WO2016203925A1 - Élément de conversion photoélectrique - Google Patents

Élément de conversion photoélectrique Download PDF

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Publication number
WO2016203925A1
WO2016203925A1 PCT/JP2016/065605 JP2016065605W WO2016203925A1 WO 2016203925 A1 WO2016203925 A1 WO 2016203925A1 JP 2016065605 W JP2016065605 W JP 2016065605W WO 2016203925 A1 WO2016203925 A1 WO 2016203925A1
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photoelectric conversion
plane
quinacridone
distance
crystal
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PCT/JP2016/065605
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English (en)
Japanese (ja)
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小林　一
戸木田　裕一
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ソニー株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to a photoelectric conversion element using, for example, quinacridone or a quinacridone derivative as an organic semiconductor material.
  • Patent Document 1 for example, in one pixel, for example, an organic photoelectric conversion unit that detects green light and generates a signal charge corresponding thereto, and a photodiode that detects red light and blue light ( There is disclosed a solid-state imaging device in which a decrease in sensitivity is improved by providing an inorganic photoelectric conversion unit) and obtaining signals of three colors in one pixel.
  • the photoelectric conversion layer constituting the organic photoelectric conversion unit in this solid-state imaging device has a bulk heterostructure in which a p-type organic semiconductor material and an n-type organic semiconductor material are randomly mixed.
  • quinacridone having excellent spectral characteristics is widely used as a p-type organic semiconductor material.
  • quinacridone in Non-Patent Document 1, at least five kinds of crystal structures ( ⁇ -QD crystal phase, ⁇ 1 -QD crystal phase, ⁇ 2 -QD crystal phase, ⁇ 3 -QD crystal phase, ⁇ -QD crystal phase, ) has been confirmed experimentally. Since these crystal structures all have a large lattice energy of about 80 kcal / mol, they are easily crystallized during the film forming process. For this reason, many crystal grains and crystal grain boundaries exist in the quinacridone film.
  • Non-Patent Documents 2 to 10 Although the crystal grain boundary increases the charge separation interface to improve the photoelectric conversion efficiency, it has been reported in Non-Patent Documents 2 to 10 that the charge mobility (charge mobility) is lowered. When the charge mobility is lowered, the time required for the charge generated at the charge separation interface to reach the electrode becomes longer, and the afterimage characteristics are lowered. Therefore, there is a demand for a method for improving the afterimage characteristics while maintaining the photoelectric conversion efficiency.
  • a photoelectric conversion element is provided between a first electrode and a second electrode that are arranged to face each other, and between the first electrode and the second electrode, and an anisotropy coefficient related to charge transfer is 0. And a photoelectric conversion layer containing crystal grains that are 3 or more and 1 or less.
  • a photoelectric conversion including crystal grains having an anisotropy coefficient related to charge transfer of 0.3 or more and 1 or less between a first electrode and a second electrode arranged to face each other. A layer was provided. Thereby, a charge conduction network is formed between the crystal grains, the electric field is easily moved, and the electric field mobility in the photoelectric conversion layer is improved.
  • the photoelectric conversion layer includes crystal grains having an anisotropy coefficient related to charge transfer of 0.3 or more and 1 or less. A network is formed. Therefore, the movement of charges between crystal grains is facilitated, and the charge mobility in the photoelectric conversion layer is improved. That is, it is possible to improve the afterimage characteristics. Note that the effects described here are not necessarily limited, and may be any effects described in the present disclosure.
  • FIG. 5A It is sectional drawing showing schematic structure of the photoelectric conversion element which concerns on 1st Embodiment of this indication. It is a top view showing the formation positional relationship of an organic photoelectric converting layer, a protective film (upper electrode), and a contact hole. It is sectional drawing showing the example of 1 structure of an inorganic photoelectric conversion part. It is other sectional drawing of the inorganic photoelectric conversion part shown to FIG. 3A. It is sectional drawing showing the structure (lower side electron extraction) of the electric charge (electron) storage layer of an organic photoelectric conversion part. It is sectional drawing for demonstrating the manufacturing method of the photoelectric conversion element shown in FIG. It is sectional drawing showing the process of following FIG. 5A. It is sectional drawing showing the process of following FIG. 5B.
  • FIG. 6A It is sectional drawing showing the process of following FIG. 6A. It is sectional drawing showing the process of following FIG. 6B. It is sectional drawing showing the process of following FIG. 7A. It is sectional drawing showing the process of following FIG. 7B. It is principal part sectional drawing explaining the effect
  • FIG. 6 is a characteristic diagram showing the relationship between the distance between the grain boundaries of the ⁇ -QD crystal phase and the charge transfer rate between HOMOs of adjacent crystal grains.
  • FIG. 6 is a characteristic diagram showing the relationship between the distance between the grain boundaries of the ⁇ -QD crystal phase and the charge transfer rate between LUMOs of adjacent crystal grains.
  • FIG. 6 is a characteristic diagram showing the relationship between the distance between the grain boundaries of the ⁇ 2 -QD crystal phase and the charge transfer rate between HOMOs of adjacent crystal grains.
  • FIG. 6 is a characteristic diagram showing the relationship between the distance between the grain boundaries of the ⁇ 2 -QD crystal phase and the charge transfer rate between LUMOs of adjacent crystal grains.
  • FIG. 6 is a characteristic diagram showing the relationship between the distance between the grain boundaries of the ⁇ -QD crystal phase and the charge transfer rate between HOMOs of adjacent crystal grains.
  • FIG. 6 is a characteristic diagram showing the relationship between the distance between crystal grain boundaries of a ⁇ -QD crystal phase and the charge transfer rate between LUMOs of adjacent crystal grains. It is sectional drawing showing schematic structure of the photoelectric conversion element which concerns on 2nd Embodiment of this indication. It is a schematic diagram explaining a charge conduction network.
  • FIG. 1 illustrates a cross-sectional configuration of the photoelectric conversion element (photoelectric conversion element 10) according to the first embodiment of the present disclosure.
  • the photoelectric conversion element 10 constitutes one pixel in a solid-state imaging device (described later) such as a CCD image sensor or a CMOS image sensor.
  • the photoelectric conversion element 10 includes a pixel transistor (including transfer transistors Tr1 to 3 described later) formed on the surface (surface S2 opposite to the light receiving surface; second surface) side of the semiconductor substrate 11, and multilayer wiring. It has a layer (multilayer wiring layer 51).
  • one organic photoelectric conversion unit 11G that selectively detects light in different wavelength ranges and performs photoelectric conversion, and two inorganic photoelectric conversion units 11B and 11R are in the vertical direction.
  • the organic photoelectric conversion part 11G has an organic photoelectric conversion layer 17 containing quinacridone or a quinacridone derivative.
  • This quinacridone or quinacridone derivative has an ⁇ crystal phase, a ⁇ 2 crystal phase, or a ⁇ crystal phase including crystal planes each having a (001) plane, a (010) plane, and a (100) plane in the organic photoelectric conversion layer 17.
  • a plurality of crystal grains composed of any one of them, and the distance between adjacent crystal grains in each crystal phase has a predetermined range for each facing surface.
  • the photoelectric conversion element 10 has a laminated structure of one organic photoelectric conversion unit 11G and two inorganic photoelectric conversion units 11B and 11R. With this, red (R) and green (G) are obtained with one element. , Blue (B) color signals can be acquired.
  • the organic photoelectric conversion unit 11G is formed on the back surface (surface S1; first surface) of the semiconductor substrate 11, and the inorganic photoelectric conversion units 11B and 11R are embedded in the semiconductor substrate 11.
  • the organic photoelectric conversion unit 11G is an organic photoelectric conversion element that generates an electron-hole pair by absorbing light in a selective wavelength range (here, green light) using an organic semiconductor material.
  • the organic photoelectric conversion unit 11G has a configuration in which the organic photoelectric conversion layer 17 is sandwiched between a pair of electrodes (lower electrode 15a and upper electrode 18) for extracting signal charges.
  • the lower electrode 15a and the upper electrode 18 are electrically connected to conductive plugs 120a1 and 120b1 embedded in the semiconductor substrate 11 through a wiring layer and a contact metal layer, as will be described later.
  • interlayer insulating films 12 and 14 are formed on the surface S1 of the semiconductor substrate 11, and the interlayer insulating film 12 is opposed to respective conductive plugs 120a1 and 120b1 described later. Through-holes are provided in the regions to be conducted, and conductive plugs 120a2 and 120b2 are embedded in the respective through-holes.
  • wiring layers 13a and 13b are embedded in regions facing the conductive plugs 120a2 and 120b2, respectively.
  • a lower electrode 15 a is provided on the interlayer insulating film 14, and a wiring layer 15 b electrically separated by the lower electrode 15 a and the insulating film 16 is provided.
  • the organic photoelectric conversion layer 17 is formed on the lower electrode 15 a, and the upper electrode 18 is formed so as to cover the organic photoelectric conversion layer 17.
  • a protective film 19 is formed on the upper electrode 18 so as to cover the surface thereof.
  • a contact hole H is provided in a predetermined region of the protective film 19, and a contact metal layer 20 is formed on the protective film 19 so as to fill the contact hole H and extend to the upper surface of the wiring layer 15b.
  • the conductive plug 120a2 functions as a connector together with the conductive plug 120a1, and together with the conductive plug 120a1 and the wiring layer 13a, forms a charge (electron) transmission path from the lower electrode 15a to the green power storage layer 110G described later.
  • the conductive plug 120b2 functions as a connector together with the conductive plug 120b1, and together with the conductive plug 120b1, the wiring layer 13b, the wiring layer 15b, and the contact metal layer 20, provides a discharge path for charges (holes) from the upper electrode 18. To form.
  • the conductive plugs 120a2 and 120b2 are desirably formed of a laminated film of a metal material such as titanium (Ti), titanium nitride (TiN) and tungsten in order to function as a light shielding film.
  • a metal material such as titanium (Ti), titanium nitride (TiN) and tungsten in order to function as a light shielding film.
  • the use of such a laminated film is desirable because contact with silicon can be ensured even when the conductive plugs 120a1 and 120b1 are formed as n-type or p-type semiconductor layers.
  • the interlayer insulating film 12 is made of an insulating film having a small interface state in order to reduce the interface state with the semiconductor substrate 11 (silicon layer 110) and to suppress the generation of dark current from the interface with the silicon layer 110. Desirably configured.
  • an insulating film for example, a stacked film of a hafnium oxide (HfO 2 ) film and a silicon oxide (SiO 2 ) film can be used.
  • the interlayer insulating film 14 is composed of, for example, a single layer film made of one of silicon oxide, silicon nitride, silicon oxynitride (SiON), or the like, or a laminated film made of two or more of these. .
  • the insulating film 16 is formed of, for example, a single layer film made of one of silicon oxide, silicon nitride, silicon oxynitride (SiON), or the like, or a laminated film made of two or more of these.
  • the surface of the insulating film 16 is flattened, and has a shape and a pattern substantially free of steps from the lower electrode 15a.
  • the insulating film 16 has a function of electrically separating the lower electrodes 15a of each pixel when the photoelectric conversion element 10 is used as a pixel of a solid-state imaging device.
  • the lower electrode 15a is provided in a region covering the light receiving surfaces facing the light receiving surfaces of the inorganic photoelectric conversion portions 11B and 11R formed in the semiconductor substrate 11.
  • the lower electrode 15a is made of a light-transmitting conductive film, for example, ITO (Indium Tin Oxide).
  • ITO Indium Tin Oxide
  • a tin oxide (SnO 2 ) -based material to which a dopant is added, or a zinc oxide-based material obtained by adding a dopant to aluminum zinc oxide (ZnO) May be used.
  • zinc oxide-based material examples include aluminum zinc oxide (AZO) to which aluminum (Al) is added as a dopant, gallium zinc oxide (GZO) to which gallium (Ga) is added, and indium zinc oxide to which indium (In) is added. (IZO).
  • AZO aluminum zinc oxide
  • GZO gallium zinc oxide
  • Indium zinc oxide to which indium (In) is added.
  • IZO indium zinc oxide
  • CuI, InSbO 4 , ZnMgO, CuInO 2 , MgIN 2 O 4 , CdO, ZnSnO 3, or the like may be used.
  • signal charges are taken out from the lower electrode 15a, the lower electrode 15a is separated for each pixel in a solid-state imaging device described later using the photoelectric conversion element 10 as a pixel. Formed.
  • the organic photoelectric conversion layer 17 includes, for example, quinacridone or a quinacridone derivative as an organic semiconductor material that photoelectrically converts light in a selective wavelength range and transmits light in other wavelength ranges.
  • the organic photoelectric conversion layer 17 is preferably configured to include one or both of an organic p-type semiconductor and an organic n-type semiconductor, and the organic p-type semiconductor and the organic n-type semiconductor are the quinacridone or the quinacridone derivative, or The organic semiconductor material shown below. That is, the organic photoelectric conversion layer 17 uses subphthalocyanine or a derivative thereof, or fullerene or a derivative thereof together with quinacridone or a quinacridone derivative.
  • quinacridone and a quinacridone derivative act as a p-type semiconductor
  • subphthalocyanine and a derivative thereof, fullerene and a derivative thereof act as an n-type semiconductor.
  • the material which comprises the organic photoelectric converting layer 17 with a quinacridone or a quinacridone derivative is not specifically limited.
  • any one of naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives is preferably used.
  • a polymer such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, or a derivative thereof may be used.
  • metal complex dyes cyanine dyes, merocyanine dyes, phenylxanthene dyes, triphenylmethane dyes, rhodacyanine dyes, xanthene dyes, macrocyclic azaannulene dyes, azulene dyes, naphthoquinone, anthraquinone dyes, Condensed polycyclic aromatic compounds such as anthracene and pyrene and chain compounds condensed with aromatic or heterocyclic compounds, or two compounds such as quinoline, benzothiazole and benzoxazole having a squarylium group and a croconic methine group as a linking chain.
  • a cyanine-like dye or the like bonded by a nitrogen heterocycle or a squarylium group and a croconite methine group can be preferably used.
  • the metal complex dye is preferably a dithiol metal complex dye, a metal phthalocyanine dye, a metal porphyrin dye, or a ruthenium complex dye, but is not limited thereto.
  • the organic photoelectric conversion layer 17 can photoelectrically convert green light corresponding to a part or all of the wavelength range of 495 nm to 570 nm, for example.
  • the thickness of such an organic photoelectric conversion layer 17 is, for example, 50 nm to 500 nm.
  • the quinacridone or quinacridone derivative contained in the organic photoelectric conversion layer 17 includes a plurality of crystal grains composed of an ⁇ crystal phase, a ⁇ 1 crystal phase, a ⁇ 2 crystal phase, a ⁇ 3 crystal phase, or a ⁇ crystal phase in the organic photoelectric conversion layer 17.
  • Have These crystal phases include crystal planes having (001) plane, (010) plane, and (100) plane, respectively.
  • it is preferable that the plurality of crystal grains made of each crystal phase have the smallest possible distance between the faces facing each other (that is, crystal grain boundaries).
  • the organic photoelectric conversion layer 17 includes a structure in which the distance between the crystal grain boundaries of quinacridone or a quinacridone derivative is in the following range, so that the decrease in charge mobility due to the crystal grain boundaries is reduced.
  • the crystal grains composed of ⁇ 1 crystal phase, ⁇ 2 crystal phase and ⁇ 3 crystal phase will be described in detail later, but the ⁇ 2 crystal phase has the highest probability of existence of the stable ⁇ 2 crystal phase with the smallest lattice energy. Defines the distance between crystal grains composed of ⁇ 2 crystal phase.
  • the distances between the mutually facing faces of the plurality of crystal grains composed of the ⁇ crystal phase are 2.8 ⁇ 10 ⁇ 10 m or less facing each other on the (001) face and the (001) face facing each other.
  • the (001) plane and the (010) plane are 2.8 ⁇ 10 ⁇ 10 m or less, and the (001) plane and the (100) plane are 3.1 ⁇ 10 ⁇ 10 m or less and the (010) plane facing each other.
  • And (010) plane is 4.1 ⁇ 10 ⁇ 10 m or less, and the (010) plane and (100) plane facing each other are 3.6 ⁇ 10 ⁇ 10 m or less and the (100) plane and (100) facing each other In terms of surface, it is preferable that at least one condition of 3.2 ⁇ 10 ⁇ 10 m or less is satisfied.
  • the distance between the mutually facing faces of the plurality of crystal grains composed of ⁇ 2 crystal phase is 2.3 ⁇ 10 ⁇ 10 m or less between the (001) face and the (001) face facing each other, and the (001) faces facing each other.
  • And (010) plane is 2.9 ⁇ 10 ⁇ 10 m or less
  • (001) plane and (100) plane facing each other are 3.3 ⁇ 10 ⁇ 10 m or less and (010) plane and (010) facing each other 3.2 ⁇ 10 ⁇ 10 m or less on the surface, 3.7 ⁇ 10 ⁇ 10 m or less on the (010) plane and (100) plane facing each other, and 4. on the (100) plane and (100) plane facing each other. It is preferable that at least one condition of 1 ⁇ 10 ⁇ 10 m or less is satisfied.
  • the distances between the mutually opposing faces of the plurality of crystal grains composed of the ⁇ crystal phase are 1.7 ⁇ 10 ⁇ 10 m or less for the (001) face and the (001) face facing each other, and the (001) face facing each other.
  • the (010) plane is 2.7 ⁇ 10 ⁇ 10 m or less, and the (001) plane and (100) plane facing each other are 2.1 ⁇ 10 ⁇ 10 m or less and the (010) plane and (010) plane facing each other.
  • Is 3.9 ⁇ 10 ⁇ 10 m or less, (010) plane and (100) plane facing each other is 3.2 ⁇ 10 ⁇ 10 m or less, and (100) plane and (100) plane facing each other are 2.7. It is preferable that at least one condition of ⁇ 10 ⁇ 10 m or less is satisfied.
  • the quinacridone derivative is represented by the following formula (1), and specific examples include compounds represented by the following formulas (1-1) to (1-3).
  • R1 and R2 are each independently a hydrogen atom, halogen atom, mercapto group, amino group, nitro group, cyano group, carboxyl group, sulfonic acid group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group.
  • R4 each independently represents a hydrogen atom, a halogen atom, a mercapto group, an amino group, a nitro group, a cyano group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group Substituted or unsubstituted carboxylic acid ester group, substituted or unsubstituted carboxylic acid amide group, substituted or unsubstituted sulfonic acid ester group, substituted
  • buffer layers buffer layers 212 and 214.
  • buffer layers 212 and 214 may be provided between the lower electrode 15a of the organic photoelectric conversion layer 17 and the upper electrode 18 (see FIG. 10).
  • an undercoat film, a hole transport layer, an electron blocking film, an organic photoelectric conversion layer 17, a hole blocking film, a buffer film, an electron transport layer, and a work function adjusting film are stacked in this order from the lower electrode 15a side. It may be.
  • the upper electrode 18 is composed of a conductive film having the same optical transparency as the lower electrode 15a.
  • the upper electrode 18 may be separated for each pixel, or may be formed as a common electrode for each pixel.
  • the thickness of the upper electrode 18 is, for example, 10 nm to 200 nm.
  • the protective film 19 is made of a light-transmitting material.
  • the protective film 19 is a single-layer film made of any of silicon oxide, silicon nitride, silicon oxynitride, or the like, or a laminated film made of two or more of them. It is.
  • the thickness of the protective film 19 is, for example, 100 nm to 30000 nm.
  • the contact metal layer 20 is made of, for example, any one of titanium, tungsten, titanium nitride, aluminum and the like, or a laminated film made of two or more of them.
  • FIG. 2 shows a planar configuration of the organic photoelectric conversion layer 17, the protective film 19 (upper electrode 18), and the contact hole H.
  • the peripheral edge e2 of the protective film 19 (the same applies to the upper electrode 18) is located outside the peripheral edge e1 of the organic photoelectric conversion layer 17, and the protective film 19 and the upper electrode 18 are organic photoelectric photoelectric. It is formed to protrude outward from the conversion layer 17.
  • the upper electrode 18 is formed so as to cover the upper surface and side surfaces of the organic photoelectric conversion layer 17 and to extend onto the insulating film 16.
  • the protective film 19 covers the upper surface of the upper electrode 18 and is formed in the same planar shape as the upper electrode 18.
  • the contact hole H is provided in a region of the protective film 19 that is not opposed to the organic photoelectric conversion layer 17 (a region outside the peripheral edge e1) and exposes a part of the surface of the upper electrode 18.
  • the distance between the peripheral portions e1 and e2 is not particularly limited, but is, for example, 1 ⁇ m to 500 ⁇ m.
  • one rectangular contact hole H is provided along the edge of the organic photoelectric conversion layer 17, but the shape and number of the contact holes H are not limited to this, and other shapes (for example, , Circular, square, etc.) or a plurality of them may be provided.
  • a planarizing film 21 is formed on the protective film 19 and the contact metal layer 20 so as to cover the entire surface.
  • an on-chip lens 22 (microlens) is provided on the planarization film 21, an on-chip lens 22 (microlens) is provided.
  • the on-chip lens 22 focuses light incident from above on the light receiving surfaces of the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R.
  • the multilayer wiring layer 51 is formed on the surface S2 side of the semiconductor substrate 11, the light receiving surfaces of the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R are arranged close to each other. Thus, it is possible to reduce the variation in sensitivity between the colors depending on the F value of the on-chip lens 22.
  • the photoelectric conversion element 10 of the present embodiment signal charges (electrons) are taken out from the lower electrode 15a. Therefore, in the solid-state imaging device using this as a pixel, the upper electrode 18 may be used as a common electrode. In this case, the transmission path including the contact hole H, the contact metal layer 20, the wiring layers 15b and 13b, and the conductive plugs 120b1 and 120b2 may be formed in at least one place for all the pixels.
  • the semiconductor substrate 11 is, for example, formed by embedding inorganic photoelectric conversion portions 11B and 11R and a green power storage layer 110G in a predetermined region of an n-type silicon (Si) layer 111.
  • the semiconductor substrate 11 is also embedded with conductive plugs 120a1 and 120b1 serving as a transmission path for charges (electrons or holes (holes)) from the organic photoelectric conversion unit 11G.
  • the back surface (surface S1) of the semiconductor substrate 11 can be said to be a light receiving surface.
  • a plurality of pixel transistors (including transfer transistors Tr1 to Tr3) corresponding to the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R are formed on the surface (surface S2) side of the semiconductor substrate 11.
  • a plurality of pixel transistors (including transfer transistors Tr1 to Tr3) corresponding to the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R are formed.
  • Examples of the pixel transistor include a transfer transistor, a reset transistor, an amplification transistor, and a selection transistor.
  • Each of these pixel transistors is composed of, for example, a MOS transistor, and is formed in a p-type semiconductor well region on the surface S2.
  • a circuit including such a pixel transistor is formed for each of the red, green, and blue photoelectric conversion units.
  • Each circuit may have a three-transistor configuration including a total of three transistors including a transfer transistor, a reset transistor, and an amplifying transistor, among these pixel transistors.
  • a transistor configuration may be used.
  • the transfer transistors Tr1 to Tr3 are shown and described.
  • pixel transistors other than the transfer transistor can be shared between photoelectric conversion units or between pixels. Further, a so-called pixel sharing structure that shares a floating diffusion can also be applied.
  • the transfer transistors Tr1 to Tr3 include gate electrodes (gate electrodes TG1 to TG3) and floating diffusions (FDs 113, 114, and 116).
  • the transfer transistor Tr1 transfers the signal charge corresponding to green (electrons in the present embodiment) generated in the organic photoelectric conversion unit 11G and accumulated in the green power storage layer 110G to a vertical signal line Lsig described later. It is.
  • the transfer transistor Tr2 transfers the signal charge (electrons in the present embodiment) corresponding to blue generated and accumulated in the inorganic photoelectric conversion unit 11B to a vertical signal line Lsig described later.
  • the transfer transistor Tr3 transfers signal charges (electrons in the present embodiment) corresponding to red color generated and accumulated in the inorganic photoelectric conversion unit 11R to a vertical signal line Lsig described later.
  • the inorganic photoelectric conversion units 11B and 11R are photodiodes having pn junctions (Photo-Diodes), and are formed in the order of the inorganic photoelectric conversion units 11B and 11R from the surface S1 side on the optical path in the semiconductor substrate 11.
  • the inorganic photoelectric conversion unit 11B selectively detects blue light and accumulates signal charges corresponding to blue. For example, from a selective region along the surface S1 of the semiconductor substrate 11, It is formed to extend over a region near the interface with the multilayer wiring layer 51.
  • the inorganic photoelectric conversion unit 11R selectively detects red light and accumulates signal charges corresponding to red.
  • the inorganic photoelectric conversion unit 11R is formed over a lower layer (surface S2 side) than the inorganic photoelectric conversion unit 11B.
  • blue (B) is a color corresponding to a wavelength range of 450 nm to 495 nm
  • red (R) is a color corresponding to a wavelength range of 620 nm to 750 nm, for example, and the inorganic photoelectric conversion units 11B and 11R are respectively It is only necessary that light in a part or all of the wavelength range can be detected.
  • FIG. 3A shows a detailed configuration example of the inorganic photoelectric conversion units 11B and 11R.
  • FIG. 3B corresponds to a structure in another cross section of FIG. Note that in this embodiment, a case where electrons are read out as signal charges out of a pair of electrons and holes generated by photoelectric conversion (when an n-type semiconductor region is used as a photoelectric conversion layer) will be described.
  • “+ (plus)” superscripted on “p” and “n” represents a high p-type or n-type impurity concentration.
  • the gate electrodes TG2 and TG3 of the transfer transistors Tr2 and Tr3 are also shown.
  • the inorganic photoelectric conversion unit 11B includes, for example, a p-type semiconductor region (hereinafter simply referred to as a p-type region, also referred to as an n-type) 111p serving as a hole accumulation layer, and an n-type photoelectric conversion layer serving as an electron accumulation layer. (N-type region) 111n.
  • a p-type semiconductor region hereinafter simply referred to as a p-type region, also referred to as an n-type
  • N-type photoelectric conversion layer serving as an electron accumulation layer.
  • N-type region 111n.
  • Each of the p-type region 111p and the n-type photoelectric conversion layer 111n is formed in a selective region in the vicinity of the surface S1, and a part thereof is bent so as to extend to reach the interface with the surface S2. .
  • the p-type region 111p is connected to a p-type semiconductor well region (not shown) on the surface S1 side.
  • the n-type photoelectric conversion layer 111n is connected to the FD 113 (n-type region) of the blue transfer transistor Tr2. Note that a p-type region 113p (hole accumulation layer) is formed in the vicinity of the interface between each end of the p-type region 111p and the n-type photoelectric conversion layer 111n on the surface S2 side and the surface S2.
  • the inorganic photoelectric conversion unit 11R is formed, for example, by sandwiching an n-type photoelectric conversion layer 112n (electron storage layer) between p-type regions 112p1112p2 (hole storage layer) (a pnp stacked structure). Have). A part of the n-type photoelectric conversion layer 112n is bent and extended so as to reach the interface with the surface S2. The n-type photoelectric conversion layer 112n is connected to the FD 114 (n-type region) of the red transfer transistor Tr3. A p-type region 113p (hole accumulation layer) is formed at least near the interface between the end of the n-type photoelectric conversion layer 111n on the surface S2 side and the surface S2.
  • FIG. 4 shows a detailed configuration example of the green electricity storage layer 110G.
  • a description will be given of a case where electrons out of the pair of electrons and holes generated by the organic photoelectric conversion unit 11G are read from the lower electrode 15a side as signal charges.
  • FIG. 4 also shows the gate electrode TG1 of the transfer transistor Tr1 among the pixel transistors.
  • the green power storage layer 110G includes an n-type region 115n that serves as an electron storage layer.
  • a part of the n-type region 115n is connected to the conductive plug 120a1, and accumulates electrons transmitted from the lower electrode 15a side through the conductive plug 120a1.
  • the n-type region 115n is also connected to the FD 116 (n-type region) of the green transfer transistor Tr1.
  • a p-type region 115p (hole accumulation layer) is formed in the vicinity of the interface between the n-type region 115n and the surface S2.
  • the conductive plug 120a1 is electrically connected to the lower electrode 15a of the organic photoelectric conversion unit 11G and is connected to the green power storage layer 110G.
  • the conductive plug 120b1 is electrically connected to the upper electrode 18 of the organic photoelectric conversion unit 11G, and serves as a wiring for discharging holes.
  • Each of these conductive plugs 120a1 and 120b1 is made of, for example, a conductive semiconductor layer and is embedded in the semiconductor substrate 11.
  • the conductive plug 120a1 may be n-type (because it becomes an electron transmission path), and the conductive plug 120b1 may be p-type (because it becomes a hole transmission path).
  • the conductive plugs 120a1 and 120b1 may be, for example, those in which a conductive film material such as tungsten is embedded in the through via.
  • the via side surface be covered with an insulating film such as silicon oxide (SiO 2 ) or silicon nitride (SiN).
  • a multilayer wiring layer 51 is formed on the surface S2 of the semiconductor substrate 11.
  • a plurality of wirings 51 a are arranged via an interlayer insulating film 52.
  • the multilayer wiring layer 51 is formed on the side opposite to the light receiving surface, and a so-called back-illuminated solid-state imaging device can be realized.
  • a support substrate 53 made of silicon is bonded to the multilayer wiring layer 51.
  • 7A to 7C show only the main configuration of the photoelectric conversion element 10.
  • the semiconductor substrate 11 is formed. Specifically, a so-called SOI substrate in which a silicon layer 110 is formed on a silicon substrate 1111 via a silicon oxide film 1112 is prepared. The surface of the silicon layer 110 on the silicon oxide film 1112 side is the back surface (surface S1) of the semiconductor substrate 11. 5A and 5B, the structure shown in FIG. 1 is shown upside down. Subsequently, as shown in FIG. 5A, conductive plugs 120 a 1 and 120 b 1 are formed in the silicon layer 110. At this time, the conductive plugs 120a1 and 120b1 are formed by, for example, forming a through via in the silicon layer 110 and then burying the barrier metal such as silicon nitride and tungsten as described above in the through via.
  • the barrier metal such as silicon nitride and tungsten
  • a conductive impurity semiconductor layer may be formed by ion implantation into the silicon layer 110.
  • the conductive plug 120a1 is formed as an n-type semiconductor layer
  • the conductive plug 120b1 is formed as a p-type semiconductor layer.
  • inorganic photoelectric conversion units 11B and 11R each having a p-type region and an n-type region as shown in FIG. 3A, for example, in regions with different depths in the silicon layer 110 (so as to overlap each other) It is formed by ion implantation.
  • a green storage layer 111G is formed by ion implantation in a region adjacent to the conductive plug 120a1. In this way, the semiconductor substrate 11 is formed.
  • a multilayer wiring layer 51 is formed by forming a plurality of layers of wirings 51 a via the interlayer insulating film 52. Subsequently, after a support substrate 53 made of silicon is pasted on the multilayer wiring layer 51, the silicon substrate 1111 and the silicon oxide film 1112 are peeled off from the surface S1 side of the semiconductor substrate 11, and the surface S1 of the semiconductor substrate 11 is removed. Expose.
  • the organic photoelectric conversion unit 11G is formed on the surface S1 of the semiconductor substrate 11. Specifically, first, as shown in FIG. 6A, on the surface S1 of the semiconductor substrate 11, the interlayer insulating film 12 made of the laminated film of the hafnium oxide film and the silicon oxide film as described above is formed. For example, after forming a hafnium oxide film by an ALD (atomic layer deposition) method, a silicon oxide film is formed by, for example, a plasma CVD (Chemical Vapor Deposition) method.
  • ALD atomic layer deposition
  • a silicon oxide film is formed by, for example, a plasma CVD (Chemical Vapor Deposition) method.
  • contact holes H1a and H1b are formed at positions facing the conductive plugs 120a1 and 120b1 of the interlayer insulating film 12, and the conductive plugs made of the above-described materials so as to embed these contact holes H1a and H1b, respectively.
  • 120a2 and 120b2 are formed.
  • the conductive plugs 120a2 and 120b2 may be formed so as to extend to a region where light shielding is desired (so as to cover the region where light shielding is desired), or a light shielding layer may be formed in a region separated from the conductive plugs 120a2 and 120b2. May be.
  • the interlayer insulating film 14 made of the above-described material is formed by, for example, a plasma CVD method.
  • a plasma CVD method it is desirable to planarize the surface of the interlayer insulating film 14 by, for example, a CMP (Chemical Mechanical Polishing) method.
  • contact holes are respectively opened at positions of the interlayer insulating film 14 facing the conductive plugs 120a2 and 120b2, and the wiring layers 13a and 13b are formed by embedding the above-described materials.
  • a lower electrode 15 a is formed on the interlayer insulating film 14. Specifically, first, the above-described transparent conductive film is formed over the entire surface of the interlayer insulating film 14 by, eg, sputtering. Thereafter, the lower electrode 15a is removed by removing a selective portion using, for example, dry etching or wet etching using a photolithography method (exposure, development, post-bake, etc. of the photoresist film). Form. At this time, the lower electrode 15a is formed in a region facing the wiring layer 13a. Further, when the transparent conductive film is processed, the transparent conductive film is also left in the region facing the wiring layer 13b, so that the wiring layer 15b constituting a part of the hole transmission path is formed together with the lower electrode 15a. Form.
  • an insulating film 16 is formed.
  • the insulating film 16 made of the above-described material is formed by, for example, a plasma CVD method so as to cover the entire surface of the semiconductor substrate 11 so as to cover the interlayer insulating film 14, the lower electrode 15a, and the wiring layer 15b.
  • the formed insulating film 16 is polished by, for example, a CMP method so that the lower electrode 15a and the wiring layer 15b are exposed from the insulating film 16, and the lower electrode 15a and the insulating film 16 are insulated. Steps between the films 16 are alleviated (preferably planarized).
  • the organic photoelectric conversion layer 17 is formed on the lower electrode 15a.
  • the photoelectric conversion material made of the above-described material is patterned by, for example, a vacuum deposition method using a metal mask.
  • a vacuum deposition method using a metal mask.
  • each layer is used in the vacuum process using the same metal mask. It is desirable to form continuously (in a vacuum consistent process).
  • the method for forming the organic photoelectric conversion layer 17 is not necessarily limited to the method using the metal mask as described above, and other methods such as a printing technique may be used.
  • the grain boundary formed in the organic photoelectric conversion layer 17 is preferably as small as possible.
  • a wet method can be mentioned.
  • an organic semiconductor film in which an organic semiconductor material (2,7-dioctyl [1] benzothieno [3,2-b] [1] benzothiophene (C 8 -BTBT)) is formed by a wet method exceeds 30 cm 2 / Vs.
  • High mobility has been reported (H. Minemawari1, T. Yamada, H. Matsui, J. Tsutsumi, S. Haas, R. Chiba, R. Kumai, T. Hasegawa, Nature 475, 364 (2011) ).
  • the mobility corresponds to a charge mobility of 1 ⁇ 10 15 s ⁇ 1 or more.
  • a film having a small grain boundary can be formed by controlling the type, concentration, and drying conditions of the solvent, and high mobility can be obtained.
  • C 8 -BTBT is a low-molecular electron conjugated semiconductor like quinacridone, it is presumed that the mobility of the quinacridone film can also be improved by a wet method.
  • the wet method include a dip coating method, a spin coating method, and an ink jet method.
  • the dip coating method is a method in which a substrate is immersed in a solution at a certain angle, pulled up at a constant speed, and a coating film adhered to the substrate is dried to form a film.
  • the spin coating method is a method in which a coating solution is dropped on a substrate that rotates at high speed, and the coating solution is spread over the entire substrate by centrifugal force to form a uniform film, and a laminated film can also be formed.
  • the inkjet method is a process technology that manufactures devices by applying inkjet technology that prints characters and photos. It is a method that ejects minute ink droplets from a fine nozzle and sprays them directly onto the substrate, without using a mask. Can be formed.
  • the upper electrode 18 and the protective film 19 are formed.
  • the upper electrode 18 made of the above-described transparent conductive film is formed over the entire surface of the substrate so as to cover the upper surface and side surfaces of the organic photoelectric conversion layer 17 by, for example, vacuum deposition or sputtering. Note that the characteristics of the organic photoelectric conversion layer 17 are likely to fluctuate due to the influence of moisture, oxygen, hydrogen, etc., and therefore it is desirable that the upper electrode 18 be formed with the organic photoelectric conversion layer 17 by a consistent vacuum process.
  • the protective film 19 made of the above-described material is formed by, for example, a plasma CVD method so as to cover the upper surface of the upper electrode 18.
  • the upper electrode 18 is processed.
  • a contact hole H is formed in the protective film 19 by etching using, for example, a photolithography method.
  • the contact hole H is desirably formed in a region not facing the organic photoelectric conversion layer 17.
  • the upper electrode 18 is exposed from the protective film 19 in a region facing the contact hole H in order to remove the photoresist and perform cleaning using a chemical solution as described above. become. For this reason, in consideration of the generation of pin holes as described above, it is desirable to provide the contact hole H while avoiding the formation region of the organic photoelectric conversion layer 17.
  • the contact metal layer 20 made of the above-described material is formed using, for example, a sputtering method.
  • the contact metal layer 20 is formed on the protective film 19 so as to bury the contact hole H and extend to the upper surface of the wiring layer 15b.
  • the planarization film 21 is formed over the entire surface of the semiconductor substrate 11, the on-chip lens 22 is formed on the planarization film 21, thereby completing the photoelectric conversion element 10 shown in FIG.
  • signal charges are acquired as pixels of a solid-state imaging device as follows. That is, as shown in FIG. 8, when the light L is incident on the photoelectric conversion element 10 via the on-chip lens 22 (not shown in FIG. 8), the light L is converted into the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion element.
  • the conversion units 11B and 11R pass in order, and photoelectric conversion is performed for each of the red, green, and blue color lights in the passing process.
  • FIG. 9 schematically shows the flow of signal charge (electron) acquisition based on incident light.
  • signal charge electron
  • the green light Lg is selectively detected (absorbed) by the organic photoelectric conversion unit 11G and subjected to photoelectric conversion.
  • electrons Eg out of the generated electron-hole pairs are taken out from the lower electrode 15a side, and then transferred to the green power storage layer 110G via the transmission path A (the wiring layer 13a and the conductive plugs 120a1 and 120a2). Accumulated.
  • the accumulated electron Eg is transferred to the FD 116 during a read operation.
  • the holes Hg are discharged from the upper electrode 18 side through the transmission path B (contact metal layer 20, wiring layers 13b and 15b, and conductive plugs 120b1 and 120b2).
  • signal charges are accumulated as follows. That is, in the present embodiment, for example, a predetermined negative potential VL ( ⁇ 0 V) is applied to the lower electrode 15a, and a potential VU ( ⁇ VL) lower than the potential VL is applied to the upper electrode 18. .
  • the potential VL is applied to the lower electrode 15a from the wiring 51a in the multilayer wiring layer 51 through the transmission path A, for example.
  • the potential VL is applied to the upper electrode 18 from the wiring 51a in the multilayer wiring layer 51 through the transmission path B, for example.
  • the electrode 15a side It is led to the electrode 15a side (holes are led to the upper electrode 18 side).
  • the electrons Eg are extracted from the lower electrode 15a and accumulated in the green power storage layer 110G (specifically, the n-type region 115n) via the transmission path A.
  • the potential VL of the lower electrode 15a connected to the green power storage layer 110G also varies.
  • the amount of change in the potential VL corresponds to the signal potential (here, the potential of the green signal).
  • the transfer transistor Tr1 is turned on, and the electron Eg stored in the green power storage layer 110G is transferred to the FD.
  • a green signal based on the amount of received light of the green light Lg is read out to a vertical signal line Lsig described later through another pixel transistor (not shown).
  • the reset transistor and transfer transistor Tr1 are turned on, and the FD 116, which is the n-type region, and the power storage region (n-type region 115n) of the green power storage layer 110G are reset to the power supply voltage VDD, for example. .
  • electrons Er corresponding to the incident red light are accumulated in the n-type region (n-type photoelectric conversion layer 112n), and the accumulated electrons Er are transferred to the FD 114 during the read operation. Transferred. Holes are accumulated in a p-type region (not shown).
  • the negative potential VL is applied to the lower electrode 15a of the organic photoelectric conversion unit 11G. Therefore, the p-type region (in FIG. 2) that is the hole accumulation layer of the inorganic photoelectric conversion unit 11B.
  • the hole concentration of the p-type region 111p tends to increase. For this reason, generation of dark current at the interface between the p-type region 111p and the interlayer insulating film 12 can be suppressed.
  • the transfer transistors Tr2 and Tr3 are turned on, and the electrons Eb and Er accumulated in the n-type photoelectric conversion layers 111n and 112n are transferred to the FDs 113 and 114, respectively. Is done.
  • a blue signal based on the amount of received light of the blue light Lb and a red signal based on the amount of received light of the red light Lr are read out to a vertical signal line Lsig described later through another pixel transistor (not shown).
  • the reset transistor and transfer transistors Tr2, 3 (not shown) are turned on, and the FDs 113, 114, which are n-type regions, are reset to the power supply voltage VDD, for example.
  • the organic photoelectric conversion unit 11G in the vertical direction and the inorganic photoelectric conversion units 11B and 11R, the red, green and blue color lights are separated and detected without providing a color filter. A signal charge can be obtained. Thereby, it is possible to suppress light loss (sensitivity reduction) due to color light absorption of the color filter and generation of false color associated with pixel interpolation processing.
  • FIG. 10 illustrates a cross-sectional configuration of the organic photoelectric conversion unit 200 including the photoelectric conversion layer 213 having a bulk heterostructure.
  • the photoelectric conversion layer 213 is composed of a p-type semiconductor material and an n-type semiconductor material, and the p-type semiconductor layer 213a and the n-type semiconductor layer 213b are mixed in the photoelectric conversion layer 213. is doing.
  • the light L incident from the outside is converted into a charge at the boundary between the p-type semiconductor layer 213a and the n-type semiconductor layer 213b, that is, the P / N interface.
  • Electrons are transported to electrodes (for example, holes are transferred to the lower electrode 211 and electrons are transferred to the upper electrode 215) that are opposed to each other by an n-type organic semiconductor material. For this reason, in order to obtain high responsiveness in the organic photoelectric conversion unit 200 having the bulk heterostructure as shown in FIG. 10, both the p-type organic semiconductor material and the n-type organic semiconductor material have high charge transport characteristics. Is required.
  • quinacridone having excellent spectral characteristics is widely used as a p-type organic semiconductor material.
  • quinacridone has at least five kinds of crystal structures ( ⁇ -QD crystal phase, ⁇ 1 -QD crystal phase, ⁇ 2 -QD crystal phase, ⁇ 3 -QD crystal phase, ⁇ -QD crystal phase).
  • the existence probability of these crystal structures can be estimated by calculating the lattice energy using the density functional method.
  • the lattice energy is obtained by subtracting the total energy of isolated quinacridone molecules from the total energy of one quinacridone molecule in the crystal structure.
  • the PBE functional was used for the calculation, and the cutoff energy of the wave function was 40 Ry.
  • Table 1 summarizes the lattice energy in each crystal structure. From Table 1, it can be seen that the ⁇ 2 -QD crystal phase has the smallest lattice energy and is stable. Therefore, it is presumed that the existence probability of the ⁇ 2 -QD crystal phase is the highest among the five types of crystal structures.
  • quinacridone has a large lattice energy of about 80 kcal / mol, and thus is easily crystallized during the film forming process. Therefore, in the photoelectric conversion layer using quinacridone, as shown in FIG. 11, a large number of crystal grains 1231 are generated, and a discontinuous boundary surface, that is, a crystal grain, is formed between the crystal grains 1231. A field 1232 is formed. The crystal grain boundary 1232 increases the charge separation interface to improve the photoelectric conversion efficiency, but reduces the charge mobility.
  • an ⁇ crystal phase including crystal planes each having a (001) plane, a (010) plane, and a (100) plane between the lower electrode 15a and the upper electrode 18 arranged to face each other.
  • FIG. 12 illustrates an example of a structure of a crystal grain boundary formed between a large number of crystal grains of quinacridone in the organic photoelectric conversion layer 17 in the present embodiment. Specifically, it shows the structure when the (001) plane and the (010) plane of the ⁇ -QD crystal phase face each other. The crystal planes of the two crystal grains are parallel to each other, and the distance between the atoms (outermost surface atoms) existing on the crystal plane is defined as the distance d of the crystal grain boundary.
  • the organic photoelectric conversion layer 17 containing quinacridone or a quinacridone derivative has (001) and (010) planes of the ⁇ -QD crystal phase as the interface between crystal grains consisting of the ⁇ -QD crystal phase.
  • Plane, (001) plane and (001) plane, (001) plane and (100) plane, (010) plane and (010) plane, (010) ) Plane and (100) plane, and (100) plane and (100) plane face each other, and six kinds of crystal grain boundaries are formed. These six crystal grain boundaries are also formed between crystal grains composed of ⁇ 2 -QD crystal phases and crystal grains composed of ⁇ -QD crystal phases.
  • the charge transfer rate between these grain boundaries is calculated by the density functional method (H. Kobayashi, N. Kobayashi, S. Hosoi, N. Koshitani, D. Murakami, R. Shirasawa, Y. Kudo, D. Hobara, Y. Tokita, and M. Itabashi, J. Chem. Phys. 139, 014707 (2013)).
  • the transfer integral was calculated by systematically changing the positional relationship of the other molecule (molecule B) with respect to the molecule A with one molecule (molecule A) as a reference.
  • the charge transfer rate is obtained based on Marcus theory.
  • a B3LYP functional was used, and 3-21 + G (d) was used as the basis function.
  • d distance between crystal grain boundaries
  • 10 points were calculated. Specifically, the relative position in the yz plane parallel to the crystal plane is 25 points indicated by black circles in FIG. 14, and the rotation angle ⁇ around the axis perpendicular to the crystal plane is 4 points (0 °). , 90 [deg.], 180 [deg.], 270 [deg.]), And calculating the average of charge transfer rates at 100 points with respect to the distance (d) of one crystal grain boundary.
  • FIG. 15A and FIG. 15B show the relationship between the distance (d) of the grain boundary in each facing surface of the ⁇ -QD crystal phase and the charge transfer rate.
  • FIG. 15A shows the charge transfer rate between the highest occupied molecular orbitals (HOMO)
  • FIG. 15B shows the charge transfer rate between the lowest unoccupied molecular orbitals (LUMO)
  • FIG. 15A and FIG. 15B respectively, the distance (d) of the grain boundary and the charge transfer at the opposing faces of the ⁇ 2 crystal phase (FIGS. 16A and 16B) and the ⁇ crystal phase (FIGS. 17A and 17B), respectively. It represents the relationship with the rate.
  • Table 2 summarizes the range of the grain boundary distance (d) in the ⁇ crystal phase, ⁇ 2 crystal phase, and ⁇ crystal phase that satisfy this condition.
  • the charge transfer rate of 1 ⁇ 10 10 s ⁇ 1 or more at the grain boundary including the (001) plane of the ⁇ -QD crystal phase is 2.8 ⁇ 10 ⁇ 10 when the distance (d) of the grain boundary is It can be seen that it can be obtained at m or less.
  • the crystal grain boundary distance (d) is 2.8 ⁇ 10 ⁇ 10 m or less at the crystal grain boundary including the (010) plane, and the crystal grain boundary distance (d) is at the crystal grain boundary including the (100) plane. It can be seen that it is 3.1 ⁇ 10 ⁇ 10 m or less.
  • the charge transfer rate of 1 ⁇ 10 10 s ⁇ 1 or more has a crystal grain boundary distance (d) of 2.3 ⁇ 10 ⁇ 10 m or less.
  • the grain boundary distance (d) is 2.9 ⁇ 10 ⁇ 10 m or less at the crystal grain boundary including the (010) plane, and the crystal grain boundary distance (d) is at the crystal grain boundary including the (100) plane. It can be seen that it can be obtained at 3.3 ⁇ 10 ⁇ 10 m or less.
  • the charge transfer rate of 1 ⁇ 10 10 s ⁇ 1 or more at a grain boundary including the (001) plane of the ⁇ -QD crystal phase is such that the distance (d) of the crystal grain boundary is 1.7 ⁇ 10 ⁇ 10 m or less.
  • the crystal grain boundary distance (d) is 2.7 ⁇ 10 ⁇ 10 m or less at the crystal grain boundary including the (010) plane, and the crystal grain boundary distance (d) is 2 at the crystal grain boundary including the (100) plane. It can be seen that it is 1 ⁇ 10 ⁇ 10 m or less.
  • the distance between the mutually facing surfaces of the plurality of crystal grains composed of the ⁇ crystal phase is 2.8 ⁇ 10 ⁇ 10 m or less in the (001) plane and the (001) plane facing each other.
  • the (001) plane and the (010) plane are 2.8 ⁇ 10 ⁇ 10 m or less, and the (001) plane and the (100) plane are 3.1 ⁇ 10 ⁇ 10 m or less and the (010) plane facing each other.
  • And (010) plane is 4.1 ⁇ 10 ⁇ 10 m or less, and the (010) plane and (100) plane facing each other are 3.6 ⁇ 10 ⁇ 10 m or less, or the (100) plane and (100 ) Surface, it is preferable that at least one condition of 3.2 ⁇ 10 ⁇ 10 m or less is satisfied.
  • the distance between the mutually facing faces of the plurality of crystal grains composed of ⁇ 2 crystal phase is 2.3 ⁇ 10 ⁇ 10 m or less between the (001) face and the (001) face facing each other, and the (001) faces facing each other.
  • And (010) plane is 2.9 ⁇ 10 ⁇ 10 m or less
  • (001) plane and (100) plane facing each other are 3.3 ⁇ 10 ⁇ 10 m or less and (010) plane and (010) facing each other 3.2 ⁇ 10 ⁇ 10 m or less for the surface, 3.7 ⁇ 10 ⁇ 10 m or less for the (010) plane and (100) plane facing each other, or 4 for the (100) plane and (100) plane facing each other. It is preferable that at least one condition of 1 ⁇ 10 ⁇ 10 m or less is satisfied.
  • the distances between the mutually opposing faces of the plurality of crystal grains composed of the ⁇ crystal phase are 1.7 ⁇ 10 ⁇ 10 m or less for the (001) face and the (001) face facing each other, and the (001) face facing each other.
  • the (010) plane is 2.7 ⁇ 10 ⁇ 10 m or less, and the (001) plane and (100) plane facing each other are 2.1 ⁇ 10 ⁇ 10 m or less and the (010) plane and (010) plane facing each other.
  • Is 3.9 ⁇ 10 ⁇ 10 m or less, and the (010) plane and (100) plane facing each other are 3.2 ⁇ 10 ⁇ 10 m or less, or the (100) plane and (100) plane facing each other are 2.
  • the charge mobility at the crystal grain boundary of each crystal phase is achieved by setting the distance between the mutually opposing faces of the crystal grains in each crystal phase (distance of the crystal grain boundary) within the above range. Is suppressed.
  • the organic photoelectric conversion layer 17 is formed from an ⁇ crystal phase, a ⁇ 2 crystal phase, or a ⁇ crystal phase including crystal planes each having a (001) plane, a (010) plane, and a (100) plane. Formed by using quinacridone or a quinacridone derivative that forms a plurality of crystal grains, and the organic photoelectric conversion layer 17 containing the quinacridone or quinacridone derivative is adjacent to each other among the plurality of crystal grains in each crystal phase. A structure in which the distance between the opposing surfaces has a value within the above range is included. Accordingly, it is possible to provide a photoelectric conversion element in which a decrease in charge mobility at a crystal grain boundary is suppressed and an afterimage characteristic is improved, that is, generation of an afterimage can be suppressed.
  • FIG. 18 illustrates a cross-sectional configuration of a photoelectric conversion element (photoelectric conversion element 60) according to the second embodiment of the present disclosure.
  • the photoelectric conversion element 60 constitutes one pixel in a solid-state imaging device such as a CCD image sensor or a CMOS image sensor, for example, in the same manner as the photoelectric conversion element 10 in the first embodiment.
  • pixel transistors including transfer transistors Tr1 to 3 described later
  • multilayer wiring It has a layer (multilayer wiring layer 51).
  • the organic photoelectric conversion unit 61G includes an organic photoelectric conversion layer 67 formed using an organic semiconductor material.
  • the organic semiconductor material constituting the organic photoelectric conversion layer 67 forms a plurality of crystal grains in the organic photoelectric conversion layer 67, and the crystal grains have an anisotropy coefficient ( ⁇ ) relating to charge transfer in the crystal grains of 0. .3 or more and 1 or less.
  • the organic photoelectric conversion layer 67 of the present embodiment is a specific example of “photoelectric conversion layer” in the present disclosure.
  • the photoelectric conversion element 60 has the same configuration as that of the photoelectric conversion element 10, and has a stacked structure of one organic photoelectric conversion unit 61G and two inorganic photoelectric conversion units 11B and 11R as described above. Yes. Thereby, the photoelectric conversion element 60 acquires each color signal of red (R), green (G), and blue (B) with one element.
  • the organic photoelectric conversion layer 67 is configured using an organic semiconductor material that photoelectrically converts light in a selective wavelength range while transmitting light in other wavelength ranges.
  • This organic semiconductor material forms a plurality of crystal grains having an anisotropy coefficient ( ⁇ ) relating to charge transfer of 0.3 or more and 1 or less in the organic photoelectric conversion layer 67.
  • Organic semiconductor materials constituting the organic photoelectric conversion layer 67 of the present embodiment include quinacridone and quinacridone derivatives, chlorinated boron subphthalocyanine and chlorinated boron subphthalocyanine derivatives, pentacene and pentacene that form an ⁇ crystal phase or a ⁇ crystal phase. Derivatives, benzothienobenzothiophene and benzothienobenzothiophene derivatives, fullerenes and fullerene derivatives.
  • the organic photoelectric conversion layer 67 includes one or more of the above organic semiconductor materials. These organic semiconductor materials act as a p-type semiconductor or an n-type semiconductor in the organic photoelectric conversion layer 67.
  • the organic photoelectric conversion layer 67 is preferably configured to include one or both of an organic p-type semiconductor and an organic n-type semiconductor.
  • the organic semiconductor material acts as a p-type semiconductor or an n-type semiconductor depending on the combination with the organic semiconductor material used together. The combination of each material and the role in that case are the same as in the first embodiment.
  • the organic photoelectric conversion layer 67 may contain, for example, naphthalene, anthracene, phenanthrene, tetracene, pyrene, perylene, fluoranthene, or derivatives thereof in addition to the organic semiconductor material.
  • a polymer such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, acetylene, diacetylene, or a derivative thereof may be used.
  • metal complex dyes cyanine dyes, merocyanine dyes, phenylxanthene dyes, triphenylmethane dyes, rhodacyanine dyes, xanthene dyes, macrocyclic azaannulene dyes, azulene dyes, naphthoquinone, anthraquinone dyes, Condensed polycyclic aromatic compounds such as anthracene and pyrene and chain compounds condensed with aromatic or heterocyclic compounds, or two compounds such as quinoline, benzothiazole and benzoxazole having a squarylium group and a croconic methine group as a linking chain.
  • a cyanine-like dye or the like bonded by a nitrogen heterocycle or a squarylium group and a croconite methine group can be preferably used.
  • the metal complex dye is preferably a dithiol metal complex dye, a metal phthalocyanine dye, a metal porphyrin dye, or a ruthenium complex dye, but is not limited thereto.
  • the organic photoelectric conversion layer 67 can photoelectrically convert green light corresponding to a part or all of the wavelength range of 495 nm to 570 nm, for example.
  • the thickness of such an organic photoelectric conversion layer 67 is, for example, 50 nm to 500 nm.
  • the charge transfer rate between molecules varies depending on the charge transfer direction.
  • 20A to 20C show three types of conductivity of crystal grains of the organic semiconductor material.
  • the crystal grain shown in FIG. 20A is a one-dimensional conduction crystal (charge diffusion coefficient D 1 ) capable of diffusing charges only in a one-dimensional direction, and the crystal grain shown in FIG. It is a two-dimensional conductive crystal (charge diffusion coefficients D 1 and D 2 ) capable of diffusing charges in the direction.
  • the crystal grains shown in FIG. 20C are three-dimensional conductive crystals (charge diffusion coefficients D 1 , D 2 , D 3 ) capable of diffusing charges in a three-dimensional direction. In the crystal grains in FIG.
  • each crystal grain of the organic semiconductor material often has anisotropy in the charge diffusion coefficient.
  • the degree of anisotropy of the charge diffusion coefficient in each crystal grain greatly depends on the molecular structure and crystal structure of the organic semiconductor material.
  • FIG. 21 schematically shows the conductivity of the charge conduction network including only the two-dimensional conduction crystal shown in FIG. 20 (B).
  • FIG. 21A if a path in which the diffusible crystal orientation is connected between adjacent crystal grains is formed, a charge conduction network is formed as indicated by an arrow, and a large network mobility is obtained ( Percolation).
  • FIG. 21B when the crystal orientation that can be diffused is interrupted between adjacent crystal grains and a narrow path is formed, the charge conduction network is interrupted and the network is interrupted. Mobility decreases (non-percolation-like). Whether the charge conduction network is percolated or non-percolated is largely related to the anisotropy of charge transfer.
  • the time required for the charge generated at the charge separation interface to reach the electrode becomes longer. That is, even if there is no gap at the crystal grain boundary, when crystal grains having anisotropy of the charge diffusion coefficient are aggregated, the charge mobility is lowered and the afterimage characteristic is lowered. was there.
  • FIG. 22 schematically shows the structure of the crystal grains 1231 included in the organic photoelectric conversion layer 67 in the present embodiment.
  • the anisotropy coefficient ( ⁇ ) relating to the charge transfer in the crystal grains is defined by the following formula (1) using the charge diffusion coefficients D 1 , D 2 , and D 3 .
  • the charge diffusion coefficients D 1 , D 2 , and D 3 are defined by the diffusion coefficients Dx, Dy, and Dz in the X-axis, Y-axis, and Z-axis directions orthogonal to each other in descending order.
  • the X axis is defined as the a axis of the crystal, and the Y axis is defined so that the XY plane coincides with the ab plane of the crystal.
  • ⁇ takes a value from 0 to 1, and as it approaches 1, it is three-dimensionally conductive as shown in FIG. 20C, and as it is close to 0, it is one-dimensionally conductive as shown in FIG. Indicates that there is.
  • Table 3 shows quinacridone in the ⁇ crystal phase ( ⁇ -QD), quinacridone in the ⁇ 2 crystal phase ( ⁇ 2 -QD), quinacridone in the ⁇ crystal phase ( ⁇ -QD), chlorinated boron subphthalocyanine (SubPc-Cl),
  • a summary of diffusion coefficients D 1 , D 2 , D 3 and ⁇ in each crystal grain of fullerene (C 60 ), pentacene, rubrene and dioctylbenzothienobenzothiophene (C 8 -BTBT). is there.
  • the diffusion coefficients D 1 , D 2 and D 3 of the organic semiconductor material are obtained from Marcus theory, and the anisotropy coefficient ( ⁇ ) is calculated by applying this to the above equation (1).
  • the network mobility can be calculated using the following method, for example.
  • the calculation method described below was developed to calculate network mobility and is referred to as a coarse-grained kinetic-Monte-Carlo (kMC) method.
  • each of the crystal grain i and the crystal grain j is a cube having one side a, and the charge is present only at the center of the crystal grain.
  • the charge transfer rate between the two crystal grains is expressed by the following formula (2).
  • Di is the charge diffusion coefficient of crystal grain i in the direction of crystal grain j
  • Dj is the charge diffusion coefficient of crystal grain j in the direction of crystal grain i.
  • the charge mobility ⁇ can be obtained from the following Einstein relational expression (4).
  • FIG. 26 shows a state in which crystal orientations of crystal grains are aligned (single crystal; FIG. 26A) and a case where crystal orientations are random (polycrystal; FIG. 26B).
  • Table 4 summarizes the network mobility ( ⁇ s ) in the single crystal state, the network mobility ( ⁇ p ) and the charge conduction network efficiency ( ⁇ ) in the polycrystalline state of the organic semiconductor material.
  • the network mobility ( ⁇ s , ⁇ p ) of each crystal state was calculated using the coarse-grained kMC method.
  • the charge conduction network efficiency ( ⁇ ) was defined by the following equation (5).
  • FIG. 27 shows the relationship between the anisotropy coefficient ( ⁇ ) and the charge conduction network efficiency ( ⁇ ). From FIG. 27, it can be seen that the following equation (6) holds between the two. That is, it can be seen that the charge conduction network efficiency ( ⁇ ) can be predicted from the anisotropy coefficient ( ⁇ ) of the crystal grains.
  • the charge mobility is different between the gap of the crystal grain boundary 1232 and the charge mobility in the crystal grain 1231. Decreased by two factors, the directionality. That is, by reducing both of these two factors of reduction, the charge transfer rate can be increased by a synergistic effect, and the charge transfer rate of the single crystal can be approached.
  • the charge transfer rate is expressed by the following equation (7).
  • ⁇ is the overall charge transfer rate
  • ⁇ sc is the charge transfer rate of the single crystal
  • ⁇ is the rate of decrease of the charge transfer rate at the grain boundaries. Note that the overall charge transfer rate of ⁇ is the charge transfer rate of the organic photoelectric conversion layer 67 here.
  • the charge transfer rate ( ⁇ sc ) of a typical organic single crystal is 1 ⁇ 10 13 to 1 ⁇ 10 14 s ⁇ 1 .
  • the rate of decrease in charge transfer rate at the grain boundary ( ⁇ ) varies depending on the film formation process conditions (film formation temperature, growth rate, annealing conditions, etc.), but in a dense structure fabricated under optimum process conditions, the crystal grains The gap in the field is narrowed.
  • the rate of decrease in the charge transfer rate ( ⁇ ) at the grain boundary is about 0.01.
  • the crystal grain boundary widens, and thus the rate of decrease in charge transfer rate ( ⁇ ) at the crystal grain boundary generally decreases to about 0.003.
  • the charge transfer rate of the photoelectric conversion element is 1 ⁇ 10 10 s ⁇ 1 or more. desirable.
  • the charge transfer rate ( ⁇ sc ) of the organic single crystal is 1 ⁇ 10 13 s ⁇ 1 and the rate of decrease of the charge transfer rate ( ⁇ ) at the grain boundary is 0.003, ⁇ > 1 ⁇ 10 10 s ⁇ 1 It can be seen that ⁇ > 0.3 is necessary to realize.
  • the organic photoelectric conversion layer 67 is preferably formed using crystal grains having an anisotropy coefficient of charge transfer of 0.3 or more.
  • a charge conduction network having a high charge transfer rate of 1 ⁇ 10 10 s ⁇ 1 or more is formed between crystal grains.
  • the upper limit of the anisotropy coefficient regarding charge transfer in the present embodiment is a value when the organic semiconductor material constituting the organic photoelectric conversion layer 67 is a single crystal.
  • the organic photoelectric conversion layer 67 is formed using crystal grains having an anisotropy coefficient of charge transfer of 0.3 or more. As a result, a charge conduction network having a high charge transfer rate of, for example, 1 ⁇ 10 10 s ⁇ 1 or more is formed between crystal grains. That is, it is possible to provide the photoelectric conversion element 60 with improved afterimage characteristics.
  • the photoelectric conversion element of this indication is good also as a structure which combined the photoelectric conversion element 10 in the said 1st Embodiment, and the photoelectric conversion element 60 in the said 2nd Embodiment.
  • the organic photoelectric conversion layer constituting the organic photoelectric conversion unit is formed of a plurality of crystal grains composed of an ⁇ crystal phase or a ⁇ crystal phase each including a crystal plane having a (001) plane, a (010) plane, and a (100) plane.
  • the adjacent crystal grains among the plurality of crystal grains in each crystal phase have a distance between the faces facing each other within the range described in the first embodiment.
  • the anisotropy coefficient relating to the charge transfer in the crystal grains is 0.3 to 1 inclusive.
  • the decrease in charge mobility is caused by the fact that crystal grain boundaries included in the organic photoelectric conversion layer and crystals having anisotropy in the charge diffusion coefficient aggregate to form a polycrystalline structure. Arise.
  • the technique in the first embodiment that suppresses the decrease in charge mobility at the crystal grain boundary of each crystal phase and the second that suppresses the decrease in charge mobility between crystal grains forming each crystal phase.
  • an organic photoelectric conversion layer having a higher charge transfer rate can be formed. That is, it is possible to provide a photoelectric conversion element with improved afterimage characteristics.
  • FIG. 28 illustrates an overall configuration of a solid-state imaging device (solid-state imaging device 1) using the photoelectric conversion element 10 described in the above embodiment for each pixel.
  • the solid-state imaging device 1 is a CMOS image sensor, and has a pixel unit 1a as an imaging area on a semiconductor substrate 11, and, for example, a row scanning unit 131 and a horizontal selection unit 133 in a peripheral region of the pixel unit 1a.
  • the peripheral circuit unit 130 includes a column scanning unit 134 and a system control unit 132.
  • the pixel unit 1a has, for example, a plurality of unit pixels P (corresponding to the photoelectric conversion element 10) arranged two-dimensionally in a matrix.
  • a pixel drive line Lread (specifically, a row selection line and a reset control line) is wired for each pixel row, and a vertical signal line Lsig is wired for each pixel column.
  • the pixel drive line Lread transmits a drive signal for reading a signal from the pixel.
  • One end of the pixel drive line Lread is connected to an output end corresponding to each row of the row scanning unit 131.
  • the row scanning unit 131 is configured by a shift register, an address decoder, or the like, and is a pixel driving unit that drives each unit pixel P of the pixel unit 1a, for example, in units of rows.
  • a signal output from each unit pixel P of the pixel row that is selectively scanned by the row scanning unit 131 is supplied to the horizontal selection unit 133 through each of the vertical signal lines Lsig.
  • the horizontal selection unit 133 is configured by an amplifier, a horizontal selection switch, and the like provided for each vertical signal line Lsig.
  • the column scanning unit 134 includes a shift register, an address decoder, and the like, and drives the horizontal selection switches in the horizontal selection unit 133 in order while scanning. By the selective scanning by the column scanning unit 134, the signal of each pixel transmitted through each of the vertical signal lines Lsig is sequentially output to the horizontal signal line 135 and transmitted to the outside of the semiconductor substrate 11 through the horizontal signal line 135. .
  • the circuit portion including the row scanning unit 131, the horizontal selection unit 133, the column scanning unit 134, and the horizontal signal line 135 may be formed directly on the semiconductor substrate 11, or provided in the external control IC. It may be. In addition, these circuit portions may be formed on another substrate connected by a cable or the like.
  • the system control unit 132 receives a clock given from the outside of the semiconductor substrate 11, data for instructing an operation mode, and the like, and outputs data such as internal information of the solid-state imaging device 1.
  • the system control unit 132 further includes a timing generator that generates various timing signals, and the row scanning unit 131, the horizontal selection unit 133, the column scanning unit 134, and the like based on the various timing signals generated by the timing generator. Peripheral circuit drive control.
  • FIG. 29 shows a schematic configuration of the electronic apparatus 2 (camera) as an example.
  • the electronic device 2 is, for example, a video camera capable of taking a still image or a moving image, and includes a solid-state imaging device 1, an optical system (optical lens) 310, a shutter device 311, the solid-state imaging device 1 and the shutter device 311.
  • a driving unit 313 for driving and a signal processing unit 312 are included.
  • the optical system 310 guides image light (incident light) from a subject to the pixel unit 1 a of the solid-state imaging device 1.
  • the optical system 310 may be composed of a plurality of optical lenses.
  • the shutter device 311 controls the light irradiation period and the light shielding period for the solid-state imaging device 1.
  • the drive unit 313 controls the transfer operation of the solid-state imaging device 1 and the shutter operation of the shutter device 311.
  • the signal processing unit 312 performs various types of signal processing on the signal output from the solid-state imaging device 1.
  • the video signal Dout after the signal processing is stored in a storage medium such as a memory, or is output to a monitor or the like.
  • the present disclosure is not limited to the above-described embodiments and the like, and various modifications can be made.
  • a photoelectric conversion element solid-state imaging device
  • an organic photoelectric conversion unit 11G that detects green light
  • inorganic photoelectric conversion units 11B and 11R that detect blue light and red light
  • the present disclosure is not limited to such a structure. That is, red light or blue light may be detected in the organic photoelectric conversion unit, or green light may be detected in the inorganic photoelectric conversion unit.
  • the number and ratio of these organic photoelectric conversion units and inorganic photoelectric conversion units are not limited, and two or more organic photoelectric conversion units may be provided. A signal may be obtained.
  • the organic photoelectric conversion part and the inorganic photoelectric conversion part are not limited to the structure in which the organic photoelectric conversion part and the inorganic photoelectric conversion part are stacked in the vertical direction, but may be arranged in parallel along the substrate surface.
  • the configuration of the back-illuminated solid-state imaging device has been exemplified.
  • the present disclosure can also be applied to a front-illuminated solid-state imaging device.
  • the solid-state imaging device (photoelectric conversion element) of the present disclosure does not have to include all the components described in the first embodiment, and may include other layers.
  • the present disclosure may be configured as follows. (1) A first electrode and a second electrode disposed opposite to each other; A photoelectric conversion element comprising: a photoelectric conversion layer that is provided between the first electrode and the second electrode and includes crystal grains having an anisotropy coefficient related to charge transfer of 0.3 or more and 1 or less. (2) The photoelectric conversion layer contains quinacridone or a quinacridone derivative, The said crystal grain is a photoelectric conversion element as described in said (1) comprised by the said quinacridone of the (alpha) crystal phase, or the said quinacridone derivative.
  • the photoelectric conversion layer contains quinacridone or a quinacridone derivative, The photoelectric conversion element according to (1) or (2), wherein the crystal grains are constituted by the quinacridone or the quinacridone derivative having a ⁇ crystal phase.
  • the photoelectric conversion layer includes a chlorinated boron subphthalocyanine or a chlorinated boron subphthalocyanine derivative, The photoelectric conversion element according to any one of (1) to (3), wherein the crystal grains are configured by the chlorinated boron subphthalocyanine or the chlorinated boron subphthalocyanine derivative.
  • the photoelectric conversion layer contains pentacene or a pentacene derivative, The photoelectric conversion element according to any one of (1) to (4), wherein the crystal grain is configured by the pentacene or the pentacene derivative.
  • the photoelectric conversion layer includes benzothienobenzothiophene or a benzothienobenzothiophene derivative, The photoelectric conversion element according to any one of (1) to (5), wherein the crystal grain is configured by the benzothienobenzothiophene or the benzothienobenzothiophene derivative.
  • the photoelectric conversion layer contains fullerene or a fullerene derivative, The photoelectric conversion element according to any one of (1) to (6), wherein the crystal grains are configured by the fullerene or the fullerene derivative.
  • the photoelectric conversion layer includes two or more of quinacridone, a quinacridone derivative, a chlorinated boron subphthalocyanine, a chlorinated boron subphthalocyanine derivative, a pentacene, a pentacene derivative, a benzothienobenzothiophene, a benzothienobenzothiophene derivative, a fullerene, and a fullerene derivative.
  • the photoelectric conversion element according to any one of (7) to (9).
  • (11) In each pixel, an organic photoelectric conversion unit having one or more of the photoelectric conversion layers and one or more inorganic photoelectric conversion units that perform photoelectric conversion in a wavelength region different from the organic photoelectric conversion unit are stacked.
  • (12) The inorganic photoelectric conversion part is embedded in a semiconductor substrate, The said organic photoelectric conversion part is a photoelectric conversion element as described in said (11) currently formed in the 1st surface side of the said semiconductor substrate.
  • the organic photoelectric conversion unit performs green light photoelectric conversion, The photoelectric conversion according to (12) or (13), wherein an inorganic photoelectric conversion unit that performs photoelectric conversion of blue light and an inorganic photoelectric conversion unit that performs photoelectric conversion of red light are stacked in the semiconductor substrate. element.
  • the photoelectric conversion layer includes a plurality of the crystal grains composed of a quinacridone derivative or a quinacridone derivative having a ⁇ 2 crystal phase
  • the quinacridone or the quinacridone derivative of the ⁇ 2 crystal phase includes crystal planes each having a (001) plane, a (010) plane, and a (100) plane, Among adjacent crystal grains among the plurality of crystal grains,
  • the distance between the (001) plane and the (001) plane facing each other is 2.3 ⁇ 10 ⁇ 10 m or less
  • the distance between the (001) plane and the (010) plane facing each other is 2.9 ⁇ 10 ⁇ 10 m or less
  • the distance between the (001) plane and the (100) plane facing each other is 3.3 ⁇ 10 ⁇ 10 m or less
  • the distance between the (010) plane and the (010) plane facing each other is 3.2 ⁇ 10 ⁇ 10 m or less
  • the distance between the (010) plane and the (100) plane facing each other is 3.7 ⁇ 10 ⁇ 10 m
  • the plurality of crystal grains constituted by the quinacridone or the quinacridone derivative in the ⁇ crystal phase each include a crystal plane having a (001) plane, a (010) plane, and a (100) plane, Among adjacent crystal grains among the plurality of crystal grains,
  • the distance between the (001) plane and the (001) plane facing each other is 2.8 ⁇ 10 ⁇ 10 m or less
  • the distance between the (001) plane and the (010) plane facing each other is 2.8 ⁇ 10 ⁇ 10 m or less
  • the distance between the (001) plane and the (100) plane facing each other is 3.1 ⁇ 10 ⁇ 10 m or less
  • the distance between the (010) plane and the (010) plane facing each other is 4.1 ⁇ 10 ⁇ 10 m or less
  • the distance between the (010) plane and the (100) plane facing each other is 3.6 ⁇ 10 ⁇ 10 m or less
  • the distance between the (100) plane and the (100) plane facing each other is 3.2 ⁇ 10 ⁇ 10 m
  • the plurality of crystal grains constituted by the quinacridone or the quinacridone derivative of the ⁇ crystal phase include crystal planes each having a (001) plane, a (010) plane, and a (100) plane, Among adjacent crystal grains among the plurality of crystal grains, The distance between the (001) plane and the (001) plane facing each other is 1.7 ⁇ 10 ⁇ 10 mm or less, The distance between the (001) plane and the (010) plane facing each other is 2.7 ⁇ 10 ⁇ 10 mm or less, The distance between the (001) plane and the (100) plane facing each other is 2.1 ⁇ 10 ⁇ 10 mm or less, The distance between the (010) plane and the (010) plane facing each other is 3.9 ⁇ 10 ⁇ 10 m or less, The distance between the (010) plane and the (100) plane facing each other is 3.2 ⁇ 10 ⁇ 10 m or less, and the distance between the (100) plane and the (100) plane facing each other is 2.7 ⁇ 10 ⁇ 10 m
  • the quinacridone or the quinacridone derivative forms a plurality of crystal grains composed of ⁇ 2 crystal phase each including a crystal plane having a (001) plane, a (010) plane, and a (100) plane, Among adjacent crystal grains among the plurality of crystal grains,
  • the distance between the (001) plane and the (001) plane facing each other is 2.3 ⁇ 10 ⁇ 10 m or less, The distance between the (001) plane and the (010) plane facing each other is 2.9 ⁇ 10 ⁇ 10 m or less, The distance between the (001) plane and the (100) plane facing each other is 3.3 ⁇ 10 ⁇ 10 m or less,
  • the distance between the (010) plane and the (010) plane facing each other is 3.2 ⁇ 10 ⁇ 10 m or less,
  • the quinacridone or the quinacridone derivative forms a plurality of crystal grains composed of an ⁇ crystal phase each including a crystal plane having a (001) plane, a (010) plane, and a (100) plane, Among adjacent crystal grains among the plurality of crystal grains,
  • the distance between the (001) plane and the (001) plane facing each other is 2.8 ⁇ 10 ⁇ 10 m or less
  • the distance between the (001) plane and the (010) plane facing each other is 2.8 ⁇ 10 ⁇ 10 m or less
  • the distance between the (001) plane and the (010) plane facing each other is 3.1 ⁇ 10 ⁇ 10 m or less
  • the distance between the (010) plane and the (010) plane facing each other is 4.1 ⁇ 10 ⁇ 10 m or less
  • the quinacridone or the quinacridone derivative forms a plurality of crystal grains each composed of a ⁇ crystal phase including a crystal plane having a (001) plane, a (010) plane, and a (100) plane, Among adjacent crystal grains among the plurality of crystal grains,
  • the distance between the (001) plane and the (001) plane facing each other is 1.7 ⁇ 10 ⁇ 10 mm or less, The distance between the (001) plane and the (010) plane facing each other is 2.7 ⁇ 10 ⁇ 10 mm or less, The distance between the (001) plane and the (100) plane facing each other is 2.1 ⁇ 10 ⁇ 10 mm or less,
  • the distance between the (010) plane and the (010) plane facing each other is 3.9 ⁇ 10 ⁇ 10 m or less,

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Abstract

Selon un mode de réalisation de la présente invention, un élément de conversion photoélectrique comprend une première électrode et une seconde électrode disposées l'une en face de l'autre, et une couche de conversion photoélectrique disposée entre la première électrode et la seconde électrode, la couche de conversion photoélectrique incluant des grains cristallins ayant un coefficient d'anisotropie par rapport au transfert de charge compris enter 0,3 et 1.
PCT/JP2016/065605 2015-06-17 2016-05-26 Élément de conversion photoélectrique WO2016203925A1 (fr)

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