ m or more, and may be appropriately determined according to the specifications of the photoelectric conversion element (imaging element). The same applies to the following description.
  • the light is disposed on the light incident side of the photon upconversion layer, and 0.9 ⁇ m or more, preferably 1.
  • An embodiment comprising an optical interference film that reflects light of 0 ⁇ m or more and reflects light that is emitted from the photon upconversion layer to less than 0.9 ⁇ m, preferably less than 1.0 ⁇ m, and returns it to the photon upconversion layer It can be.
  • the sensitivity of the photoelectric conversion element can be improved. It is preferable to form a first planarization film between the photon upconversion layer and the optical interference film from the viewpoint of forming a uniform and homogeneous optical interference film.
  • the light-absorbing layer is disposed on the light incident side of the photon up-conversion layer and absorbs light of less than 0.9 ⁇ m, preferably less than 1.0 ⁇ m, out of the light incident on the photon up-conversion layer. It can be in the form.
  • a light absorption layer By providing such a light absorption layer, only light of 0.9 ⁇ m or more, preferably 1.0 ⁇ m or more is incident on the photon upconversion layer, and 0.9 ⁇ m or more, preferably 1.0 ⁇ m, is input to the photoelectric conversion element. Sensitivity to the above light can be reliably imparted.
  • a light absorbing layer and an optical interference film may be disposed from the light incident side.
  • the wavelength is shorter than the red light that is disposed on the light incident side of the photon upconversion layer and incident on the photon upconversion layer.
  • a filter layer that allows light of 0.9 ⁇ m or more (preferably 1.0 ⁇ m or more) to pass therethrough.
  • Such a filter layer is referred to as a “second type filter layer” for convenience.
  • the second imaging element in the imaging device according to the first aspect of the present disclosure also preferably includes a second type filter layer, which improves the color reproducibility of the second imaging element. Can be planned.
  • the first type filter layer provided in the second imaging element in the imaging device according to the second aspect of the present disclosure may be substantially the same as the second filter layer. It is possible to form a second planarizing film between the photon upconversion layer and the second type filter layer (or the first type filter layer), so that the uniform and homogeneous second type filter layer (or the first type filter layer) From the viewpoint of film formation of one type of filter layer).
  • the state of the infrared light incident on the photon up-conversion layer can be in an incoherent state.
  • an interlayer insulating layer between the photoelectric conversion portion and the photon upconversion layer.
  • a material constituting the interlayer insulating layer or as a material constituting the first planarizing film or the second planarizing film a silicon oxide-based material; silicon nitride (SiN Y ); aluminum oxide (Al 2 O 3 ), etc.
  • polymethyl methacrylate PMMA
  • polyvinylphenol PVP
  • polyvinyl alcohol PVA
  • polyimide polycarbonate
  • PC polyethylene terephthalate
  • PET PET
  • silanol derivatives silanol derivatives (silane coupling agents) such as N-2 (aminoethyl) 3-aminopropyltrimethoxysilane (AEAPTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), octadecyltrichlorosilane (OTS), etc.
  • a novolac type phenolic resin Fluorine-based resins; organic insulating materials (organic polymers) exemplified by linear hydrocarbons having a functional group capable of binding to the control electrode at one end, such as octadecanethiol and dodecyl isocyanate, etc. A combination of these can also be used.
  • Silicon oxide-based materials include silicon oxide (SiO x ), BPSG, PSG, BSG, AsSG, PbSG, silicon oxynitride (SiON), SOG (spin-on-glass), low dielectric constant materials (for example, polyaryl ether, cyclohexane) Examples thereof include perfluorocarbon polymer and benzocyclobutene, cyclic fluororesin, polytetrafluoroethylene, fluorinated aryl ether, fluorinated polyimide, amorphous carbon, and organic SOG).
  • An insulating layer to be described later can also be made of the same material.
  • the photoelectric conversion element of the present disclosure including the various preferred embodiments described above is the first imaging element in the imaging device according to the first aspect to the second aspect of the present disclosure including the various preferable forms described above. Can be applied to.
  • the donor molecule (sensitizer) constituting the photon up-conversion layer absorbs light incident on the photon up-conversion layer and becomes a singlet excited state, and then crosses between terms (also referred to as intersystem crossing) to form a triplet. It becomes a term excited state. Furthermore, triplet energy is transferred from the donor molecule to the acceptor molecule (light emitting agent). When two acceptor molecules in such a triplet excited state collide, one acceptor molecule becomes an excited singlet state higher than the triplet excited state, and generates high energy light. Such a phenomenon is called triplet-triplet annihilation (TTA).
  • TTA triplet-triplet annihilation
  • FIG. 30 shows triplet-triplet annihilation in an energy level diagram. Based on the triplet-triplet annihilation, two-photons are basically absorbed to emit up-converted high-energy light. Although two photons are used here, light with higher energy may be emitted by absorbing three or more photons.
  • the wavelength of light incident on the photon up-conversion layer is ⁇ in and the wavelength of light emitted from the photon up-conversion layer is ⁇ out
  • 0.5 ⁇ ⁇ out / ⁇ in ⁇ 1.0 Can be illustrated.
  • FIG. 31 shows absorption of light having a wavelength of 980 nm.
  • the surface of the nanoparticle may be modified with a ligand.
  • the acceptor molecule (luminescent agent)
  • a molecule that fluoresces and emits light in a wavelength region where silicon absorbs for example, a wavelength of less than 1.0 ⁇ m
  • B A molecule having a difference in energy between the excited triplet state and the ground state of at least 0.62 eV (wavelength 1 It is required to be greater than half of the energy of light of .0 ⁇ m 1.24 eV)
  • C In addition to (b), a molecule in which the energy difference between the excited triplet state and the ground state is smaller than the energy difference between the excited triplet state and the ground state of the sensitizer (d) the lifetime of the excited triplet state is long. What is necessary is just to select suitably from a molecule
  • the donor (sensitizer)
  • A Molecule whose energy difference between excited singlet state and ground state is smaller than 1.24 eV (that is, molecule having maximum absorption below 1.0 ⁇ m)
  • B A molecule in which the energy difference between the excited triplet state and the ground state is larger than the energy difference between the excited triplet state and the ground state of the luminescent agent
  • C Crossing between terms, and the molecule from which the excited triplet is easily generated It may be selected as appropriate.
  • the organic substance constituting the donor molecule for example, at least one selected from the group consisting of phthalocyanine, porphyrin, metal complex having a dithiolene ligand, diimonium, squarylium, croconium and cyanine Mention may be made of types of substances.
  • the organic substance constituting the acceptor molecule include at least one substance selected from the group consisting of quatarylene, rubrene, perylene, and anthracene.
  • nanoparticle material having a narrow band gap As a narrow gap semiconductor material (nanoparticle material having a narrow band gap) constituting the nanoparticles, Ge (0.67 eV), GaSb (0.7 eV), InN (0.7 eV), InAs (0.36 eV), PbSe (0.27 eV), PbS (0.37 eV), PbTe (0.29 eV), InSb (0.17 eV) can be exemplified. The value in parentheses indicates the band gap.
  • Photon upconversion may be generated in a cascade manner by combining a plurality of donor molecules (sensitizers) and acceptor molecules (luminescent agents). That is, for example, sensitizer-2 absorbs light emitted from luminescent agent-1 upon receiving energy transfer from sensitizer-1, and luminescent agent-2 emits light upon receiving energy transfer from sensitizer-2. It can be a system such as. However, since the energy transfer in the excited state occurs only in a system that generates a lower excited state, in this case, as shown in FIG. 32, the excited triplet state (T * ) and the ground state (S 0 ). It is necessary to select substances appropriately so that the energy difference increases step by step.
  • an energy transfer auxiliary agent that bridges the energy transfer of the luminescent agent from the sensitizer may be added.
  • the energy difference between the excited triple state and the ground state is exactly the difference between the excited triplet state and the ground state energy of the sensitizer, and the excited triplet state and the ground state energy difference of the luminescent agent. It is desirable to choose between. That is, the relationship between the excited triplet state and the ground state energy difference preferably satisfies the following relationship. Energy difference between excited triplet state and ground state of sensitizer> Energy difference between excited triplet state and ground state of energy transfer aid> Energy difference between excited triplet state and ground state of luminescent agent
  • nanoparticles can be used as a sensitizer.
  • organic dyes and organometallic complex dyes having a maximum absorption at 1.0 ⁇ m or more have a large molecular size, and there are many problems in solubility and synthesis difficulty.
  • the energy transfer aid may be used as a protective film (ligand) for the nanoparticles, or may be added separately.
  • the optical interference film, the first type filter layer, and the second type filter layer have, for example, a structure in which a large number of dielectric films are stacked.
  • the dielectric material include oxides and nitrides such as Si, Mg, Al, Hf, Nb, Zr, Sc, Ta, Ga, Zn, Y, B, and Ti (for example, SiN, AlN, AlGaN, and GaN). , BN, etc.) or fluorides. Specifically, there can be mentioned SiO 2, TiO 2, Nb 2 O 5, ZrO 2, Ta 2 O 5, ZnO, Al 2 O 3, HfO 2, SiN, AlN , or the like.
  • an optical interference film, a first type filter layer, and a second type filter are formed by alternately laminating two or more types of dielectric films made of dielectric materials having different refractive indexes.
  • a layer can be obtained.
  • the material, film thickness, number of stacked layers, and the like constituting each dielectric film may be appropriately selected.
  • the thickness of each dielectric film may be appropriately adjusted depending on the material used.
  • the optical interference film, the first type filter layer, and the second type filter layer can be formed based on a physical vapor deposition method (PVD method) such as a vacuum deposition method or a sputtering method.
  • PVD method physical vapor deposition method
  • a material that absorbs 99% or more of visible light examples include carbon, metal thin film, heat-resistant organic resin, glass paste, organic pigment (for example, pigment and dye), and specifically, photosensitive polyimide resin, chromium oxide, A chromium oxide / chromium laminated film can be exemplified.
  • the light absorption layer depends on the material used, for example, a combination of a vacuum deposition method, a sputtering method and an etching method, a combination of a vacuum deposition method, a sputtering method, a spin coating method and a lift-off method, a screen printing method, a lithography technique, etc. Thus, it can be formed by an appropriately selected method.
  • an ultraviolet cut filter may be provided on the light incident side.
  • a photoelectric conversion element constitutes a CCD (Charge Coupled Device), CMOS (Complementary Metal Oxide Semiconductor) image sensor, CIS (Contact Image Sensor), and CMD (Charge Modulation Device) type signal amplification type image sensor.
  • CCD Charge Coupled Device
  • CMOS Complementary Metal Oxide Semiconductor
  • CIS Contact Image Sensor
  • CMD Charge Modulation Device
  • an electronic device having an imaging function such as a digital still camera, a video camera, a camcorder, an in-vehicle camera, a surveillance camera, a mobile phone, or the like can be configured from the imaging device.
  • the photoelectric conversion unit and the first photoelectric conversion unit include a first electrode, a photoelectric conversion layer, and a second electrode. Are laminated. In some cases, the first electrode may not be provided. Further, in the second imaging element constituting the imaging device according to the first aspect to the second aspect of the present disclosure including the various preferable embodiments described above, the second photoelectric conversion unit also includes the first electrode, The photoelectric conversion layer and the second electrode are laminated. In some cases, the first electrode may not be provided. Here, it is assumed that light enters from the second electrode side.
  • the configuration and structure of the photoelectric conversion unit, the first photoelectric conversion unit, and the second photoelectric conversion unit can be a known configuration and structure.
  • the photoelectric conversion unit and the first photoelectric conversion unit may be formed in the silicon layer as described above.
  • the second photoelectric conversion unit may be formed in the silicon layer.
  • the first photoelectric conversion unit is formed in the first silicon layer.
  • the second photoelectric conversion portion may be formed in the second silicon layer, and the first silicon layer and the second silicon layer may be bonded based on a known method.
  • the first photoelectric conversion unit may be formed on the silicon layer, and the second photoelectric conversion unit may be provided on or above the silicon layer.
  • the second photoelectric conversion unit may be an organic photoelectric conversion material. It is preferable to comprise from.
  • the silicon layer may be composed of a silicon semiconductor substrate, or may be composed of a silicon layer formed by epitaxial growth, an SOI substrate, or the like.
  • the second imaging element can be configured by one type of photoelectric conversion unit, or a plurality of types (for example, two types, three types, or more) arranged in parallel. It is also possible to configure it from a photoelectric conversion unit of the type).
  • the second imaging element can be configured by one type of photoelectric conversion unit, or a plurality of types (for example, two types, three types, or It can also be composed of a photoelectric conversion unit of more types).
  • the second photoelectric conversion unit when the second photoelectric conversion unit is configured from one type of photoelectric conversion unit, the second photoelectric conversion unit may be configured to have sensitivity to the entire visible light (white), for example,
  • the second photoelectric conversion unit is composed of two types of photoelectric conversion units, the second photoelectric conversion unit is composed of, for example, a photoelectric conversion unit having sensitivity to primary colors and a photoelectric conversion unit having sensitivity to complementary colors.
  • the second photoelectric conversion unit is, for example, a red photoelectric conversion unit having sensitivity to red light, and a sensitivity to green light.
  • the photoelectric conversion unit is, for example, a red photoelectric conversion unit, a green photoelectric conversion unit, or a blue color
  • a photoelectric conversion unit and a blue-green photoelectric conversion unit sensitive to blue-green (emerald) light may be configured, and a photoelectric conversion in which a color filter is not provided in place of the blue-green photoelectric conversion unit You may comprise from a part (what is called a white pixel).
  • a stacked structure of a second photoelectric conversion unit having a red photoelectric conversion unit and a first photoelectric conversion unit, and a second photoelectric conversion unit having a green photoelectric conversion unit And the first photoelectric conversion unit, and the combination of the second photoelectric conversion unit having the blue photoelectric conversion unit and the first photoelectric conversion unit may be used to form an image sensor unit.
  • examples of the array of the second photoelectric conversion units include a Bayer array described in the following imaging device according to the first aspect of the present disclosure.
  • a second photoelectric conversion unit having a red photoelectric conversion unit, a second photoelectric conversion unit having a green photoelectric conversion unit, and a second photoelectric conversion unit having a blue photoelectric conversion unit on the first photoelectric conversion unit can also be set as the image pick-up element unit formed by laminating the photoelectric conversion parts.
  • the arrangement order of the photoelectric conversion units in the vertical direction is: From the light incident side to the blue photoelectric converter, the green photoelectric converter, and the red photoelectric converter, or from the light incident side to the green photoelectric converter, the blue photoelectric converter, and the red photoelectric converter.
  • the first image sensor and the second image sensor are combined to form one pixel.
  • a Bayer array Others Interline array, G stripe RB checkered array, G stripe RB complete checkered array, checkered complementary color array, stripe array, diagonal stripe array, primary color difference array, field color difference sequential array, frame color difference sequential array, MOS type array, improved MOS Examples include a type array, a frame interleaved array, and a field interleaved array.
  • one pixel is constituted by one image sensor.
  • the second photoelectric conversion unit (photoelectric conversion layer) is composed of an organic photoelectric conversion material
  • the second photoelectric conversion unit (photoelectric conversion layer) is (1)
  • a p-type organic semiconductor is used.
  • (2) It consists of an n-type organic semiconductor.
  • (3) It is composed of a laminated structure of p-type organic semiconductor layer / n-type organic semiconductor layer. It is composed of a stacked structure of p-type organic semiconductor layer / mixed layer of p-type organic semiconductor and n-type organic semiconductor (bulk heterostructure) / n-type organic semiconductor layer. It is comprised from the laminated structure of the mixed layer (bulk heterostructure) of p-type organic-semiconductor layer / p-type organic semiconductor and n-type organic semiconductor.
  • a mixture of p-type organic semiconductor and n-type organic semiconductor (bulk heterostructure). It can be set as either of the 4 aspects. However, the stacking order can be arbitrarily changed.
  • naphthalene derivatives As p-type organic semiconductors, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, perylene derivatives, tetracene derivatives, pentacene derivatives, quinacridone derivatives, thiophene derivatives, thienothiophene derivatives, benzothiophene derivatives, triallylamine derivatives, carbazole derivatives, perylene derivatives , Picene derivatives, chrysene derivatives, fluoranthene derivatives, phthalocyanine derivatives, subphthalocyanine derivatives, subporphyrazine derivatives, metal complexes having heterocyclic compounds as ligands, polythiophene derivatives, polybenzothiadiazole derivatives, polyfluorene derivatives, etc.
  • n-type organic semiconductors include fullerenes and fullerene derivatives, organic semiconductors having larger (deep) HOMO and LUMO than p-type organic semiconductors, and transparent inorganic metal oxides.
  • Specific examples of n-type organic semiconductors include heterocyclic compounds containing nitrogen, oxygen, and sulfur atoms, such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, quinoxaline derivatives, isoquinoline derivatives, acridines.
  • Derivatives phenazine derivatives, phenanthroline derivatives, tetrazole derivatives, pyrazole derivatives, imidazole derivatives, thiazole derivatives, oxazole derivatives, imidazole derivatives, benzimidazole derivatives, benzotriazole derivatives, benzoxazole derivatives, carbazole derivatives, benzofuran derivatives, dibenzofuran derivatives, subporphyrazine Derivatives, polyphenylene vinylene derivatives, polybenzothiadiazole derivatives, polyfluorene derivatives, etc. as part of the molecular skeleton Organic molecules, mention may be made of organic metal complexes or sub-phthalocyanine derivative.
  • the thickness of the second photoelectric conversion part (which may be referred to as “organic photoelectric conversion layer”) made of an organic photoelectric conversion material is not limited, but, for example, 1 ⁇ 10 ⁇ 8 m to 5 ⁇ 10 ⁇ 7 m, preferably 2.5 ⁇ 10 ⁇ 8 m to 3 ⁇ 10 ⁇ 7 m, more preferably 2.5 ⁇ 10 ⁇ 8 m to 2 ⁇ 10 ⁇ 7 m, more preferably 1 ⁇ 10 ⁇ 7 m m to 1.8 ⁇ 10 ⁇ 7 m can be exemplified.
  • Organic semiconductors are often classified as p-type and n-type, and p-type means that holes are easily transported, and n-type means that electrons are easily transported. It is not limited to the interpretation of having holes or electrons as majority carriers for thermal excitation as in a semiconductor.
  • examples of the material constituting the second photoelectric conversion unit (organic photoelectric conversion layer) that photoelectrically converts light having a green wavelength include rhodamine dyes, melocyanine dyes, quinacridone derivatives, and subphthalocyanine dyes.
  • a material constituting the second photoelectric conversion unit (organic photoelectric conversion layer) that photoelectrically converts blue light for example, coumaric acid dye, tris-8-hydroxyquinolinium (Alq3), melocyanine type A dye etc. can be mentioned
  • As a material which comprises the 2nd photoelectric conversion part (organic photoelectric conversion layer) which photoelectrically converts red light a phthalocyanine dye and a sub phthalocyanine dye can be mentioned, for example.
  • Examples of the method for forming various organic layers include a dry film forming method and a wet film forming method.
  • Dry deposition methods include vacuum deposition using resistance heating or high frequency heating, EB deposition, various sputtering methods (magnetron sputtering, RF-DC coupled bias sputtering, ECR sputtering, counter target sputtering, high frequency sputtering. Method), ion plating method, laser ablation method, molecular beam epitaxy method, and laser transfer method.
  • Examples of the CVD method include a plasma CVD method, a thermal CVD method, an MOCVD method, and a photo CVD method.
  • a spin coating method an ink jet method, a spray coating method, a stamp method, a micro contact printing method, a flexographic printing method, an offset printing method, a gravure printing method, a dip method, or the like
  • patterning methods include chemical etching such as shadow mask, laser transfer, and photolithography, and physical etching using ultraviolet rays or laser.
  • a planarization technique for various organic layers a laser planarization method, a reflow method, or the like can be used.
  • crystalline silicon, amorphous silicon, microcrystalline silicon, crystalline selenium, amorphous selenium, and CIGS which is a chalcopyrite compound
  • CIS CuInSe 2
  • CuInS 2 CuAlS 2 , CuAlSe 2 , CuGaS 2 , CuGaSe 2 , AgAlS 2 , AgAlSe 2 , AgInS 2 , AgInSe 2
  • the imaging apparatus unlike the imaging apparatus including the Bayer array imaging element (that is, not performing blue, green, and red spectroscopy using a color filter), If one pixel is formed by stacking the second photoelectric conversion units having sensitivity to light of a plurality of wavelengths in the light incident direction in the same pixel, the sensitivity is improved and the pixel density per unit volume is increased. Can be improved. Moreover, when comprising a 2nd photoelectric conversion part (photoelectric conversion layer) from an organic photoelectric conversion material, since the organic photoelectric conversion material has a high absorption coefficient, the film thickness of an organic photoelectric conversion layer is compared with the conventional Si type photoelectric conversion layer.
  • the thickness can be reduced, and light leakage from adjacent pixels and the limitation on the incident angle of light are alleviated. Furthermore, in the conventional Si-based image sensor, false color occurs because interpolation processing is performed between pixels of three colors to create a color signal. In the imaging device according to the second aspect of the present disclosure, Generation of false colors can be suppressed. Since the organic photoelectric conversion layer itself also functions as a color filter, color separation is possible without providing a color filter.
  • the photoelectric conversion element can be a back-illuminated type or a front-illuminated type.
  • a single-plate color solid-state imaging device can be configured by the imaging devices according to the first to second aspects of the present disclosure.
  • the photoelectric conversion element or the imaging device may be provided with an on-chip micro lens or a light shielding film for preventing unnecessary external light from entering the photoelectric conversion unit, if necessary. Examples of the material constituting the light shielding film include chromium (Cr), copper (Cu), aluminum (Al), and tungsten (W).
  • a control unit, a drive circuit, and wiring for driving the photoelectric conversion element (imaging element) are provided.
  • a shutter for controlling the incidence of light on the photoelectric conversion element may be provided as necessary.
  • chromium (Cr), copper (Cu), aluminum (Al), tungsten (W) is provided between the imaging element and the imaging element.
  • the light-shielding layer (inter-element light-shielding layer) may be provided, thereby preventing light leakage (optical crosstalk) to the adjacent image sensor more effectively. And sensitivity can be improved.
  • the pixel region in which a plurality of imaging elements are arranged includes pixels that are regularly arranged in a two-dimensional array.
  • the pixel area usually includes an effective pixel area that actually receives light, amplifies the signal charge generated by photoelectric conversion, and reads it to the drive circuit, and a black reference pixel for outputting optical black that serves as a black level reference It is composed of areas.
  • the black reference pixel region is usually arranged on the outer periphery of the effective pixel region.
  • connection portions can be stacked so that the connection portions come into contact with each other, and the connection portions can be joined to each other, and the connection portions can be joined together by using solder bumps or the like.
  • the photoelectric conversion element of the present disclosure including the various preferable forms described above, light is irradiated, photoelectric conversion occurs in the photoelectric conversion layer, and holes and electrons are carrier-separated.
  • An electrode from which holes are extracted is an anode
  • an electrode from which electrons are extracted is a cathode.
  • the first electrode constitutes an anode and the second electrode constitutes a cathode
  • the first electrode constitutes a cathode and the second electrode constitutes an anode.
  • the first electrode may not be provided in some cases.
  • the first electrode and the second electrode that configure the second imaging element are formed of a transparent conductive material. It can be in the form.
  • An electrode made of a transparent conductive material may be referred to as a “transparent electrode”.
  • the transparent conductive material constituting the transparent electrode include conductive metal oxides, specifically, indium oxide, indium tin oxide (ITO, Indium Tin Oxide, Sn-doped In).
  • ITO indium zinc oxide with indium added as a dopant to zinc oxide
  • IGO indium gallium oxide with indium added as a dopant to gallium oxide
  • ITZO indium-gallium-zinc oxide
  • IFO F-doped In 2 O 3
  • tin oxide SnO 2
  • ATO SnO 2 and Sb-doped
  • FTO SnO 2 of F-doped
  • dough zinc oxide other elements
  • a transparent electrode having a base layer of gallium oxide, titanium oxide, niobium oxide, nickel oxide, or the like can be given.
  • the thickness of the transparent electrode include 2 ⁇ 10 ⁇ 8 m to 2 ⁇ 10 ⁇ 7 m, preferably 3 ⁇ 10 ⁇ 8 m to 1 ⁇ 10 ⁇ 7 m.
  • Alkali metals eg Li, Na, K etc. and their fluorides or oxides, alkaline earth metals (eg Mg, Ca etc.) and their fluorides or oxides, aluminum (Al), zinc (Zn), tin (Sn), thallium (Tl), sodium-potassium alloy, aluminum-lithium alloy, magnesium-silver alloy, rare earth metals such as indium and ytterbium, and alloys thereof.
  • organic materials such as poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid [PEDOT / PSS] can be cited as materials constituting the anode and the cathode.
  • these conductive materials may be mixed with a binder (polymer) to form a paste or ink, which may be used as an electrode.
  • the materials constituting the first electrode and the second electrode may be appropriately selected from the materials described above.
  • a dry method or a wet method can be used as a method for forming the first electrode or the like or the second electrode (anode or cathode).
  • the dry method include a PVD method and a chemical vapor deposition method (CVD method).
  • Film formation methods using the principle of the PVD method include vacuum evaporation using resistance heating or high frequency heating, EB (electron beam) evaporation, various sputtering methods (magnetron sputtering, RF-DC coupled bias sputtering, ECR Sputtering method, counter target sputtering method, high-frequency sputtering method), ion plating method, laser ablation method, molecular beam epitaxy method, and laser transfer method.
  • Examples of the CVD method include a plasma CVD method, a thermal CVD method, an organic metal (MO) CVD method, and a photo CVD method.
  • patterning methods include chemical etching such as shadow mask, laser transfer, and photolithography, and physical etching using ultraviolet rays or laser.
  • a planarization technique for the first electrode or the like or the second electrode a laser planarization method, a reflow method, a CMP (Chemical-Mechanical-Polishing) method, or the like can be used.
  • a first carrier blocking layer may be provided between the organic photoelectric conversion layer and the first electrode, or a second carrier blocking layer may be provided between the organic photoelectric conversion layer and the second electrode. Further, a first charge injection layer may be provided between the first carrier blocking layer and the first electrode, or a second charge injection layer may be provided between the second carrier blocking layer and the second electrode.
  • an alkali metal such as lithium (Li), sodium (Na), or potassium (K) and its fluoride or oxide
  • an alkaline earth such as magnesium (Mg), calcium (Ca), etc. And the like, and fluorides and oxides thereof.
  • Example 1 relates to a photoelectric conversion element of the present disclosure, and further relates to an imaging apparatus having sensitivity only to infrared rays using the photoelectric conversion element as an imaging element.
  • FIG. 1 shows a schematic partial cross-sectional view of the photoelectric conversion element (specifically, imaging element) of Example 1, and includes a reset transistor, an amplification transistor, and a control unit that control the operation of the photoelectric conversion element.
  • FIG. 12 shows an equivalent circuit diagram of the selection transistor
  • FIG. 13 shows a conceptual diagram of the imaging apparatus of the first embodiment.
  • FIG. 1 shows a state where two photoelectric conversion elements are juxtaposed.
  • the photoelectric conversion element (imaging element) was a back-illuminated type.
  • the photoelectric conversion element 11 may be expressed as “imaging element 11”.
  • the photoelectric conversion element (specifically, image pickup element) 11 of Example 1 is: Photoelectric conversion unit 20, and Photon up-conversion that is arranged on the light incident side with respect to the photoelectric conversion unit 20 and converts infrared light into light having a shorter wavelength than the infrared light and having a wavelength in which the photoelectric conversion unit 20 has sensitivity.
  • the imaging apparatus of the first embodiment is configured by arranging the photoelectric conversion elements (imaging elements) 11 of the first embodiment in a two-dimensional matrix. More specifically, the image sensor 11 is composed of a CMOS image sensor. In addition, for example, an in-vehicle camera and a monitoring camera are configured from the imaging device.
  • the photoelectric conversion unit 20 is formed in a silicon layer (first silicon layer) 43 made of a p-type silicon semiconductor. Specifically, the p + layer 21, an n-type semiconductor region (photoelectric conversion). Layer) 22 and p + layer 23, and has a known structure and structure.
  • the light incident surface in the silicon layer 43 is set as the upper side, and the opposite side of the silicon layer 43 from the light incident surface is set as the lower side.
  • the light incident surface in the silicon layer 43 is referred to as “second surface 43B” for convenience, and the surface opposite to the light incident surface in the silicon layer 43 is referred to as “first surface 43A” for convenience.
  • a p + layer 21 is provided between the n-type semiconductor region 22 and the first surface 43A of the silicon layer 43 to suppress the generation of dark current. Further, the side surface of the n-type semiconductor region 22 is to being surrounded by the p + layer 23, the p + layer 23 on the top surface of the n-type semiconductor region 22 is formed. Although the second electrode is formed on the p + layer 23, the second electrode is not shown.
  • a photon upconversion layer 24 is formed on the second surface 43B of the silicon layer 43.
  • the photon upconversion layer 24 is formed by mixing, for example, a donor molecule (sensitizer) made of PbSe nanoparticles and an acceptor molecule (luminescent agent) made of rubrene.
  • a donor molecule (sensitizer) composed of InN nanoparticles and an acceptor molecule (luminescent agent) composed of 6,13-diphenylpentacene are mixed.
  • Donor molecule (sensitizer) -1 PbSe nanoparticle acceptor molecule (luminescent agent) -1: Lubronner molecule (sensitizer) -2: Tetraphenyloctamethoxytetranaphthoporphyrin (see structural formula (A) below)
  • Acceptor molecule (luminescent agent) -2 5,12-bis (phenylethynyl) naphthacene (see structural formula (B) below)
  • a planarizing film may be formed between the second surface 43B of the silicon layer 43 and the photon upconversion layer 24.
  • the wavelength of infrared light incident on the photon upconversion layer 24 is 1.0 ⁇ m or more, and the wavelength of light emitted from the photon upconversion layer 24 to the photoelectric conversion unit 20 is less than 1.0 ⁇ m.
  • the wavelength of light incident on the photon up-conversion layer 24 is ⁇ in and the wavelength of light emitted from the photon up-conversion layer 24 is ⁇ out
  • two-photon absorption occurs, 0.5 ⁇ ⁇ out / ⁇ in ⁇ 1.0 Satisfied.
  • a first planarizing film 44 is formed on the photon upconversion layer 24.
  • An optical interference film 25 is formed on the first planarization film 44 (that is, closer to the light incident side than the photon upconversion layer 24).
  • the optical interference film 25 reflects light having a wavelength of less than 1.0 ⁇ m out of light incident on the photon upconversion layer 24 and reflects light having a wavelength of less than 1.0 ⁇ m emitted from the photon upconversion layer 24. Return to the upconversion layer 24.
  • the optical interference film 25 formed based on the vacuum deposition method is, for example, SiN / TiO 2 film / SiO 2 film / TiO 2 film / SiO 2 film / TiO 2 film / SiO 2 film / TiO 2 film / SiO 2 film / SiO 2 film.
  • a second planarization film 45 is formed on the optical interference film 25, and the photon upconversion layer 24 is disposed on the second planarization film 45 (that is, on the light incident side with respect to the photon upconversion layer 24).
  • a filter layer (second type filter layer 46) that allows light having a wavelength shorter than that of red light incident on the light and light having a wavelength of 1.0 ⁇ m or more to pass therethrough is formed.
  • the second type filter layer 46 corresponds to a near-infrared cut filter and is formed by a vacuum deposition method. For example, SiN / TiO 2 film / SiO 2 film / TiO 2 film / SiO 2 film / TiO 2.
  • each film thickness is 0.201 ⁇ m / 0.075 ⁇ m / 0. 136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.136 ⁇ m / 0.075 ⁇ m / 0.201 ⁇ m.
  • a graph showing the light transmission spectrum of the second type filter layer 46 is shown in FIG. 10B.
  • the filter layer (the second type filter layer 46) can be configured to pass only light of 1.0 ⁇ m or more, for example (see, for example, the light reflection spectrum shown in FIG. 10A). In this case, the filter layer (second type filter layer 46) may be omitted, and only the optical interference film 25 may be provided.
  • a protective layer 47 is formed on the second planarization film 45, and the on-chip micro lens 26 is provided on the protective layer 47. Further, a light shielding layer (inter-element light shielding layer 48) is provided between the image sensor 11 and the image sensor 11. A filter layer (second type filter layer 46) may be disposed above the on-chip micro lens 26.
  • a silicon layer 43 is provided on an insulating layer 41 made of SiO 2 formed on a support member 40 made of a silicon semiconductor substrate.
  • the insulating layer 41 is provided with a wiring layer (not shown) composed of a plurality of wirings.
  • An element isolation region 51 is formed on the first surface 43A side of the silicon layer 43, and an oxide film 42 is formed on the first surface 43A of the silicon layer 43.
  • a transfer transistor TR trs and a reset transistor TR rst that constitute a control unit that controls the operation of the imaging device 11 are provided.
  • An amplifying transistor TR amp and a selection transistor TR sel are provided.
  • the gate part 52 is connected to the transfer gate line TG.
  • a floating diffusion layer 53 is provided in the region of the silicon layer 43 in the vicinity of the gate portion 52 of the transfer transistor TR trs . The charges accumulated in the n-type semiconductor region 22 are read out to the floating diffusion layer 53 through the transfer channel 54 formed along the gate portion 52.
  • the reset transistor TR rst includes a gate portion, a channel formation region, and a source / drain region.
  • the gate of the reset transistor TR rst is connected to the reset line RST, one source / drain region of the reset transistor TR rst is connected to the power supply V DD , and the other source / drain region also serves as the floating diffusion layer 53. Yes.
  • the amplification transistor TR amp is composed of a gate portion, a channel formation region, and a source / drain region.
  • the gate portion is connected to the other source / drain region (floating diffusion layer 53) of the reset transistor TR rst .
  • One source / drain region shares the same region as one of the source / drain regions constituting the reset transistor TR rst and is connected to the power supply V DD .
  • the selection transistor TR sel includes a gate portion, a channel formation region, and a source / drain region.
  • the gate part is connected to the selection line SEL.
  • one source / drain region shares a region with the other source / drain region constituting the amplification transistor TRamp , and the other source / drain region is connected to a signal line (data output line) VSL. Has been.
  • the reset line RST, the selection line SEL, and the transfer gate line TG are connected to the vertical drive circuit 112 constituting the drive circuit, and the signal line (data output line) VSL is connected to the column signal processing circuit 113 constituting the drive circuit. ing.
  • the operations of the transfer transistor TR trs , the reset transistor TR rst , the amplifying transistor TR amp and the selection transistor TR sel constituting the control unit that controls the operation of the image sensor 11 are the same as those of the conventional transistors, and are well known. Therefore, detailed description is omitted.
  • a series of operations such as charge accumulation, reset operation, and charge transfer are the same as conventional series of operations such as charge accumulation, reset operation, and charge transfer.
  • the reset noise of the floating diffusion layer 53 can be removed by a correlated double sampling (CDS) process as in the prior art.
  • CDS correlated double sampling
  • the state of infrared light incident on the photon upconversion layer 24 is in an incoherent state. That is, light including visible light and infrared light, which is natural light having a random phase, enters the image sensor 11. Then, it first passes through the on-chip micro lens 26 and further passes through the filter layer (second type filter layer 46). As described above, the light passing through the second type filter layer 46 is light having a shorter wavelength than red light and light having a wavelength of 1.0 ⁇ m or more. As described above, in some cases, the second type filter layer 46 may have a structure that allows only light of 1.0 ⁇ m or more to pass through. These lights are incident on the optical interference film 25.
  • the optical interference film 25 reflects light of less than 1.0 ⁇ m and allows light of 1.0 ⁇ m or more to pass through.
  • the light of 1.0 ⁇ m or more that has passed through the optical interference film 25 enters the photon up-conversion layer 24, and the incident light of 1.0 ⁇ m or more is up-converted to light of less than 1.0 ⁇ m in the photon up-conversion layer 24.
  • the A part of the up-converted light is directed to the photoelectric conversion unit 20 and the remaining part is returned to the optical interference film 25.
  • the optical interference film 25 reflects light of less than 1.0 ⁇ m. It returns to the up-conversion layer 24 and finally goes to the photoelectric conversion unit 20.
  • the light incident on the photoelectric conversion unit 20 is photoelectrically converted and finally output as an electric signal.
  • Thermal noise which is a main cause of dark current, is noise generated due to thermal excitation (transition) of carriers from the valence band to the conduction band. Therefore, it increases as the band gap becomes narrower.
  • Figure 14A Shown in Figure 14A the relationship of the band gap and the intrinsic carrier concentration n i at room temperature 300K. The generation of intrinsic carriers here is due to thermal excitation, indicating the magnitude of thermal noise.
  • the intrinsic carrier concentration n i of InGaAs which is lattice-matched to InP substrates, it can be seen that approximately three orders of magnitude higher compared to the intrinsic carrier concentration n i of silicon (Si). This means that the thermal noise of InGaAs is about three orders of magnitude higher than that of silicon (Si).
  • the intrinsic carrier concentration ni is represented by the following formula (A).
  • E g is the band gap
  • h is the Planck constant
  • k is the Boltzmann constant
  • m is the mass
  • T absolute temperature.
  • the subject is close to black. 22-No. It can be seen that this difference is large on the dark image side of 24, and the difference is widened by about 15 dB.
  • This result is a comparison of infrared light images of 1.0 ⁇ m or more, but when compared with visible light images, the difference between the two is further widened, and the image pickup apparatus of Example 1 provides higher image quality. Can do.
  • the photoelectric conversion element (imaging element) of Example 1 As described above, in the photoelectric conversion element (imaging element) of Example 1, light having a wavelength that cannot be absorbed by the silicon material by the photon up-conversion layer (specifically, for example, infrared light of 1.0 ⁇ m or more) ) Is converted into short-wavelength light that can be absorbed by the silicon material so that it can be detected by the photoelectric conversion unit. Therefore, it is possible to provide a photoelectric conversion element (imaging element) and an imaging apparatus that can be applied to a wide range of applications and usage environments. Moreover, as described above, the dark current can be reduced and a high S / N ratio can be achieved as compared with the conventional InGaAs-based sensor that images short-wavelength infrared light. A photoelectric conversion element (imaging element) and an imaging apparatus can be provided. Furthermore, since a photoelectric conversion element (imaging element) can be manufactured over a large-diameter silicon semiconductor substrate, high mass productivity can be achieved and manufacturing cost can
  • the image pickup apparatus 100 of the first embodiment includes an image pickup area in which the image pickup elements 11 (represented by the image pickup element 101 in FIG. 13) are arranged in a two-dimensional array. 111, a vertical drive circuit 112 as a drive circuit (peripheral circuit), a column signal processing circuit 113, a horizontal drive circuit 114, an output circuit 115, a drive control circuit 116, and the like.
  • these circuits can be configured from known circuits, and are configured using other circuit configurations (for example, various circuits used in conventional CCD type imaging devices and CMOS type imaging devices). It goes without saying that it can be done.
  • the display of the reference number “101” on the image sensor 101 is only one line.
  • the drive control circuit 116 generates a clock signal and a control signal that serve as a reference for the operation of the vertical drive circuit 112, the column signal processing circuit 113, and the horizontal drive circuit 114 based on the vertical synchronization signal, the horizontal synchronization signal, and the master clock.
  • the generated clock signal and control signal are input to the vertical drive circuit 112, the column signal processing circuit 113, and the horizontal drive circuit 114.
  • the vertical drive circuit 112 is configured by, for example, a shift register, and selectively scans each imaging element 101 in the imaging region 111 in the vertical direction sequentially in units of rows.
  • a pixel signal (image signal) based on a current (signal) generated according to the amount of light received by each image sensor 101 is sent to the column signal processing circuit 113 via a signal line (data output line) 117 and VSL.
  • the column signal processing circuit 113 is disposed, for example, for each column of the image sensor 101, and outputs an image signal output from the image sensor 101 for one row for each image sensor as a black reference pixel (not shown, but an effective pixel region). Signal processing for signal removal and signal amplification.
  • a horizontal selection switch (not shown) is connected between the horizontal signal line 118 and provided.
  • the horizontal drive circuit 114 is constituted by, for example, a shift register, and sequentially selects each of the column signal processing circuits 113 by sequentially outputting horizontal scanning pulses, and a signal is sent from each of the column signal processing circuits 113 to the horizontal signal line 118. Output.
  • the output circuit 115 performs signal processing on the signals sequentially supplied from each of the column signal processing circuits 113 via the horizontal signal line 118 and outputs the signals.
  • the photoelectric conversion element (imaging element) of Example 1 can be manufactured based on the following method, for example. That is, first, an SOI substrate is prepared. Then, a first silicon layer is formed on the surface of the SOI substrate based on an epitaxial growth method, and ap + layer 23 is formed on the first silicon layer. Next, a second silicon layer is formed on the first silicon layer based on an epitaxial growth method, and an element isolation region 51, an oxide film 42, a p + layer 21, an n-type semiconductor region 22, and a p + layer are formed on the second silicon layer. 23 is formed.
  • various transistors for controlling the image sensor are formed on the second silicon layer, and further, a wiring layer, an insulating layer 41, and various wirings are formed thereon, and then the insulating layer 41 and the support substrate 40 are formed. to paste together. Thereafter, the SOI substrate is removed to expose the first silicon layer.
  • the surface of the second silicon layer corresponds to the first surface 43A of the silicon layer 43
  • the surface of the first silicon layer corresponds to the second surface 43B of the silicon layer 43.
  • the first silicon layer and the second silicon layer are collectively expressed as a silicon layer (first silicon layer) 43.
  • the photon upconversion layer 24 is formed on the second surface 43B side of the silicon layer 43, and further, the light shielding layer (inter-element light shielding layer) 48, the first planarizing film 44, the optical interference film 25, the second A planarizing film 45, a filter layer (second type filter layer 46), a protective layer 47, and an on-chip micro lens 26 are formed.
  • the photoelectric conversion element (imaging element) of Example 1 can be obtained.
  • the photon up-conversion layer 24 is formed by spin coating, spray coating, dip coating, slit coating, die coating, bar coating, screen printing, ink jet printing, or flat printing. This can be done based on the forming method.
  • the above-mentioned two kinds of materials ⁇ donor molecule (sensitizer) and acceptor molecule (luminescent agent)> are mixed with a polymer (matrix of polymer), and the photon upconversion layer 24 Form.
  • the polymer may be any polymer as long as the photon up-conversion layer 24 absorbs and emits light in a wavelength region that does not absorb (that is, is transparent).
  • an epoxy resin, an acrylic resin, a silicone (siloxane) resin examples thereof include polycarbonate resins and polyethylene resins.
  • the photon upconversion layer 24 can be formed by mixing donor molecules (sensitizers) and acceptor molecules based on a co-evaporation method or the like. The formation of other layers and films can be performed based on a known method.
  • FIG. 2 shows a schematic partial cross-sectional view of a modification of the photoelectric conversion element (imaging element) and the imaging apparatus according to the first embodiment.
  • a light absorption layer 27 is provided which is disposed on the light incident side of the photon upconversion layer 24 and absorbs light of less than 1.0 ⁇ m out of the light incident on the photon upconversion layer 24.
  • the light absorption layer 27 is made of, for example, a photosensitive polyimide resin containing a dye that can absorb light of less than 1.0 ⁇ m, and is formed by a screen printing method.
  • a resin containing a blue pigment, a green pigment, and a red pigment, that is, a black color filter may be used.
  • the same effect can be obtained with only a blue pigment and a red pigment.
  • a dye that absorbs infrared light of less than 1.0 ⁇ m may be added and contained.
  • a graph showing a light absorption spectrum of the light absorption layer 27 is shown in FIG.
  • the light absorption layer 27 and the optical interference film 25 may be disposed from the light incident side. Since the light absorption layer 27 can be formed by a simpler coating process than the multilayer film deposition process, the manufacturing cost can be reduced.
  • Example 2 relates to an imaging apparatus according to the first aspect of the present disclosure.
  • FIG. 3 is a schematic partial sectional view of the image pickup apparatus according to the second embodiment.
  • the arrangement state of the first image sensor 11 and the second image sensor 12 is schematically illustrated in FIGS. 18, 19, and 20.
  • IR indicates the first image sensor
  • R has sensitivity to red light.
  • a second imaging element including a second red photoelectric conversion unit is indicated, and “G” indicates a second imaging element including a second green photoelectric conversion unit having sensitivity to green light.
  • “B” indicates a second image sensor including a second blue photoelectric conversion unit sensitive to blue light.
  • the photoelectric conversion element (imaging element) was a back irradiation type.
  • the imaging device of Example 2 is A plurality of image sensor units each including a first image sensor 11 and a second image sensor 12 juxtaposed with the first image sensor 11;
  • the first image sensor 11 is First photoelectric conversion unit 20, and Light that is disposed closer to the light incident side than the first photoelectric conversion unit 20 and that has infrared light having a wavelength shorter than that of the infrared light, and in which the first photoelectric conversion unit 20 has sensitivity.
  • the second image sensor 12 includes a second photoelectric conversion unit 30 that is sensitive to visible light.
  • the first photoelectric conversion unit 20 includes the photoelectric conversion unit 20 in the photoelectric conversion element 11 described in Example 1.
  • the plurality of image sensor units are arranged in a two-dimensional matrix. More specifically, the second image sensor 12 is composed of a CMOS image sensor.
  • an in-vehicle camera and a monitoring camera are configured from the imaging device.
  • the second imaging element 12 further includes a color filter 34 that is disposed on the light incident side of the second photoelectric conversion unit 30 and allows visible light to pass therethrough.
  • the color filter 34 includes, for example, an on-chip color filter (OCCF) for performing color separation of red, green, and blue.
  • OCCF on-chip color filter
  • An image sensor including an on-chip color filter for performing red color separation corresponds to the second image sensor R including a second red photoelectric conversion unit having sensitivity to red light.
  • the image sensor including an on-chip color filter for performing green color separation corresponds to the second image sensor G including a second green photoelectric conversion unit having sensitivity to green light.
  • the image sensor provided with the on-chip color filter for performing blue color separation corresponds to the second image sensor B provided with the second blue photoelectric conversion unit having sensitivity to blue light. That is, the second image sensor is composed of a plurality of types (specifically, three types) of photoelectric conversion units arranged in parallel.
  • the first photoelectric conversion unit 20 and the second photoelectric conversion unit 30 are formed in the silicon layer 43.
  • the second photoelectric conversion unit 30 is formed in the silicon layer (first silicon layer) 43 made of a p-type silicon semiconductor.
  • the p + layer 31 the n-type is formed. It has a well-known configuration and structure including a semiconductor region (photoelectric conversion layer) 32 and a p + layer 33.
  • a p + layer 31 is provided between the n-type semiconductor region 32 and the first surface 43A of the silicon layer 43 to suppress dark current generation.
  • the side surface of the n-type semiconductor region 32 is to being surrounded by the p + layer 33, the p + layer 33 on the top surface of the n-type semiconductor region 32 is formed.
  • the second electrode is formed on the p + layer 33, the second electrode is not shown.
  • a color filter 34 is formed on the second surface 43 ⁇ / b> B of the silicon layer 43.
  • a planarizing film may be formed between the second surface 43 ⁇ / b> B of the silicon layer 43 and the photon upconversion layer 24 and the color filter 34.
  • a first planarization film 44 is formed on the color filter 34, and a second planarization film 45 is further formed on the first planarization film 44, and a filter layer ( A second type filter layer 46) is formed.
  • a protective layer 47 is formed on the second type filter layer 46, and an on-chip micro lens 36 is provided on the protective layer 47. Further, a light shielding layer (inter-element light shielding layer 48) is provided between the first image sensor 11 and the second image sensor 12.
  • An element isolation region 51 is formed on the first surface 43 ⁇ / b> A side of the silicon layer 43, and an oxide film 42 is formed on the first surface 43 ⁇ / b> A of the silicon layer 43. Furthermore, on the first surface 43A side of the silicon layer 43, a transfer transistor TR trs , a reset transistor TR rst , an amplifying transistor TR amp and a selection transistor that constitute a control unit that controls the operation of the second imaging element 12 are arranged. TR sel is provided. In FIG. 3, only the gate part 55 and the floating diffusion layer 56 of the transfer transistor TR trs are shown, and other components of the control part are not shown. The gate unit 55 is connected to the transfer gate line TG.
  • a floating diffusion layer 56 is provided in the region of the silicon layer 43 in the vicinity of the gate portion 55 of the transfer transistor TR trs .
  • the charges accumulated in the n-type semiconductor region 32 are read out to the floating diffusion layer 56 via the transfer channel 57 formed along the gate portion 55. Since the configuration of the transfer transistor TR trs , the reset transistor TR rst , the amplification transistor TR amp , and the selection transistor TR sel can be the same as those described in the first embodiment, detailed description thereof is omitted.
  • the second photoelectric conversion element When light including visible light and infrared light, which is natural light having a random phase, is incident on the second photoelectric conversion element, it first passes through the on-chip micro lens 36 and further passes through a filter layer (second type filter). Through layer 46). As described above, the light passing through the second type filter layer 46 is light having a shorter wavelength than red light and light having a wavelength of 1.0 ⁇ m or more. These lights are incident on the color filter 34, partly absorbed by the color filter 34, and the remaining part passes through the color filter 34 and travels toward the second photoelectric conversion unit 30. Then, the light incident on the second photoelectric conversion unit 30 is photoelectrically converted and finally output as an electric signal. Since the second photoelectric conversion unit 30 does not have sensitivity to light of 1.0 ⁇ m or more, the light of 1.0 ⁇ m or more does not appear in the image finally obtained based on the second image sensor 12. Does not affect.
  • the photon up-conversion layer allows light having a wavelength that cannot be absorbed by the silicon material (specifically, for example, infrared light of 1.0 ⁇ m or more) using the silicon material.
  • the light is converted into short-wavelength light that can be absorbed so that it can be detected by the photoelectric conversion unit. Therefore, it is possible to provide an imaging apparatus that can be applied to a wide range of applications and usage environments.
  • the second image sensor having sensitivity to visible light is provided, an image based on visible light and an image based on infrared light can be simultaneously captured.
  • the dark current can be reduced and a high S / N ratio can be achieved as compared with a conventional InGaAs-based sensor that images short-wavelength infrared light.
  • the imaging device can be provided.
  • a photoelectric conversion element imaging element
  • high mass productivity can be achieved and manufacturing cost can be reduced.
  • FIG. 4 shows an example in which the photoelectric conversion element (imaging element) is a surface irradiation type.
  • the first photoelectric conversion unit 20 and the second photoelectric conversion unit 30 are formed on the silicon semiconductor substrate 40A based on a known method, and have a known configuration and structure.
  • An interlayer insulating layer 49 is formed on the silicon semiconductor substrate 40A.
  • the interlayer insulating layer 49 is provided with a wiring layer (not shown) composed of a plurality of wirings.
  • the photon upconversion layer 24 and the color filter 34 are formed on the interlayer insulating layer 49, and further, the above-described various components are provided thereon.
  • a planarizing film may be formed between the interlayer insulating layer 49 and the photon upconversion layer 24 and the color filter 34.
  • the modified example of the imaging apparatus of the second embodiment illustrated in FIG. 4 may have the same configuration and structure as the imaging apparatus of the second embodiment illustrated in FIG. Since it can, detailed description is abbreviate
  • FIG. 5 A modification of the imaging device shown in FIG. 3 is shown in FIG. 5, and a modification of the imaging device shown in FIG. 4 is shown in FIG. May be provided on the light incident side, and may include a light absorption layer 27 that absorbs light of less than 1.0 ⁇ m among light incident on the photon upconversion layer 24.
  • Infrared light images have a lower resolution in principle than visible light images. This is because the resolution ⁇ of the imaging lens is determined by the following formula (B) depending on the diffraction limit.
  • NA the numerical aperture of the imaging lens
  • NA sin ( ⁇ )
  • ⁇ the maximum incident angle of the light beam with respect to the optical axis.
  • the first image sensor 11 can adopt a form larger than that of the second image sensor 11.
  • the size of the planar shape of the first image sensor 11 is twice the size of the planar shape of the second image sensor 12, four times the size, broadly m ⁇ n times (m, n is a positive integer and can be exemplified as m).
  • one second image sensor unit may be provided corresponding to one first image sensor ( 21), three second image sensor units may be provided (see FIG. 22), or eight second image sensor units may be provided (see FIG. 23).
  • one second image sensor unit includes a second image sensor R including a second red photoelectric conversion unit sensitive to one red light, and two green lights. From the second image sensor G having a second green photoelectric conversion unit having sensitivity and the second image sensor B having a second blue photoelectric conversion unit having sensitivity to one blue light. These second image sensors have a Bayer array.
  • Example 3 relates to an imaging apparatus according to the third aspect of the present disclosure.
  • FIG. 7 is a schematic partial cross-sectional view of the imaging apparatus according to the third embodiment.
  • FIG. 24 schematically illustrates an arrangement state of the first image sensor 11 and the second image sensor 13.
  • R represents a second photoelectric conversion unit having a red photoelectric conversion unit
  • G represents green color.
  • a second photoelectric conversion unit having a photoelectric conversion unit is represented, and “B” represents a second photoelectric conversion unit having a blue photoelectric conversion unit.
  • the arrangement state of the second image sensor 13 is not limited to this.
  • the photoelectric conversion element is a backside illumination type, it can also be a frontside illumination type.
  • “IR” indicates the first image sensor, and the first image sensor is indicated by a dotted line.
  • the imaging apparatus of Example 3 is A plurality of image sensor units each including a first image sensor 11 and a second image sensor 13 disposed above the first image sensor 11; Light is incident on the second image sensor 13, infrared light that has passed through the second image sensor 13 is incident on the first image sensor 11,
  • the first image sensor 11 is First photoelectric conversion unit 20, and Light that is disposed closer to the light incident side than the first photoelectric conversion unit 20 and that has infrared light having a wavelength shorter than that of the infrared light, and in which the first photoelectric conversion unit 20 has sensitivity.
  • the second imaging element 13 includes a second photoelectric conversion unit 30 that is sensitive to visible light.
  • the first photoelectric conversion unit 20 is formed in the first silicon layer 43, and the second photoelectric conversion unit 30 is provided above the first silicon layer 43 via the interlayer insulating layer 60.
  • a silicon layer 61 (referred to as a “second silicon layer” for convenience) 61 is formed.
  • the bonding of the first silicon layer 43 and the second silicon layer 61 through the interlayer insulating layer 60 can be performed based on a known method.
  • the first photoelectric conversion unit is formed in the first silicon layer 43.
  • the second image sensor 13 is disposed on the light incident side with respect to the photoelectric conversion unit, and passes through the visible light and the infrared light to be incident on the first image sensor (first type filter layer). 46 is further provided.
  • the first type filter layer 146 provided in the second image sensor 13 in the imaging apparatus of the third embodiment is substantially the same as the second filter layer 46 described in the first and second embodiments. Can be.
  • a stacked structure of a second photoelectric conversion unit (not shown) having a red photoelectric conversion unit and a first photoelectric conversion unit 20, and a second photoelectric conversion having a green photoelectric conversion unit.
  • the imaging device unit is configured by a combination of the stacked structure of the unit 30R and the first photoelectric conversion unit 20, and the stacked structure of the second photoelectric conversion unit 30B having the blue photoelectric conversion unit and the first photoelectric conversion unit 20. ing.
  • the first photoelectric conversion unit 20 is disposed below each of the photoelectric conversion units 30R, 30G, and 30B.
  • the arrangement of the photoelectric conversion units 30R, 30G, and 30B is a Bayer arrangement (see FIG. 24).
  • the second imaging element 13 further includes a color filter 34 that is disposed on the light incident side of the second photoelectric conversion units 30R, 30G, and 30B and allows visible light to pass therethrough.
  • the color filter 34 includes, for example, an on-chip color filter (OCCF) for performing color separation of red, green, and blue.
  • An image sensor provided with an on-chip color filter 34R (not shown) for performing red color separation is used as a second image sensor R provided with a second red photoelectric conversion unit sensitive to red light. Applicable.
  • the image pickup device including the on-chip color filter 34G for performing green color separation corresponds to the second image pickup device G including the second green photoelectric conversion unit having sensitivity to green light.
  • the image pickup device including the on-chip color filter 34B for performing blue color separation corresponds to the second image pickup device B including the second blue photoelectric conversion unit having sensitivity to blue light.
  • the second image sensor is composed of a plurality of types (specifically, three types) of photoelectric conversion units arranged in parallel.
  • the second photoelectric conversion units 30R, 30G, and 30B are formed on the second silicon layer 61 made of a p-type silicon semiconductor. Specifically, the p + layer 31 and the n-type semiconductor region are formed. (Photoelectric conversion layer) 32 and a p + layer 33 have a known configuration and structure. A p + layer 31 is provided between the n-type semiconductor region 32 and the first surface 61A of the second silicon layer 61 to suppress generation of dark current. Further, the side surface of the n-type semiconductor region 32 is to being surrounded by the p + layer 33, the p + layer 33 on the top surface of the n-type semiconductor region 32 is formed.
  • a first electrode is connected to the p + layer 31, and a second electrode is formed on the p + layer 33.
  • the first electrode and the second electrode preferably have a structure that does not block light incident on the second image sensor 13 and light that passes through the second image sensor 13 as much as possible.
  • the color filter 34 (34R, 34G, 34B) is formed on the second surface 61B of the second silicon layer 61.
  • a second planarizing film 45 is formed on the color filter 34, and a first type filter layer 146 is formed on the second planarizing film 45.
  • a protective layer 47 is formed on the first type filter layer 146, and an on-chip micro lens 36 is provided on the protective layer 47.
  • a light shielding layer (inter-element light shielding layers 48 and 62) is provided between the first image sensor 11 and the second image sensor 13.
  • the configuration and structure of the control unit that controls the operations of the first image sensor 11 and the second image sensor 13 are the same as the image sensor 11 (first image sensor 11) described in the first embodiment and the second embodiment. Since the configuration and structure of the control unit of the image pickup device 12 can be the same as those in FIG.
  • the second photoelectric conversion element When light including visible light and infrared light, which is natural light having a random phase, is incident on the second photoelectric conversion element, it first passes through the on-chip micro lens 36 and further passes through the first type filter layer 146. pass. As described above, the light passing through the first type filter layer 146 is light having a shorter wavelength than red light and light having a size of 1.0 ⁇ m or more. These lights enter the color filter 34, and the light that has passed through the color filter 34 travels to the second photoelectric conversion unit 30. Then, the light incident on the second photoelectric conversion unit 30 is photoelectrically converted and finally output as an electric signal. Since the second photoelectric conversion unit 30 does not have sensitivity to light of 1.0 ⁇ m or more, the light of 1.0 ⁇ m or more does not appear in the image finally obtained based on the second image sensor 13. Does not affect.
  • the light of 1.0 ⁇ m or more is not absorbed by the second image sensor 13, passes through the second image sensor 13, and travels toward the first image sensor 11. Then, the light enters the optical interference film 25.
  • the optical interference film 25 reflects light of less than 1.0 ⁇ m and allows light of 1.0 ⁇ m or more to pass through. Since light less than 1.0 ⁇ m returns to the second image sensor 13, the sensitivity of the second image sensor 13 can be improved.
  • the light of 1.0 ⁇ m or more that has passed through the optical interference film 25 enters the photon up-conversion layer 24, and the incident light of 1.0 ⁇ m or more is up-converted to light of less than 1.0 ⁇ m in the photon up-conversion layer 24.
  • the A part of the up-converted light is directed to the first photoelectric conversion unit 20, and the remaining part is returned to the optical interference film 25.
  • the optical interference film 25 reflects light of less than 1.0 ⁇ m.
  • the remaining part is returned to the photon upconversion layer 24 and finally goes to the first photoelectric conversion unit 20.
  • the light which injected into the 1st photoelectric conversion part 20 is photoelectrically converted, and is finally output as an electrical signal.
  • the photon upconversion layer allows light having a wavelength that cannot be absorbed by the silicon material (specifically, for example, infrared light of 1.0 ⁇ m or more) using the silicon material.
  • the light is converted into short-wavelength light that can be absorbed so that it can be detected by the photoelectric conversion unit. Therefore, it is possible to provide an imaging apparatus that can be applied to a wide range of applications and usage environments.
  • the second image sensor having sensitivity to visible light is stacked, an image based on visible light and an image based on infrared light can be simultaneously captured, and the density of the image sensor can be increased. Can be planned.
  • the dark current can be reduced and a high S / N ratio can be achieved as compared with a conventional InGaAs-based sensor that images short-wavelength infrared light.
  • the imaging device can be provided.
  • a photoelectric conversion element imaging element
  • high mass productivity can be achieved and manufacturing cost can be reduced.
  • the first image sensor and the second image sensor are stacked, a reduction in resolution can be suppressed.
  • the first image sensor can be a surface irradiation type.
  • the light is disposed on the light incident side of the photon upconversion layer 24 and absorbs light of less than 1.0 ⁇ m out of the light incident on the photon upconversion layer 24.
  • the absorption layer 27 may be provided.
  • the first photoelectric conversion unit 20 is disposed below each of the photoelectric conversion units R (30R), G (30G), and B (30B).
  • one first photoelectric conversion unit 20 may be arranged below the four photoelectric conversion units 30R, 30G, and 30B.
  • the second electrodes 39A and 39B are formed in a band shape in the vicinity of the upper edge portion and the lower edge portion of the image pickup device unit constituted by two second image pickup devices.
  • the first electrodes 38A and 38B are preferably formed in a strip shape in the vicinity of the right edge and the left edge of the image sensor unit.
  • the two electrodes 39A, 39B, and 39C are formed in a strip shape in the vicinity of the upper edge portion, the lower edge portion, and the edge portion of the second image pickup device, each of which is composed of three second image pickup devices.
  • the first electrodes 38A, 38B, and 38C are formed in a strip shape in the vicinity of the right edge portion, the left edge portion, and the edge portion of the second image sensor in the image sensor unit. It is preferable.
  • the first electrode and the second electrode have a structure that does not block as much as possible the light incident on the second image sensor 13 and the light passing through the second image sensor 13.
  • Example 4 is a modification of Example 3.
  • FIG. 9 shows a schematic partial cross-sectional view of the photoelectric conversion element (imaging element) and the imaging apparatus of Example 4.
  • the second imaging element 14 includes a second photoelectric conversion unit 130 having sensitivity to visible light.
  • the second photoelectric conversion unit 130 includes an organic photoelectric conversion layer.
  • the second photoelectric conversion unit 130 is formed by stacking a first electrode, an organic photoelectric conversion layer, and a second electrode.
  • the second photoelectric conversion unit 130 is represented by one layer.
  • the organic photoelectric conversion layer in the second photoelectric conversion unit 130 is specifically composed of the organic photoelectric conversion layer as described above. More specifically, the organic photoelectric conversion layer photoelectrically converts light having a green wavelength.
  • Examples of the material constituting the second photoelectric conversion unit include rhodamine dyes, melocyanine dyes, quinacridone derivatives, subphthalocyanine dyes, and the like, and photoelectrically convert blue light.
  • Examples of the material constituting the second photoelectric conversion part (organic photoelectric conversion layer) include coumaric acid dye, tris-8-hydroxyquinolinium (Alq3), melocyanine dye, and the like.
  • Examples of the material constituting the second photoelectric conversion unit (organic photoelectric conversion layer) that photoelectrically converts phthalocyanine dyes include phthalocyanine dyes and subphthalocyanine dyes. It is possible.
  • the organic photoelectric conversion layer itself functions as a color filter, color separation is possible without providing a color filter. However, the use of a color filter can alleviate the demand for blue, green, and red spectral characteristics.
  • the imaging device including the organic photoelectric conversion layer 37R (not illustrated) that photoelectrically converts light having a red wavelength includes a second red photoelectric conversion unit that is sensitive to red light. This corresponds to the provided second image sensor R.
  • the image sensor including the organic photoelectric conversion layer 37G that photoelectrically converts light having a green wavelength corresponds to the second image sensor G including a second green photoelectric conversion unit that is sensitive to green light.
  • the image pickup device including the organic photoelectric conversion layer 37B that photoelectrically converts light having a blue wavelength corresponds to the second image pickup device B including a second blue photoelectric conversion unit that is sensitive to blue light.
  • the second image sensor is composed of a plurality of types (specifically, three types) of photoelectric conversion units arranged in parallel.
  • Example 4 the organic photoelectric conversion layers 37R, 37G, and 37B constituting the second photoelectric conversion unit 130 are formed on the interlayer insulating layer 60, and the organic photoelectric conversion layers 37R, 37G, and 37B and the interlayer insulation are formed.
  • the layer 60 is covered with a second interlayer insulating layer 63.
  • the first electrode and the second electrode are connected to the organic photoelectric conversion layers 37R, 37G, and 37B, the first electrode and the second electrode are not shown.
  • the first electrode and the second electrode are made of, for example, ITO.
  • a second planarization film 45 is formed on the second interlayer insulating layer 63, and a first type filter layer 146 is formed on the second planarization film 45.
  • a protective layer 47 is formed on the first type filter layer 146, and an on-chip micro lens 36 is provided on the protective layer 47.
  • a light shielding layer (inter-element light shielding layers 48 and 62) is provided between the first image sensor 11 and the second image sensor 14.
  • the configuration and structure of the control unit that controls the operation of the first image sensor 11 and the second image sensor 14 are the same as those of the image sensor 11 (first image sensor 11) and second described in the first and second embodiments. Since the configuration and structure of the control unit of the image pickup device 12 can be the same as those in FIG.
  • the second image sensor 14 When light including visible light and infrared light, which is natural light having a random phase, enters the second image sensor 14, it first passes through the on-chip micro lens 36 and further passes through the first type filter layer 146. pass. As described above, the light passing through the first type filter layer 146 is light having a shorter wavelength than red light and light having a size of 1.0 ⁇ m or more. Then, these lights travel to the second photoelectric conversion unit 130. The light incident on the second photoelectric conversion unit 130 is photoelectrically converted and finally output as an electrical signal. Since the second photoelectric conversion unit 130 does not have sensitivity to light of 1.0 ⁇ m or more, the light of 1.0 ⁇ m or more does not appear in the image finally obtained based on the second image sensor 14. Does not affect.
  • the light of 1.0 ⁇ m or more is not absorbed by the second image sensor 14, passes through the second image sensor 14, and travels toward the first image sensor 11. Then, the light enters the optical interference film 25.
  • the optical interference film 25 reflects light of less than 1.0 ⁇ m and allows light of 1.0 ⁇ m or more to pass through. Since light less than 1.0 ⁇ m returns to the second image sensor 14, the sensitivity of the second image sensor 14 can be improved.
  • the light of 1.0 ⁇ m or more that has passed through the optical interference film 25 enters the photon up-conversion layer 24, and the incident light of 1.0 ⁇ m or more is up-converted to light of less than 1.0 ⁇ m in the photon up-conversion layer 24.
  • the A part of the up-converted light is directed to the first photoelectric conversion unit 20, and the remaining part is returned to the optical interference film 25.
  • the optical interference film 25 reflects light of less than 1.0 ⁇ m.
  • the remaining part is returned to the photon upconversion layer 24 and finally goes to the first photoelectric conversion unit 20.
  • the light which injected into the 1st photoelectric conversion part 20 is photoelectrically converted, and is finally output as an electrical signal.
  • the first image pickup element can be of the surface irradiation type as shown in FIG.
  • the light is disposed on the light incident side of the photon upconversion layer 24 and absorbs light of less than 1.0 ⁇ m out of the light incident on the photon upconversion layer 24.
  • the absorption layer 27 may be provided.
  • the imaging apparatus having the configuration shown in FIGS. 8 and 25 can also be applied to the imaging apparatus of the fourth embodiment.
  • one organic photoelectric conversion layer is provided above the first imaging element.
  • a red organic photoelectric conversion layer is provided on the first photoelectric conversion unit.
  • a second photoelectric conversion unit having a red photoelectric conversion unit, a second photoelectric conversion unit having a green photoelectric conversion unit having a green organic photoelectric conversion layer, and a blue color having a blue organic photoelectric conversion layer It can also be set as the image pick-up element unit by which the 2nd photoelectric conversion part which has a photoelectric conversion part for layers is laminated
  • the present disclosure has been described based on the preferred embodiments, the present disclosure is not limited to these embodiments.
  • the structure and configuration of the photoelectric conversion element, the imaging element, and the imaging apparatus, the manufacturing conditions, the manufacturing method, and the materials used in the examples are examples, and can be appropriately changed.
  • an ultraviolet cut filter may be provided on the light incident side.
  • a configuration in which a light shielding film 71 is formed on the light incident side may be employed. Note that various wirings provided on the light incident side of the photoelectric conversion layer can function as a light shielding film.
  • each semiconductor region may be constituted by a semiconductor region having the opposite conductivity type.
  • the photoelectric conversion element (image sensor or first image sensor) may be an avalanche multiplication type photodiode (APD).
  • the signal reading of the second imaging element may be performed with low voltage driving
  • the signal reading of the first imaging element may be performed with high voltage driving.
  • circuit design is facilitated by providing an interlayer insulating layer between the first image sensor and the second image sensor to separate the drive.
  • a pad portion for connecting the first image sensor to an external circuit and a pad portion for connecting the second image sensor to an external circuit may be provided separately.
  • the short wavelength infrared light (atmospheric light) having a wavelength of 1.0 ⁇ m or more is used for the following reason even in the new moon and in the dark night when there is no light source in the surroundings. Pour down.
  • a graph showing the spectrum of atmospheric light is shown in FIG. (1) Recombination of ions generated by photoionization reaction with sunlight in the daytime (2) Luminescence by cosmic rays radiated to the upper atmosphere (3) Oxygen and nitrogen are hydroxides above several hundred km Chemiluminescence by reacting with ions Therefore, if short-wavelength infrared light of 1.0 ⁇ m or more can be detected and imaged, imaging can be performed without an illumination light source.
  • the imaging device of the present disclosure can be applied to such a field.
  • FIG. 29 shows a graph of a light absorption spectrum showing a so-called biological window.
  • a biological tissue such as water, hemoglobin, or melanin called a biological window.
  • A represents the light absorption spectrum of water
  • B represents the light absorption spectrum of deoxygenated hemoglobin
  • C represents the light absorption spectrum of oxygenated hemoglobin
  • D Indicates the light absorption spectrum of melanin.
  • the imaging apparatus of the present disclosure is useful as a biological sensor such as a brain function test in this wavelength region, vein authentication, or iris authentication.
  • the characteristics of the optical interference film 25, the filter layer (second type filter layer) 46, and the first type filter layer 146 may be optimized.
  • a visible light image and an infrared light image having a wavelength of 1.0 ⁇ m or more can be captured by one camera (imaging device), for example, when applied to a monitoring camera, only darkness of atmospheric light. Capable of imaging from the environment to a bright environment in the daytime.
  • a visible light image and an infrared light image having a wavelength of 1.0 ⁇ m or more can be simultaneously captured, biometric authentication can be performed by linking with the visible light image, and biological information such as hemoglobin and melanin can be obtained. Images can be obtained and can be applied to health and medical examinations. That is, it can be applied to a biological information collecting camera.
  • the present invention is not limited to application to an imaging apparatus, and can also be applied to a CCD type imaging apparatus.
  • the signal charge is transferred in the vertical direction by a vertical transfer register having a CCD structure, transferred in the horizontal direction by a horizontal transfer register, and amplified to output a pixel signal (image signal).
  • the present invention is not limited to the entire column type imaging apparatus in which pixels are formed in a two-dimensional matrix and a column signal processing circuit is arranged for each pixel column. Further, in some cases, the selection transistor can be omitted.
  • the photoelectric conversion element, the imaging element, and the imaging device according to the present disclosure are not limited to application to an imaging device that detects the distribution of the amount of incident light of infrared rays or infrared rays and visible light, and captures an image as an image.
  • the present invention can also be applied to an imaging apparatus that captures the distribution of images as an image.
  • the present invention can be applied to all imaging devices (physical quantity distribution detection devices) such as fingerprint detection sensors that detect the distribution of other physical quantities such as pressure and capacitance and take images as images. As described above, application to imaging of veins and glows is also possible.
  • the present invention is not limited to an image pickup apparatus that sequentially scans each unit pixel in the image pickup region in units of rows and reads a pixel signal from each unit pixel.
  • the present invention is also applicable to an XY address type imaging apparatus that selects an arbitrary pixel in pixel units and reads out pixel signals from the selected pixel in pixel units.
  • the imaging device may be formed as a single chip, or may be in the form of a module having an imaging function in which an imaging region and a drive circuit or an optical system are packaged.
  • the electronic device 200 includes an imaging device 201, an optical lens 210, a shutter device 211, a drive circuit 212, and a signal processing circuit 213.
  • the optical lens 210 forms image light (incident light) from the subject on the imaging surface of the imaging device 201.
  • signal charges are accumulated in the imaging device 201 for a certain period.
  • the shutter device 211 controls a light irradiation period and a light shielding period for the imaging apparatus 201.
  • the drive circuit 212 supplies a drive signal for controlling the transfer operation and the like of the imaging device 201 and the shutter operation of the shutter device 211.
  • Signal transfer of the imaging apparatus 201 is performed by a drive signal (timing signal) supplied from the drive circuit 212.
  • the signal processing circuit 213 performs various signal processing.
  • the video signal subjected to the signal processing is stored in a storage medium such as a memory, or is output to a monitor.
  • the electronic device 200 to which the imaging device 201 can be applied is not limited to a camera, but can be applied to an imaging device such as a digital still camera, a camera module for mobile devices such as a mobile phone.
  • Photoelectric conversion element >> A photoelectric conversion unit, and A photon up-conversion layer that is arranged on the light incident side of the photoelectric conversion unit and converts infrared light into light having a wavelength shorter than that of the infrared light and having a sensitivity of the photoelectric conversion unit,
  • a photoelectric conversion element comprising: [A02] The photoelectric conversion element according to [A01], wherein the wavelength of infrared light incident on the photon upconversion layer is 1.0 ⁇ m or more. [A03] The photoelectric conversion element according to [A02], in which the wavelength of light emitted from the photon upconversion layer to the photoelectric conversion unit is less than 1.0 ⁇ m.
  • [A04] 1.0 ⁇ m arranged on the light incident side of the photon upconversion layer, reflects light less than 1.0 ⁇ m out of the light incident on the photon upconversion layer, and is emitted from the photon upconversion layer
  • the photoelectric conversion element according to any one of [A01] to [A03], further including an optical interference film that reflects less than the light and returns the light to the photon upconversion layer.
  • a light absorption layer that is disposed on the light incident side of the photon upconversion layer and absorbs light of less than 1.0 ⁇ m out of the light incident on the photon upconversion layer [A01] to [A03] The photoelectric conversion element of any one of these.
  • the filter layer is disposed on the light incident side of the photon upconversion layer and includes a filter layer that allows light having a wavelength shorter than red light incident on the photon upconversion layer and light of 1.0 ⁇ m or more to pass therethrough [A01]. Thru
  • Imaging apparatus A plurality of image sensor units each including a first image sensor and a second image sensor juxtaposed with the first image sensor;
  • the first image sensor is A first photoelectric conversion unit; and Photon-up that is arranged on the light incident side of the photoelectric conversion unit and converts infrared light into light having a shorter wavelength than the infrared light and having a wavelength in which the first photoelectric conversion unit has sensitivity.
  • Conversion tier With The second imaging device is an imaging device including a second photoelectric conversion unit having sensitivity to visible light.
  • a plurality of image sensor units each including a first image sensor and a second image sensor disposed above the first image sensor; Light is incident on the second image sensor, infrared light that has passed through the second image sensor is incident on the first image sensor,
  • the first image sensor is A first photoelectric conversion unit; and Photon-up that is arranged on the light incident side of the photoelectric conversion unit and converts infrared light into light having a shorter wavelength than the infrared light and having a wavelength in which the first photoelectric conversion unit has sensitivity.
  • Conversion tier With The second imaging device is an imaging device including a second photoelectric conversion unit having sensitivity to visible light.
  • the second image pickup device is further provided with a filter layer that is disposed on the light incident side of the photoelectric conversion unit and allows visible light and infrared light to be incident on the first image pickup device to pass therethrough [C01].
  • the imaging device described in 1. [C03] The imaging device according to [C01] or [C02], wherein the first photoelectric conversion unit is formed in a silicon layer.
  • Imaging device third aspect >> A photoelectric conversion unit, and A photon up-conversion layer that is arranged on the light incident side of the photoelectric conversion unit and converts infrared light into light having a wavelength shorter than that of the infrared light and having a sensitivity of the photoelectric conversion unit,
  • An imaging device comprising a plurality of photoelectric conversion elements comprising [E01] ⁇ Monitoring camera >> A surveillance camera comprising the imaging device according to any one of [B01] to [D01].
  • ⁇ In-vehicle camera >> A vehicle-mounted camera including the imaging device according to any one of [B01] to [D01].
  • ⁇ Camera for collecting biological information >> A biological information collection camera comprising the imaging device according to any one of [B01] to [D01].
  • SYMBOLS 11 Photoelectric conversion element (imaging element, 1st imaging element) 12, 13, 14 ... 2nd imaging element, 20, 30, 30A, 30R, 30G, 30B, 130 ... Photoelectric conversion , 21, 31... P + layer, 22, 32... N-type semiconductor region (photoelectric conversion layer), 23, 33... P + layer, 24.
  • imaging device 101 ... imaging element, 111 ... imaging region, 112 ... vertical drive circuit 113 ... Column signal processing circuit, 114 ... Horizontal drive circuit, 115 ... Output circuit, 116 ... Drive control circuit, 118 ... Horizontal signal line, 200 ... Electronic device (camera), DESCRIPTION OF SYMBOLS 201 ... Imaging device, 210 ... Optical lens, 211 ... Shutter device, 212 ... Drive circuit, 213 ... Signal processing circuit, TR trs ... Transfer transistor, TR amp ... Amplification Transistor, TR rst ... Reset transistor, TR sel ... Select transistor

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Signal Processing (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Multimedia (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Solid State Image Pick-Up Elements (AREA)

Abstract

L'invention concerne un élément de conversion photoélectrique, comprenant : une section de conversion photoélectrique 20 ; et une couche de conversion ascendante de photon 24 qui est disposée davantage vers le côté d'entrée de la lumière que la section de conversion photoélectrique 20, et qui convertit la lumière infrarouge en une lumière ayant une longueur d'onde plus courte que celle de la lumière infrarouge, ladite lumière étant dans une plage de longueur d'onde à laquelle la section de conversion photoélectrique 20 est sensible.
PCT/JP2017/004428 2016-03-09 2017-02-07 Élément de conversion photoélectrique et dispositif de capture d'image WO2017154444A1 (fr)

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JP2016-045808 2016-03-09

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JP2019075463A (ja) * 2017-10-16 2019-05-16 株式会社豊田中央研究所 シリコンフォトダイオード
WO2019211968A1 (fr) * 2018-05-02 2019-11-07 ソニーセミコンダクタソリューションズ株式会社 Élément de capture d'image à semi-conducteur et dispositif de capture d'image
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JP2022035262A (ja) * 2020-08-20 2022-03-04 株式会社東芝 光検出器、光検出システム、ライダー装置、及び車
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JP2019075463A (ja) * 2017-10-16 2019-05-16 株式会社豊田中央研究所 シリコンフォトダイオード
WO2019211968A1 (fr) * 2018-05-02 2019-11-07 ソニーセミコンダクタソリューションズ株式会社 Élément de capture d'image à semi-conducteur et dispositif de capture d'image
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US12034024B2 (en) 2018-08-13 2024-07-09 Sony Semiconductor Solutions Corporation Solid-state imaging device and electronic apparatus
WO2020177907A1 (fr) * 2019-03-01 2020-09-10 Solar Nanoconverter Ab Agencement de conversion de lumière et procédé associé
WO2021187076A1 (fr) * 2020-03-16 2021-09-23 ソニーセミコンダクタソリューションズ株式会社 Élément d'imagerie et instrument électronique
JP2022035262A (ja) * 2020-08-20 2022-03-04 株式会社東芝 光検出器、光検出システム、ライダー装置、及び車
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