JP2019057704A - Photoelectric conversion element and imaging apparatus - Google Patents

Abstract

To provide a photoelectric conversion element capable of improving heat resistance and an imaging apparatus.SOLUTION: A photoelectric conversion element according to an embodiment of the present disclosure includes: an anode; a cathode oppositely arranged relative to the anode; a photoelectric conversion layer provided between the anode and the cathode; and an electronic block layer that is provided between the anode and the photoelectric conversion layer and containing an organic semiconductor material represented by a general formula (1).SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to, for example, a photoelectric conversion element using an organic semiconductor material and an imaging apparatus including the photoelectric conversion element.

  An imaging element (photoelectric conversion element) using an organic semiconductor material has a problem of maintaining excellent element performance such as low dark current, high quantum efficiency, and high response speed even after a heating process in a semiconductor manufacturing process. Yes. On the other hand, for example, in Patent Document 1, the organic photoelectric conversion film is formed as an amorphous film using a p-type organic photoelectric conversion material having a glass transition point (Tg) of 100 ° C. or higher, and further, the organic photoelectric conversion film and the electrode A photoelectric conversion element with improved heat resistance by providing a blocking layer containing a blocking material having a Tg of 140 ° C. or higher is disclosed.

JP 2011-187937 A

  Thus, for example, development of a photoelectric conversion element excellent in heat resistance is required.

  It is desirable to provide a photoelectric conversion element and an imaging device that can improve heat resistance.

  A photoelectric conversion element according to an embodiment of the present disclosure is provided between an anode, a cathode disposed opposite to the anode, a photoelectric conversion layer provided between the anode and the cathode, and an anode and the photoelectric conversion layer. And an electron block layer containing an organic semiconductor material represented by the following general formula (1).

（Ｒ１，Ｒ２，Ｒ３，Ｒ４は、各々独立して、水素原子または炭素数４以上４０以下のアリール基、ヘテロアリール基、カルバゾール基、ジフェニルアミノ基あるいはそれらの誘導体であり、Ｒ１，Ｒ２，Ｒ３，Ｒ４のうちの少なくとも１つは、炭素数１２以上４０以下のカルバゾール基またはジフェニルアミノ基あるいはそれらの誘導体である。）

(R1, R2, R3 and R4 are each independently a hydrogen atom or an aryl group, heteroaryl group, carbazole group, diphenylamino group or derivatives thereof having 4 to 40 carbon atoms, and R1, R2, R3 , R4 is a carbazole group having 12 to 40 carbon atoms, a diphenylamino group, or a derivative thereof.)

  In the imaging apparatus according to an embodiment of the present disclosure, each pixel includes one or a plurality of photoelectric conversion elements, and the photoelectric conversion element according to the embodiment of the present disclosure is included as the photoelectric conversion element.

  In the photoelectric conversion element according to one embodiment of the present disclosure and the imaging device according to one embodiment, an electronic block layer including the organic semiconductor material represented by the general formula (1) is provided between the photoelectric conversion layer and the anode. I made it. This makes it possible to maintain high device characteristics even after a heating process in the semiconductor manufacturing process.

  According to the photoelectric conversion element of one embodiment of the present disclosure and the imaging device of one embodiment, an electron block layer including the organic semiconductor material represented by the general formula (1) is provided between the photoelectric conversion layer and the anode. Thus, high device characteristics are maintained even after a heating process in the semiconductor manufacturing process. That is, it is possible to provide a photoelectric conversion element and an imaging device that are excellent in heat resistance.

  Note that the effects described here are not necessarily limited, and may be any effects described in the present disclosure.

It is a cross-sectional schematic diagram showing the structure of the photoelectric conversion element which concerns on 1st Embodiment of this indication. It is a plane schematic diagram showing the structure of the unit pixel of the photoelectric conversion element shown in FIG. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the photoelectric conversion element shown in FIG. FIG. 4 is a schematic cross-sectional view illustrating a process following FIG. 3. It is sectional drawing showing an example of schematic structure of the photoelectric conversion element which concerns on 2nd Embodiment of this indication. FIG. 6 is an equivalent circuit diagram of the photoelectric conversion element shown in FIG. 5. It is a schematic diagram showing arrangement | positioning of the transistor which comprises the lower electrode and control part of the photoelectric conversion element shown in FIG. It is sectional drawing for demonstrating the manufacturing method of the photoelectric conversion element shown in FIG. FIG. 9 is a cross-sectional diagram illustrating a process following the process in FIG. 8. FIG. 10 is a cross-sectional diagram illustrating a process following the process in FIG. 9. FIG. 11 is a cross-sectional diagram illustrating a process following the process in FIG. 10. FIG. 12 is a cross-sectional diagram illustrating a process following the process in FIG. 11. FIG. 13 is a cross-sectional diagram illustrating a process following the process in FIG. 12. FIG. 6 is a timing chart illustrating an operation example of the photoelectric conversion element illustrated in FIG. 5. It is a block diagram showing the whole structure of the imaging device provided with the photoelectric conversion element shown in FIG. It is a functional block diagram showing an example of the electronic device (camera) using the imaging device shown in FIG. It is a block diagram which shows an example of a schematic structure of an in-vivo information acquisition system. 1 is a diagram illustrating an example of a schematic configuration of an endoscopic surgery system to which the present technology can be applied. It is a block diagram which shows an example of a function structure of the camera head shown in FIG. 18, and CCU. It is a block diagram which shows the schematic structural example of a vehicle control system. It is explanatory drawing which shows an example of the installation position of an imaging part.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. The following description is one specific example of the present disclosure, and the present disclosure is not limited to the following aspects. In addition, the present disclosure is not limited to the arrangement, dimensions, dimensional ratio, and the like of each component illustrated in each drawing. The order of explanation is as follows.
1. First embodiment (an example of a photoelectric conversion element having an electron block layer containing a benzodifuran derivative between an anode and a photoelectric conversion layer)
1-1. Configuration of photoelectric conversion element 1-2. Manufacturing method of photoelectric conversion element 1-3. Action / Effect Second embodiment (example in which the lower electrode is composed of a plurality of electrodes)
2-1. Configuration of photoelectric conversion element 2-2. Manufacturing method of photoelectric conversion element 2-3. Action and effect Application example 4. Example

<1. First Embodiment>
FIG. 1 illustrates a cross-sectional configuration of the photoelectric conversion element (photoelectric conversion element 10 </ b> A) according to the first embodiment of the present disclosure. The photoelectric conversion element 10A is, for example, one pixel (unit) in an imaging device (imaging device 1) such as a backside illumination type (backside light receiving type) CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor. The pixel P) is used as an imaging device (see FIG. 15). In the photoelectric conversion element 10A, 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 stacked in the vertical direction. This is a so-called longitudinal spectroscopic type. The organic photoelectric conversion unit 11G of the present embodiment has a configuration in which a lower electrode 15, an electron block layer 16, a photoelectric conversion layer 17, and an upper electrode 18 are stacked in this order. The electronic block layer 16 is formed including an organic semiconductor material represented by the general formula (1) described later.

(1-1. Configuration of photoelectric conversion element)
In the photoelectric conversion element 10A, for each unit pixel P, one organic photoelectric conversion unit 11G and two inorganic photoelectric conversion units 11B and 11R are stacked in the vertical direction. The organic photoelectric conversion unit 11G is provided on the back surface (first surface 11S1) side of the semiconductor substrate 11. The inorganic photoelectric conversion units 11 </ b> B and 11 </ b> R are embedded in the semiconductor substrate 11 and are stacked in the thickness direction of the semiconductor substrate 11. The organic photoelectric conversion unit 11G includes a p-type semiconductor and an n-type semiconductor, and includes a photoelectric conversion layer 17 having a bulk heterojunction structure in the layer. The bulk heterojunction structure is a p / n junction surface formed by mixing a p-type semiconductor and an n-type semiconductor.

  The organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R selectively detect light in different wavelength bands and perform photoelectric conversion. Specifically, the organic photoelectric conversion unit 11G acquires a green (G) color signal. In the inorganic photoelectric conversion units 11B and 11R, blue (B) and red (R) color signals are acquired based on the difference in absorption coefficient. Thereby, in the photoelectric conversion element 10A, it is possible to acquire a plurality of types of color signals in one pixel without using a color filter.

  Note that in this embodiment, a case where a hole is read as a signal charge out of a pair of electrons and holes generated by photoelectric conversion (a case where a p-type semiconductor region is a photoelectric conversion layer) will be described. In the figure, “+ (plus)” attached to “p” and “n” indicates that the p-type or n-type impurity concentration is high, and “++” indicates that the p-type or n-type impurity concentration is high. It is higher than “+”.

  The semiconductor substrate 11 is composed of, for example, an n-type silicon (Si) substrate, and has a p-well 61 in a predetermined region. On the second surface (surface of the semiconductor substrate 11) 11S2 of the p-well 61, for example, various floating diffusions (floating diffusion layers) FD (for example, FD1, FD2, FD3) and various transistors Tr (for example, vertical transistors (for example, vertical transistors) Transfer transistor) Tr1, transfer transistor Tr2, amplifier transistor (modulation element) AMP and reset transistor RST), and multilayer wiring 70 are provided. The multilayer wiring 70 has a configuration in which, for example, wiring layers 71, 72, and 73 are stacked in an insulating layer 74. A peripheral circuit (not shown) made up of a logic circuit or the like is provided in the peripheral portion of the semiconductor substrate 11.

  In FIG. 1, the first surface 11S1 side of the semiconductor substrate 11 is represented as a light incident surface S1, and the second surface 11S2 side is represented as a wiring layer side S2.

  The inorganic photoelectric conversion units 11 </ b> B and 11 </ b> R are configured by PIN (Positive Intrinsic Negative) type photodiodes, for example, and each have a pn junction in a predetermined region of the semiconductor substrate 11. The inorganic photoelectric conversion units 11B and 11R can split light in the vertical direction by utilizing the fact that the wavelength band absorbed by the silicon substrate differs depending on the incident depth of light.

  The inorganic photoelectric conversion unit 11B selectively detects blue light and accumulates signal charges corresponding to blue, and is installed at a depth at which blue light can be efficiently photoelectrically converted. The inorganic photoelectric conversion unit 11R selectively detects red light and accumulates signal charges corresponding to red, and is installed at a depth at which red light can be efficiently photoelectrically converted. Note that blue (B) is a color corresponding to a wavelength band of 450 nm to 495 nm, for example, and red (R) is a color corresponding to a wavelength band of 620 nm to 750 nm, for example. Each of the inorganic photoelectric conversion units 11B and 11R only needs to be able to detect light in a part or all of the wavelength bands.

  Specifically, as shown in FIG. 1, each of the inorganic photoelectric conversion unit 11B and the inorganic photoelectric conversion unit 11R includes, for example, a p + region that becomes a hole accumulation layer and an n region that becomes an electron accumulation layer. (Having a p-n-p stacked structure). The n region of the inorganic photoelectric conversion unit 11B is connected to the vertical transistor Tr1. The p + region of the inorganic photoelectric conversion unit 11B is bent along the vertical transistor Tr1 and connected to the p + region of the inorganic photoelectric conversion unit 11R.

  On the second surface 11S2 of the semiconductor substrate 11, as described above, for example, floating diffusions (floating diffusion layers) FD1, FD2, FD3, vertical transistors (transfer transistors) Tr1, transfer transistors Tr2, and amplifier transistors ( A modulation element AMP and a reset transistor RST are provided.

  The vertical transistor Tr1 is a transfer transistor that transfers signal charges (here, holes) corresponding to blue color generated and accumulated in the inorganic photoelectric conversion unit 11B to the floating diffusion FD1. Since the inorganic photoelectric conversion unit 11B is formed at a deep position from the second surface 11S2 of the semiconductor substrate 11, it is preferable that the transfer transistor of the inorganic photoelectric conversion unit 11B is configured by a vertical transistor Tr1.

  The transfer transistor Tr2 transfers the signal charge (here, holes) corresponding to the red color generated and accumulated in the inorganic photoelectric conversion unit 11R to the floating diffusion FD2, and is configured by, for example, a MOS transistor.

  The amplifier transistor AMP is a modulation element that modulates the amount of charge generated in the organic photoelectric conversion unit 11G into a voltage, and is configured by, for example, a MOS transistor.

  The reset transistor RST resets the charge transferred from the organic photoelectric conversion unit 11G to the floating diffusion FD3, and is configured by, for example, a MOS transistor.

  The lower first contact 75, the lower second contact 76, and the upper contact 13B are made of, for example, a doped silicon material such as PDAS (Phosphorus Doped Amorphous Silicon), or aluminum (Al), tungsten (W), titanium (Ti). , Cobalt (Co), hafnium (Hf), and tantalum (Ta).

  An organic photoelectric conversion unit 11 </ b> G is provided on the first surface 11 </ b> S <b> 1 side of the semiconductor substrate 11. The organic photoelectric conversion unit 11G has, for example, a configuration in which a lower electrode 15, an electron block layer 16, a photoelectric conversion layer 17, and an upper electrode 18 are stacked in this order from the first surface S1 side of the semiconductor substrate 11. . For example, the lower electrode 15 is separately formed for each unit pixel P. The electronic block layer 16, the photoelectric conversion layer 17, and the upper electrode 18 are provided as a continuous layer common to a plurality of unit pixels P (for example, the pixel portion 1a of the imaging device 1 illustrated in FIG. 5). The organic photoelectric conversion unit 11G absorbs green light corresponding to a part or all of a selective wavelength band (for example, 450 nm or more and 650 nm or less) and generates an electron-hole pair. It is.

  Between the first surface 11S1 of the semiconductor substrate 11 and the lower electrode 15, for example, interlayer insulating layers 12 and 14 are stacked in this order from the semiconductor substrate 11 side. The interlayer insulating layer has, for example, a configuration in which a layer (fixed charge layer) 12A having a fixed charge and a dielectric layer 12B having insulating properties are stacked. A protective layer 19 is provided on the upper electrode 18. Above the protective layer 19, an on-chip lens layer 50 that constitutes the on-chip lens 50 </ b> L and also serves as a planarization layer is disposed.

  A through electrode 63 is provided between the first surface 11S1 and the second surface 11S2 of the semiconductor substrate 11. The organic photoelectric conversion unit 11G is connected to the gate Gamp of the amplifier transistor AMP and the floating diffusion FD3 through the through electrode 63. Thereby, in the photoelectric conversion element 10A, the charge generated in the organic photoelectric conversion unit 11G on the first surface 11S1 side of the semiconductor substrate 11 is favorably transferred to the second surface 11S2 side of the semiconductor substrate 11 through the through electrode 63. It is possible to enhance the characteristics.

  The through electrode 63 is provided, for example, for each organic photoelectric conversion unit 11G of the photoelectric conversion element 10A. The through electrode 63 functions as a connector between the organic photoelectric conversion unit 11G, the gate Gamp of the amplifier transistor AMP, and the floating diffusion FD3, and serves as a transmission path for charges generated in the organic photoelectric conversion unit 11G.

  For example, the lower end of the through electrode 63 is connected to the connection portion 71A in the wiring layer 71, and the connection portion 71A and the gate Gamp of the amplifier transistor AMP are connected via the lower first contact 75. The connecting portion 71A and the floating diffusion FD3 are connected to the lower electrode 15 via the lower second contact 76. In addition, in FIG. 1, although the penetration electrode 63 was shown as a cylindrical shape, it is not restricted to this, For example, it is good also as a taper shape.

  Next to the floating diffusion FD3, as shown in FIG. 1, a reset gate Grst of the reset transistor RST is preferably arranged. As a result, the charge accumulated in the floating diffusion FD3 can be reset by the reset transistor RST.

  In the photoelectric conversion element 10 </ b> A according to the present embodiment, light incident on the organic photoelectric conversion unit 11 </ b> G from the upper electrode 18 side is absorbed by the photoelectric conversion layer 17. The excitons generated thereby move to the interface between the electron donor and the electron acceptor constituting the photoelectric conversion layer 17 and dissociate into exciton separation, that is, electrons and holes. The charges (electrons and holes) generated here are caused by diffusion due to the carrier concentration difference or an internal electric field due to the work function difference between the anode (here, the lower electrode 15) and the cathode (here, the upper electrode 18). Are carried to different electrodes and detected as photocurrents. Further, by applying a potential between the lower electrode 15 and the upper electrode 18, the transport direction of electrons and holes can be controlled.

  Hereinafter, the configuration and materials of each part will be described.

  The organic photoelectric conversion unit 11G is an organic photoelectric conversion element that absorbs light corresponding to a part or all of a selective wavelength band (for example, 450 nm or more and 750 nm or less) and generates electron-hole pairs. is there. As described above, the organic photoelectric conversion unit 11G includes, for example, the lower electrode 15 and the upper electrode 18, which are disposed to face each other, the photoelectric conversion layer 17 provided between the lower electrode 15 and the upper electrode 18, and the lower electrode 15 And an electronic block layer 16 provided between the photoelectric conversion layer 17 and the photoelectric conversion layer 17.

The lower electrode 15 is provided in a region that faces the light receiving surfaces of the inorganic photoelectric conversion units 11B and 11R formed in the semiconductor substrate 11 and covers these light receiving surfaces. The lower electrode 15 is made of a light-transmitting metal oxide. Examples of the metal atoms constituting the metal oxide used as the material of the lower electrode 15 include tin (Sn), zinc (Zn), indium (In), silicon (Si), zirconium (Zr), and aluminum (Al). Gallium (Ga), tungsten (W), chromium (Cr), cobalt (Co), nickel (Ni), tantalum (Ta), niobium (Nb) and molybdenum (Mo). Examples of the metal oxide containing one or more metal atoms include ITO (indium tin oxide). However, as a constituent material of the lower electrode 15, in addition to this ITO, 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. Examples of the zinc oxide-based material 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). In addition, CuI, InSbO ₄ , ZnMgO, CuInO ₂ , MgIn ₂ O ₄ , CdO, ZnSnO _3, or the like may be used.

  The electron block layer 16 is used to selectively transport holes to the lower electrode 15 out of charges generated in the photoelectric conversion layer 17 described later, and to inhibit the movement of electrons to the lower electrode 15 side. . The electron blocking layer 16 desirably has the following characteristics. First, it is desirable that the electron blocking layer 16 has a high hole transport property. Secondly, it is desirable that the electron blocking layer 16 is made of a material having an ionization potential comparable to the ionization potential of the hole transporting material constituting the photoelectric conversion layer 17. As described above, holes generated by the charge separation process in the photoelectric conversion layer 17 can be efficiently and promptly transported to the lower electrode 15. Third, it is desirable that the electron block layer 16 has an electron affinity of, for example, 1 eV or more lower than the work function of the adjacent anode (here, the lower electrode 15). Thereby, the electron block layer 16 becomes a barrier layer against electron injection from the anode, and generation of dark current is reduced. Fourthly, it is desirable that the electron block layer 16 has high layer surface smoothness and is uniform with few defects. Fifth, the electron blocking layer 16 has high heat resistance, light resistance, and other stability (for example, in a high humidity environment, in the presence of oxygen, in a vacuum or nitrogen, or a combination thereof). It is desirable to have

  The electron blocking layer 16 forms a stable interface with the upper and lower adjacent layers (specifically, the lower electrode 15 and the photoelectric conversion layer 17), and does not diffuse to the adjacent layers even after the heat treatment. It is desirable to adhere to the layer to be separated with an interface. Further, it is desirable that the layer formation process by vapor deposition or coating method is easy, the process yield is high, and the material is low in cost.

  The electron blocking layer 16 of the present embodiment is configured using an organic semiconductor material represented by the following general formula (1) as a material that satisfies the above conditions.

（Ｒ１，Ｒ２，Ｒ３，Ｒ４は、各々独立して、水素原子または炭素数４以上４０以下のアリール基、ヘテロアリール基、カルバゾール基、ジフェニルアミノ基あるいはそれらの誘導体であり、Ｒ１，Ｒ２，Ｒ３，Ｒ４のうちの少なくとも１つは、炭素数１２以上４０以下のカルバゾール基またはジフェニルアミノ基あるいはそれらの誘導体である。）

(R1, R2, R3 and R4 are each independently a hydrogen atom or an aryl group, heteroaryl group, carbazole group, diphenylamino group or derivatives thereof having 4 to 40 carbon atoms, and R1, R2, R3 , R4 is a carbazole group having 12 to 40 carbon atoms, a diphenylamino group, or a derivative thereof.)

  Specific examples of the organic semiconductor material represented by the general formula (1) include benzodifuran derivatives represented by the following formulas (1-1) to (1-9).

The photoelectric conversion layer 17 converts light energy into electric energy, and includes, for example, two or more organic semiconductor materials. Specifically, the photoelectric conversion layer 17 includes, for example, a color material having an absorption coefficient of 50000 cm ⁻¹ or more at a selective wavelength (for example, green light of 400 nm or more and 750 nm or less) in the visible light region. Has been. Thereby, the organic photoelectric conversion unit 11G can selectively photoelectrically convert green light of 400 nm or more and 750 nm or less, for example. Examples of such an organic semiconductor material include subphthalocyanine represented by the following general formula (2) or a derivative thereof.

（Ｒ５〜Ｒ１６は、各々独立して、水素原子、ハロゲン原子、直鎖，分岐，または環状アルキル基、チオアルキル基、チオアリール基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、ヒドロキシ基、アルコキシ基、アシルアミノ基、アシルオキシ基、フェニル基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、アシル基、スルホニル基、シアノ基およびニトロ基からなる群から選択され、且つ、隣接した任意のＲ５〜Ｒ１６は縮合脂肪族環または縮合芳香環の一部であってもよい。前記縮合脂肪族環または縮合芳香環は、炭素以外の1または複数の原子を含んでいてもよい。Ｍはホウ素または２価あるいは３価の金属である。Ｘは、ハロゲン、ヒドロキシ基、チオール基、イミド基、置換もしくは未置換のアルコキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基からなる群より選択されるいずれかの置換基である。）

(R5 to R16 are each independently a hydrogen atom, a halogen atom, a linear, branched, or cyclic alkyl group, a thioalkyl group, a thioaryl group, an arylsulfonyl group, an alkylsulfonyl group, an amino group, an alkylamino group, an arylamino group. Selected from the group consisting of a group, hydroxy group, alkoxy group, acylamino group, acyloxy group, phenyl group, carboxy group, carboxamide group, carboalkoxy group, acyl group, sulfonyl group, cyano group and nitro group, and adjacent R5 to R16 may be a part of a condensed aliphatic ring or a condensed aromatic ring, and the condensed aliphatic ring or the condensed aromatic ring may contain one or more atoms other than carbon. M is boron or a divalent or trivalent metal, X is halogen, hydroxy group, thiol group, imi Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group Any substituent.)

  In addition, the photoelectric conversion layer 17 is preferably configured to include one or more organic semiconductor materials having transparency to visible light and having hole transportability or electron transportability. Examples of the organic semiconductor material having a hole transporting property include compounds represented by the following formulas (5-1) to (5-11).

Examples of the organic semiconductor material having an electron transporting property include C ₆₀ fullerene represented by the following general formula (3) or a derivative thereof, or C ₇₀ fullerene represented by the following general formula (4) or a derivative thereof. It is done. Here, fullerene is treated as an organic semiconductor. By using at least one fullerene C ₆₀ and fullerene C ₇₀ or a derivative thereof, photoelectric conversion efficiency can be improved and dark current can be reduced.

（Ｒ１７，Ｒ１８は、水素原子、ハロゲン原子、直鎖，分岐または環状のアルキル基、フェニル基、直鎖または縮環した芳香族化合物を有する基、ハロゲン化物を有する基、パーシャルフルオロアルキル基、パーフルオロアルキル基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、アリールスルファニル基、アルキルスルファニル基、アリールスルホニル基、アルキルスルホニル基、アリールスルフィド基、アルキルスルフィド基、アミノ基、アルキルアミノ基、アリールアミノ基、ヒドロキシ基、アルコキシ基、アシルアミノ基、アシルオキシ基、カルボニル基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、アシル基、スルホニル基、シアノ基、ニトロ基、カルコゲン化物を有する基、ホスフィン基、ホスホン基あるいはそれらの誘導体である。ｎ，ｍは２以上の整数である。）

(R17 and R18 are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a phenyl group, a group having a linear or condensed aromatic compound, a group having a halide, a partial fluoroalkyl group, a perfluoroalkyl group, Fluoroalkyl group, silylalkyl group, silylalkoxy group, arylsilyl group, arylsulfanyl group, alkylsulfanyl group, arylsulfonyl group, alkylsulfonyl group, arylsulfide group, alkylsulfide group, amino group, alkylamino group, arylamino group Hydroxy group, alkoxy group, acylamino group, acyloxy group, carbonyl group, carboxy group, carboxamide group, carboalkoxy group, acyl group, sulfonyl group, cyano group, nitro group, chalcogenated group, phosphine group, phospho group Is a group, or a derivative thereof .n, m is an integer of 2 or more.)

  The photoelectric conversion layer 17 has a junction surface (p / n junction surface) between a p-type semiconductor and an n-type semiconductor in the layer. A p-type semiconductor functions relatively as an electron donor (donor), and an n-type semiconductor functions relatively as an electron acceptor. The photoelectric conversion layer 17 provides a field where excitons generated when light is absorbed are separated into electrons and holes, and at the interface (p / n junction surface) between the electron donor and the electron acceptor. , Excitons separate into electrons and holes. The thickness of the photoelectric conversion layer 17 is, for example, 50 nm to 500 nm.

  The upper electrode 18 is formed of a light-transmitting conductive film, like the lower electrode 15. In the photoelectric conversion element 10A, the upper electrode 18 may be separated for each unit pixel P, or may be formed as a common electrode for each unit pixel P. The thickness of the upper electrode 18 is, for example, 10 nm to 200 nm.

  Note that another layer may be provided between the photoelectric conversion layer 17 and the lower electrode 15 and between the photoelectric conversion layer 17 and the upper electrode 18. Specifically, for example, an undercoat layer, a hole transport layer, an electron block layer 16, a photoelectric conversion layer 17, a hole block layer, a buffer layer, an electron transport layer, a work function adjustment layer, and the like in order from the lower electrode 15 side. May be laminated.

The fixed charge layer 12A may be a film having a positive fixed charge or a film having a negative fixed charge. As a material of the film having a negative fixed charge, hafnium oxide (HfO ₂ ), aluminum oxide (Al ₂ O ₃ ), zirconium oxide (ZrO ₂ ), tantalum oxide (Ta ₂ O ₅ ), titanium oxide (TiO ₂ ) Etc. In addition to the above materials, lanthanum oxide, praseodymium oxide, cerium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holeium oxide, thulium oxide, ytterbium oxide, lutetium oxide Alternatively, an yttrium oxide, an aluminum nitride film, a hafnium oxynitride film, an aluminum oxynitride film, or the like may be used.

  The fixed charge layer 12A may have a configuration in which two or more kinds of films are stacked. Thereby, for example, in the case of a film having a negative fixed charge, the function as the hole accumulation layer can be further enhanced.

  The material of the dielectric layer 12B is not particularly limited. For example, the dielectric layer 12B is formed of a silicon oxide film, a TEOS film, a silicon nitride film, a silicon oxynitride film, or the like.

  The interlayer insulating layer 14 is, for example, a single layer film made of one of silicon oxide (SiO), silicon nitride (SiN), silicon oxynitride (SiON), etc., or a laminate made of two or more of these. It is comprised by the film | membrane.

  The protective layer 19 is made of a light-transmitting material. For example, the protective layer 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 comprised by. The thickness of the protective layer 19 is, for example, 100 nm to 30000 nm.

  An on-chip lens layer 50 is formed on the protective layer 19 so as to cover the entire surface. On the surface of the on-chip lens layer 50, a plurality of on-chip lenses 50L (microlenses) are provided. The on-chip lens 50L 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. In the present embodiment, since the multilayer wiring 70 is formed on the second surface 11S2 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. It is possible to reduce the variation in sensitivity between colors depending on the F value of the on-chip lens 50L.

  FIG. 2 shows a configuration example of a photoelectric conversion element 10A in which a plurality of photoelectric conversion units to which the technology according to the present disclosure can be applied (for example, the inorganic photoelectric conversion units 11B and 11R and the organic photoelectric conversion unit 11G) are stacked. It is a top view. That is, FIG. 2 illustrates an example of a planar configuration of the unit pixel P that configures the pixel unit 1a illustrated in FIG.

  The unit pixel P includes a red photoelectric conversion unit (inorganic photoelectric conversion unit 11 </ b> R in FIG. 1) and a blue photoelectric conversion unit (see FIG. 1) that photoelectrically convert light of each wavelength of R (Red), G (Green), and B (Blue). Inorganic photoelectric conversion unit 11B in FIG. 1 and green photoelectric conversion unit (organic photoelectric conversion unit 11G in FIG. 1) (both not shown in FIG. 2) are, for example, on the light receiving surface (light incident surface S1 in FIG. 1) side. To a photoelectric conversion region 1100 stacked in three layers in the order of a green photoelectric conversion unit, a blue photoelectric conversion unit, and a red photoelectric conversion unit. Further, the unit pixel P has a Tr group 1110, a Tr group 1120, and a Tr as charge reading units that read out charges corresponding to light of RGB wavelengths from the red photoelectric conversion unit, the green photoelectric conversion unit, and the blue photoelectric conversion unit. It has a group 1130. In the imaging device 1, in one unit pixel P, vertical spectroscopy, that is, each layer of RGB in each layer as a red photoelectric conversion unit, a green photoelectric conversion unit, and a blue photoelectric conversion unit stacked in the photoelectric conversion region 1100. Spectroscopy of light is performed.

  The Tr group 1110, the Tr group 1120, and the Tr group 1130 are formed around the photoelectric conversion region 1100. The Tr group 1110 outputs a signal charge corresponding to the R light generated and accumulated by the red photoelectric conversion unit as a pixel signal. The Tr group 1110 includes a transfer Tr (MOS FET) 1111, a reset Tr 1112, an amplification Tr 1113, and a selection Tr 1114. The Tr group 1120 outputs a signal charge corresponding to the B light generated and accumulated by the blue photoelectric conversion unit as a pixel signal. The Tr group 1120 includes a transfer Tr 1121, a reset Tr 1122, an amplification Tr 1123, and a selection Tr 1124. The Tr group 1130 outputs a signal charge corresponding to the G light generated and accumulated by the green photoelectric conversion unit as a pixel signal. The Tr group 1130 includes a transfer Tr 1131, a reset Tr 1132, an amplification Tr 1133, and a selection Tr 1134.

  The transfer Tr 1111 includes a gate G, source / drain regions S / D, and FD (floating diffusion) 1115 (source / drain regions). The transfer Tr 1121 includes a gate G, a source / drain region S / D, and an FD 1125. The transfer Tr 1131 is configured by a gate G, a green photoelectric conversion unit (source / drain region S / D connected to) of the photoelectric conversion region 1100, and an FD 1135. The source / drain region of the transfer Tr 1111 is connected to the red photoelectric conversion unit in the photoelectric conversion region 1100, and the source / drain region S / D of the transfer Tr 1121 is connected to the blue photoelectric conversion unit in the photoelectric conversion region 1100. It is connected.

  Each of the reset Trs 1112, 1132, and 1122, the amplification Trs 1113, 1133, and 1123, and the selection Trs 1114, 1134, and 1124 includes a gate G and a pair of source / drain regions S / D arranged so as to sandwich the gate G. It consists of

  The FDs 1115, 1135, and 1125 are connected to the source / drain regions S / D that are the sources of the reset Trs 1112, 1132, and 1122, respectively, and are connected to the gates G of the amplification Trs 1113, 1133, and 1123, respectively. A power source Vdd is connected to the common source / drain region S / D in each of the reset Tr 1112 and the amplification Tr 1113, the reset Tr 1132 and the amplification Tr 1133, and the reset Tr 1122 and the amplification Tr 1123. A VSL (vertical signal line) is connected to the source / drain regions S / D which are the sources of the selection Trs 1114, 1134 and 1124.

  The technology according to the present disclosure can be applied to the photoelectric conversion element as described above.

(1-2. Method for producing photoelectric conversion element)
For example, the photoelectric conversion element 10A of the present embodiment can be manufactured as follows.

  3 and 4 show the manufacturing method of the photoelectric conversion element 10A in the order of steps. First, as shown in FIG. 3, for example, a p-well 61 is formed as a first conductivity type well in the semiconductor substrate 11, and a second conductivity type (for example, n-type) inorganic is formed in the p well 61. Photoelectric converters 11B and 11R are formed. A p + region is formed in the vicinity of the first surface 11S1 of the semiconductor substrate 11.

  As shown in FIG. 3, after forming n + regions to be the floating diffusions FD1 to FD3 on the second surface 11S2 of the semiconductor substrate 11, the gate insulating layer 62, the vertical transistor Tr1, the transfer transistor Tr2, and the amplifier A gate wiring layer 64 including the gates of the transistor AMP and the reset transistor RST is formed. Thereby, the vertical transistor Tr1, the transfer transistor Tr2, the amplifier transistor AMP, and the reset transistor RST are formed. Further, the multilayer wiring 70 including the lower first contact 75, the lower second contact 76, the wiring layers 71 to 73 including the connection portion 71 </ b> A, and the insulating layer 74 is formed on the second surface 11 </ b> S <b> 2 of the semiconductor substrate 11.

  As the base of the semiconductor substrate 11, for example, an SOI (Silicon on Insulator) substrate in which a semiconductor substrate 11, a buried oxide film (not shown), and a holding substrate (not shown) are stacked is used. Although not shown in FIG. 3, the buried oxide film and the holding substrate are bonded to the first surface 11S1 of the semiconductor substrate 11. After ion implantation, annealing is performed.

  Next, a support substrate (not shown) or another semiconductor substrate is joined to the second surface 11S2 side (multilayer wiring 70 side) of the semiconductor substrate 11 and turned upside down. Subsequently, the semiconductor substrate 11 is separated from the buried oxide film of the SOI substrate and the holding substrate, and the first surface 11S1 of the semiconductor substrate 11 is exposed. The above steps can be performed by techniques used in a normal CMOS process such as ion implantation and CVD (Chemical Vapor Deposition).

  Next, as shown in FIG. 4, the semiconductor substrate 11 is processed from the first surface 11S1 side by dry etching, for example, to form an annular opening 63H. As shown in FIG. 4, the depth of the opening 63H penetrates from the first surface 11S1 to the second surface 11S2 of the semiconductor substrate 11 and reaches, for example, the connection portion 71A.

  Subsequently, as illustrated in FIG. 4, for example, a negative fixed charge layer 12 </ b> A is formed on the first surface 11 </ b> S <b> 1 of the semiconductor substrate 11 and the side surface of the opening 63 </ b> H. Two or more types of films may be stacked as the negative fixed charge layer 12A. Thereby, the function as a hole accumulation layer can be further enhanced. After forming the negative fixed charge layer 12A, the dielectric layer 12B is formed.

  Next, a through electrode 63 is formed by embedding a conductor in the opening 63H. Examples of the conductor include doped silicon materials such as PDAS (Phosphorus Doped Amorphous Silicon), aluminum (Al), tungsten (W), titanium (Ti), cobalt (Co), hafnium (Hf), and tantalum. A metal material such as (Ta) can be used.

  Subsequently, after the pad portion 13A is formed on the through electrode 63, the lower electrode 15 and the through electrode 63 (specifically, the pad portion 13A on the through electrode 63) are formed on the dielectric layer 12B and the pad portion 13A. An interlayer insulating layer 14 is formed in which an upper contact 13B and a pad portion 13C are electrically connected to the pad portion 13A.

  Next, the lower electrode 15, the electron blocking layer 16, the photoelectric conversion layer 17, the upper electrode 18, and the protective layer 19 are formed in this order on the interlayer insulating layer 14. For example, the electron block layer 16 is formed by depositing the benzodifuran derivative represented by the general formula (1) using, for example, a vacuum deposition method. For example, the photoelectric conversion layer 17 is formed by depositing the above-described three kinds of organic semiconductor materials using, for example, a vacuum deposition method. Finally, an on-chip lens layer 50 having a plurality of on-chip lenses 50L is disposed on the surface. Thus, the photoelectric conversion element 10A shown in FIG. 1 is completed.

  In addition, as mentioned above, when forming another organic layer (for example, electron blocking layer etc.) in the upper layer or lower layer of the photoelectric conversion layer 17, it forms continuously in a vacuum process (in a vacuum consistent process). It is desirable. Further, the method for forming the photoelectric conversion layer 17 is not necessarily limited to the method using the vacuum vapor deposition method, and other methods such as a spin coating technique and a printing technique may be used.

  In the photoelectric conversion element 10A, when light is incident on the organic photoelectric conversion unit 11G via the on-chip lens 50L, the light passes through the organic photoelectric conversion unit 11G and the inorganic photoelectric conversion units 11B and 11R in this order, and the passing process. The photoelectric conversion is performed for each of the green, blue, and red color lights. Hereinafter, the signal acquisition operation for each color will be described.

(Acquisition of green signal by organic photoelectric conversion unit 11G)
Of the light incident on the photoelectric conversion element 10A, first, green light is selectively detected (absorbed) in the organic photoelectric conversion unit 11G and subjected to photoelectric conversion.

  The organic photoelectric conversion unit 11G is connected to the gate Gamp of the amplifier transistor AMP and the floating diffusion FD3 through the through electrode 63. Therefore, holes in the electron-hole pairs generated in the organic photoelectric conversion unit 11G are taken out from the lower electrode 15 side, transferred to the second surface 11S2 side of the semiconductor substrate 11 through the through electrode 63, and floated. Accumulated in the diffusion FD3. At the same time, the charge amount generated in the organic photoelectric conversion unit 11G is modulated into a voltage by the amplifier transistor AMP.

  Further, a reset gate Grst of the reset transistor RST is arranged next to the floating diffusion FD3. Thereby, the electric charge accumulated in the floating diffusion FD3 is reset by the reset transistor RST.

  Here, since the organic photoelectric conversion unit 11G is connected not only to the amplifier transistor AMP but also to the floating diffusion FD3 via the through electrode 63, the charge accumulated in the floating diffusion FD3 is easily reset by the reset transistor RST. It becomes possible to do.

  On the other hand, when the through electrode 63 and the floating diffusion FD3 are not connected, it becomes difficult to reset the charge accumulated in the floating diffusion FD3, and a large voltage is applied to pull out the charge to the upper electrode 18 side. become. For this reason, the photoelectric conversion layer 17 may be damaged. In addition, a structure that can be reset in a short time causes an increase in dark noise, which is a trade-off, so that this structure is difficult.

(Acquisition of blue and red signals by the inorganic photoelectric conversion units 11B and 11R)
Subsequently, among the light transmitted through the organic photoelectric conversion unit 11G, blue light is absorbed and photoelectrically converted in order by the inorganic photoelectric conversion unit 11B and red light by the inorganic photoelectric conversion unit 11R. In the inorganic photoelectric conversion unit 11B, electrons corresponding to the incident blue light are accumulated in the n region of the inorganic photoelectric conversion unit 11B, and the accumulated electrons are transferred to the floating diffusion FD1 by the vertical transistor Tr1. Similarly, in the inorganic photoelectric conversion unit 11R, electrons corresponding to the incident red light are accumulated in the n region of the inorganic photoelectric conversion unit 11R, and the accumulated electrons are transferred to the floating diffusion FD2 by the transfer transistor Tr2.

(1-3. Action and effect)
As described above, in photoelectric conversion elements using organic semiconductor materials, it is a problem to maintain excellent element characteristics such as low dark current, high quantum efficiency, and high response speed even after a heating manufacturing process in the semiconductor manufacturing process. Various photoelectric conversion elements have been proposed.

  On the other hand, in the present embodiment, the electron blocking layer 16 containing the benzodifuran derivative represented by the above general (1) is provided between the anode (lower electrode 15) and the photoelectric conversion layer 17. . The electron block layer 16 containing the benzodifuran derivative represented by the general formula (1) has the first to fifth features described above.

  That is, the electron blocking layer 16 of the present embodiment has a high hole transport property and an ionization potential that is comparable to the ionization potential of the hole transport material that constitutes the photoelectric conversion layer 17. Thereby, the photoelectric conversion element 10A of the present embodiment can efficiently and quickly transport the success generated by the charge separation process in the photoelectric conversion layer 17 to the lower electrode 15.

  Furthermore, the electron blocking layer 16 of the present embodiment can be formed as an amorphous layer that constitutes a homogeneous layer having high smoothness on the layer surface and few defects. The benzodifuran derivative has high heat resistance, light resistance, and high stability in other environments. Therefore, the electron blocking layer 16 of the present embodiment forms a stable interface with the lower electrode 15 and the photoelectric conversion layer 17, and does not diffuse to these adjacent layers even if heat treatment is performed, and the adhesion is separated from the interface. Sex is maintained. As a result, the photoelectric conversion element 10A of the present embodiment has improved durability against a heating process in the semiconductor manufacturing process, and can maintain high element characteristics.

  As described above, in the photoelectric conversion element 10A of the present embodiment, the electron block layer 16 including the benzodifuran derivative represented by the general formula (1) is provided between the anode (lower electrode 15) and the photoelectric conversion layer 17. I made it. Thereby, low dark current, high quantum efficiency, and high response speed are maintained even after a heating process in the semiconductor manufacturing process. That is, it is possible to provide the photoelectric conversion element 10A having high element characteristics and excellent heat resistance, and the imaging device 1 including the photoelectric conversion element 10A.

  Next, a second embodiment will be described. In the following, the same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof is omitted as appropriate.

<2. Second Embodiment>
FIG. 5 illustrates a cross-sectional configuration of the photoelectric conversion element (photoelectric conversion element 10 </ b> B) according to the second embodiment of the present disclosure. 6 is an equivalent circuit diagram of the photoelectric conversion element 10B shown in FIG. FIG. 7 schematically shows the arrangement of the transistors constituting the lower electrode 21 and the control unit of the photoelectric conversion element 10 </ b> B shown in FIG. 5. Similarly to the photoelectric conversion element 10A, the photoelectric conversion element 10B is, for example, one pixel (unit pixel P) in an imaging device (imaging device 1) such as a backside illumination type (backside light receiving type) CCD image sensor or CMOS image sensor. (See FIG. 15). In the photoelectric conversion element 10A, one organic photoelectric conversion unit 20 that selectively detects light in different wavelength ranges and performs photoelectric conversion and two inorganic photoelectric conversion units 32B and 32R are stacked in the vertical direction. This is a so-called longitudinal spectroscopic type.

(2-1. Configuration of photoelectric conversion element)
The organic photoelectric conversion unit 20 is provided on the first surface (back surface) 30 </ b> A side of the semiconductor substrate 30. The inorganic photoelectric conversion units 32 </ b> B and 32 </ b> R are embedded in the semiconductor substrate 30 and are stacked in the thickness direction of the semiconductor substrate 30. In the organic photoelectric conversion unit 20 of the present embodiment, an electronic block layer 16 having the same configuration as that of the first embodiment is provided between the photoelectric conversion layer 17 and the upper electrode 18. Further, in the organic photoelectric conversion unit 20, the lower electrode 21 includes a plurality of electrodes (readout electrode 21 </ b> A and storage electrode 21 </ b> B), and the charge storage layer 23 is provided between the lower electrode 21 and the photoelectric conversion layer 17. .

  The organic photoelectric conversion unit 20 and the inorganic photoelectric conversion units 32B and 32R selectively detect light in different wavelength ranges and perform photoelectric conversion. Specifically, the organic photoelectric conversion unit 20 acquires a green (G) color signal. In the inorganic photoelectric conversion units 32B and 32R, blue (B) and red (R) color signals are acquired based on the difference in absorption coefficient. Thereby, in the photoelectric conversion element 10B, it is possible to acquire a plurality of types of color signals in one pixel without using a color filter.

  The second surface (front surface) 30B of the semiconductor substrate 30 includes, for example, a floating diffusion FD1 (region 36B in the semiconductor substrate 30), FD2 (region 37C in the semiconductor substrate 30), and FD3 (region 38C in the semiconductor substrate 30). The transfer transistors Tr2 and Tr3, the amplifier transistor AMP, the reset transistor RST, the selection transistor SEL, and the multilayer wiring 40 are provided. The multilayer wiring 40 has a configuration in which, for example, wiring layers 41, 42, and 43 are laminated in an insulating layer 44.

  In FIG. 5, the first surface 30A side of the semiconductor substrate 30 is represented as the light incident side S1, and the second surface 30B side is represented as the wiring layer side S2.

  The organic photoelectric conversion unit 20 has a configuration in which, for example, a lower electrode 21, a charge storage layer 23, a photoelectric conversion layer 17, an electron block layer 16, and an upper electrode 18 are stacked in this order from the first surface 30A side of the semiconductor substrate 30. have. An insulating layer 22 is provided between the lower electrode 21 and the charge storage layer 23. For example, the lower electrode 21 is formed separately for each photoelectric conversion element 10B, and, as will be described in detail later, includes a read electrode 21A and a storage electrode 21B that are separated from each other with an insulating layer 22 interposed therebetween. An opening 22H is provided in the insulating layer 22 on the readout electrode 21A, and the readout electrode 21A and the charge storage layer 23 are electrically connected through the opening 22H. 5 shows an example in which the electron storage layer 23, the photoelectric conversion layer 17, the electron block layer 16, and the upper electrode 18 are separately formed for each photoelectric conversion element 10B. It may be provided as a continuous layer common to the conversion element 10B. As in the first embodiment, for example, a fixed charge layer 12A, a dielectric layer 12B, and an interlayer insulating layer 14 are provided between the first surface 30A of the semiconductor substrate 30 and the lower electrode 21. ing. A protective layer 19 including a light shielding film 51 is provided on the upper electrode 18. On the protective layer 19, an optical member such as an on-chip lens layer 50 having an on-chip lens 50L is disposed.

  A through electrode 63 is provided between the first surface 30 </ b> A and the second surface 30 </ b> B of the semiconductor substrate 30. The organic photoelectric conversion unit 20 is connected to the gate Gamp of the amplifier transistor AMP and one source / drain region 36B of the reset transistor RST (reset transistor Tr1rst) also serving as the floating diffusion FD1 through the through electrode 63. Thereby, in the photoelectric conversion element 10 </ b> B, charges (here, electrons) generated in the organic photoelectric conversion unit 20 on the first surface 30 </ b> A side of the semiconductor substrate 30 are transferred to the second surface 30 </ b> B of the semiconductor substrate 30 through the through electrode 63. It is possible to improve the characteristics by transferring well to the side.

  The lower end of the through electrode 63 is connected to the connection portion 41A in the wiring layer 41, and the connection portion 41A and the gate Gamp of the amplifier transistor AMP are connected via the lower first contact 45. The connection portion 41A and the floating diffusion FD1 (region 36B) are connected via, for example, the lower second contact 46. The upper end of the through electrode 63 is connected to the readout electrode 21A via, for example, the pad portion 39A and the upper first contact 24A.

  Next to the floating diffusion FD1 (one source / drain region 36B of the reset transistor RST), the reset gate Grst of the reset transistor RST is arranged. Thereby, the charge accumulated in the floating diffusion FD1 can be reset by the reset transistor RST.

  In the photoelectric conversion element 10 </ b> B of the present embodiment, light that has entered the organic photoelectric conversion unit 20 from the upper electrode 18 side is absorbed by the photoelectric conversion layer 17 as in the photoelectric conversion element 10 </ b> A. The excitons generated thereby move to the interface between the electron donor and the electron acceptor constituting the photoelectric conversion layer 17 and dissociate into exciton separation, that is, electrons and holes. The charges (electrons and holes) generated here are carried to different electrodes by the diffusion due to the carrier concentration difference and the internal electric field due to the work function difference between the anode and the cathode, and are detected as photocurrents. In addition, by applying a potential between the lower electrode 21 and the upper electrode 18, the transport direction of electrons and holes can be controlled.

  Hereinafter, the configuration and materials of each part will be described.

  The organic photoelectric conversion unit 20 absorbs green light corresponding to a part or all of a selective wavelength range (for example, 450 nm or more and 650 nm or less) and generates an electron-hole pair. It is.

  As described above, the lower electrode 21 includes the readout electrode 21A and the storage electrode 21B that are separately formed. The readout electrode 21A is for transferring charges (electrons here) generated in the photoelectric conversion layer 17 to the floating diffusion FD1, and for example, the upper first contact 24A, the pad portion 39A, the through electrode 63, the connection The floating diffusion FD1 (36B) is connected via the portion 41A and the lower second contact 46. The storage electrode 21B is for accumulating electrons in the charge accumulation 23 as signal charges out of the charges generated in the photoelectric conversion layer 17, and for transferring the accumulated electrons to the readout electrode 21A. The storage electrode 21 </ b> B is provided in a region facing the light receiving surfaces of the inorganic photoelectric conversion units 32 </ b> B and 32 </ b> R formed in the semiconductor substrate 30. The storage electrode 21 </ b> B is preferably larger than the readout electrode 21 </ b> A, so that a large amount of charge can be stored in the charge storage layer 23.

The lower electrode 21 is made of a light-transmitting conductive film, for example, ITO (Indium Tin Oxide). However, as a constituent material of the lower electrode 21, in addition to this ITO, 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. Examples of the zinc oxide-based material 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). In addition, CuI, InSbO ₄ , ZnMgO, CuInO ₂ , MgIn ₂ O ₄ , CdO, ZnSnO _3, or the like may be used.

  As in the first embodiment, the electron blocking layer 16 selectively transports holes out of the charges generated in the photoelectric conversion layer 17 to the lower electrode 15 and moves electrons to the lower electrode 15 side. It is for inhibiting. The electron block layer 16 is configured using the organic semiconductor material represented by the general formula (1).

Similar to the first embodiment, the photoelectric conversion layer 17 converts light energy into electrical energy, and includes, for example, two or more organic semiconductor materials (p-type semiconductor material and n-type semiconductor material). It consists of In addition to the p-type semiconductor material and the n-type semiconductor material, the photoelectric conversion layer 17 has, for example, an absorption coefficient of 50000 cm ⁻¹ or more at a selective wavelength (eg, green light of 400 nm or more and 750 nm or less) in the visible light region. It is comprised including the color material which has. For the photoelectric conversion layer 17 of the present embodiment, the same organic semiconductor material as that of the first embodiment can be used. For example, as the color material, subphthalocyanine represented by the general formula (2) or a derivative thereof can be used. In addition, as the p-type semiconductor material, for example, compounds having a hole transporting property and represented by the above formulas (5-1) to (5-11) can be used. As the type semiconductor material, for example, fullerene C ₆₀ represented by the above general formula (3) or a derivative thereof, or fullerene C ₇₀ represented by the above general formula (4) or a derivative thereof having an electron transport property Can be used.

  In addition, the organic-semiconductor material which comprises the photoelectric converting layer 17 is not specifically limited. In addition to the organic semiconductor materials described above, for example, any one of naphthalene, anthracene, phenanthrene, tetracene, pyrene, perylene, and fluoranthene or derivatives thereof is preferably used. Alternatively, polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picoline, thiophene, acetylene, diacetylene, and derivatives thereof may be used. In addition, 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 rings or heterocyclic compounds, or two compounds such as quinoline, benzothiazole and benzoxazole having a squarylium group and a croconic methine group as a binding 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 thickness of the photoelectric conversion layer 17 is, for example, 50 nm to 500 nm.

  The upper electrode 18 is made of a light-transmitting conductive film as in the first embodiment. In the photoelectric conversion element 10B, the upper electrode 18 may be separated for each unit pixel P, or may be formed as a common electrode for each unit pixel P. The thickness of the upper electrode 18 is, for example, 10 nm to 200 nm.

  Note that other layers may be provided between the photoelectric conversion layer 17 and the lower electrode 15 and between the photoelectric conversion layer 17 and the upper electrode 18 in the same manner as the photoelectric conversion element 10A.

  The insulating layer 22 is for electrically separating the storage electrode 21B and the charge storage layer 23 from each other. For example, the insulating layer 22 is provided on the interlayer insulating layer 14 so as to cover the lower electrode 21. The insulating layer 22 is provided with an opening 22H on the readout electrode 21A in the lower electrode 21, and the readout electrode 21A and the charge storage layer 23 are electrically connected through the opening 22H. Yes. The insulating layer 22 can be formed using, for example, the same material as that of the interlayer insulating layer 14. Or a laminated film composed of two or more of these. The thickness of the insulating layer 22 is, for example, 20 nm to 500 nm.

  In the protective layer 19, for example, a light shielding film 51 is provided on the readout electrode 21A. The light shielding film 51 may be provided so as not to cover at least the storage electrode 21B but to cover at least the region of the readout electrode 21A in direct contact with the charge storage layer 23. For example, it is preferable that the conductive film 21a is slightly larger than the conductive film 21a formed in the same layer as the storage electrode 21B. An on-chip lens layer 50 is formed on the protective layer 19 so as to cover the entire surface. On the surface of the on-chip lens layer 50, a plurality of on-chip lenses 50L (microlenses) are provided.

  The semiconductor substrate 30 is composed of, for example, an n-type silicon (Si) substrate, and has a p-well 31 in a predetermined region. On the second surface 30B of the p-well 31, the transfer transistors Tr2 and Tr3, the amplifier transistor AMP, the reset transistor RST, the selection transistor SEL, and the like described above are provided. In addition, a peripheral circuit (not shown) including a logic circuit or the like is provided in the peripheral portion of the semiconductor substrate 30.

  The reset transistor RST (reset transistor Tr1rst) resets the charge transferred from the organic photoelectric conversion unit 20 to the floating diffusion FD1, and is configured by, for example, a MOS transistor. Specifically, the reset transistor Tr1rst includes a reset gate Grst, a channel formation region 36A, and source / drain regions 36B and 36C. The reset gate Grst is connected to the reset line RST1, and one source / drain region 36B of the reset transistor Tr1rst also serves as the floating diffusion FD1. The other source / drain region 36C constituting the reset transistor Tr1rst is connected to the power supply VDD.

  The amplifier transistor AMP is a modulation element that modulates the amount of charge generated in the organic photoelectric conversion unit 20 into a voltage, and is configured by, for example, a MOS transistor. Specifically, the amplifier transistor AMP includes a gate Gamp, a channel formation region 35A, and source / drain regions 35B and 35C. The gate Gamp is connected to the read electrode 21A and one source / drain region 36B (floating diffusion FD1) of the reset transistor Tr1rst through the lower first contact 45, the connection portion 41A, the lower second contact 46, the through electrode 63, and the like. Has been. Also, one source / drain region 35B shares a region with the other source / drain region 36C constituting the reset transistor Tr1rst and is connected to the power supply VDD.

  The selection transistor SEL (selection transistor TR1sel) includes a gate Gsel, a channel formation region 34A, and source / drain regions 34B and 34C. The gate Gsel is connected to the selection line SEL1. One source / drain region 34B shares a region with the other source / drain region 35C constituting the amplifier transistor AMP, and the other source / drain region 34C is a signal line (data output line) VSL1. It is connected to the.

  Each of the inorganic photoelectric conversion units 32 </ b> B and 32 </ b> R has a pn junction in a predetermined region of the semiconductor substrate 30. The inorganic photoelectric conversion units 32B and 32R are capable of spectrally separating light in the vertical direction by utilizing the fact that the wavelength of light absorbed in accordance with the incident depth of light in the silicon substrate is different. The inorganic photoelectric conversion unit 32B selectively detects blue light and accumulates signal charges corresponding to blue, and is installed at a depth at which blue light can be efficiently photoelectrically converted. The inorganic photoelectric conversion unit 32R selectively detects red light and accumulates signal charges corresponding to red, and is installed at a depth at which red light can be efficiently photoelectrically converted. Note that blue (B) is a color corresponding to a wavelength range of 450 nm to 495 nm, for example, and red (R) is a color corresponding to a wavelength range of 620 nm to 750 nm, for example. Each of the inorganic photoelectric conversion units 32B and 32R only needs to be able to detect light in a part or all of the wavelength ranges.

  The inorganic photoelectric conversion unit 32B includes, for example, a p + region that becomes a hole accumulation layer and an n region that becomes an electron accumulation layer. The inorganic photoelectric conversion unit 32R includes, for example, a p + region serving as a hole accumulation layer and an n region serving as an electron accumulation layer (having a p-n-p stacked structure). The n region of the inorganic photoelectric conversion unit 32B is connected to the vertical transfer transistor Tr2. The p + region of the inorganic photoelectric conversion unit 32B is bent along the transfer transistor Tr2, and is connected to the p + region of the inorganic photoelectric conversion unit 32R.

  The transfer transistor Tr2 (transfer transistor TR2trs) is for transferring the signal charge (here, electrons) corresponding to blue generated and accumulated in the inorganic photoelectric conversion unit 32B to the floating diffusion FD2. Since the inorganic photoelectric conversion unit 32B is formed at a deep position from the second surface 30B of the semiconductor substrate 30, the transfer transistor TR2trs of the inorganic photoelectric conversion unit 32B is preferably formed of a vertical transistor. The transfer transistor TR2trs is connected to the transfer gate line TG2. Further, a floating diffusion FD2 is provided in a region 37C in the vicinity of the gate Gtrs2 of the transfer transistor TR2trs. The charges accumulated in the inorganic photoelectric conversion unit 32B are read out to the floating diffusion FD2 through a transfer channel formed along the gate Gtrs2.

  The transfer transistor Tr3 (transfer transistor TR3trs) transfers the signal charge (here, electrons) generated in the inorganic photoelectric conversion unit 32R and corresponding to the accumulated red color to the floating diffusion FD3. It is configured. The transfer transistor TR3trs is connected to the transfer gate line TG3. Further, a floating diffusion FD3 is provided in a region 38C in the vicinity of the gate Gtrs3 of the transfer transistor TR3trs. The charge accumulated in the inorganic photoelectric conversion unit 32R is read out to the floating diffusion FD3 through a transfer channel formed along the gate Gtrs3.

  On the second surface 30B side of the semiconductor substrate 30, a reset transistor TR2rst, an amplifier transistor TR2amp, and a selection transistor TR2sel that form a control unit of the inorganic photoelectric conversion unit 32B are further provided. Further, a reset transistor TR3rst, an amplifier transistor TR3amp, and a selection transistor TR3sel that constitute a control unit of the inorganic photoelectric conversion unit 32R are provided.

  The reset transistor TR2rst includes a gate, a channel formation region, and a source / drain region. The gate of the reset transistor TR2rst is connected to the reset line RST2, and one source / drain region of the reset transistor TR2rst is connected to the power supply VDD. The other source / drain region of the reset transistor TR2rst also serves as the floating diffusion FD2.

  The amplifier transistor TR2amp includes a gate, a channel formation region, and a source / drain region. The gate is connected to the other source / drain region (floating diffusion FD2) of the reset transistor TR2rst. Further, one source / drain region constituting the amplifier transistor TR2amp shares a region with one source / drain region constituting the reset transistor TR2rst, and is connected to the power supply VDD.

  The selection transistor TR2sel is composed of a gate, a channel formation region, and a source / drain region. The gate is connected to the selection line SEL2. One source / drain region constituting the selection transistor TR2sel shares a region with the other source / drain region constituting the amplifier transistor TR2amp. The other source / drain region constituting the selection transistor TR2sel is connected to a signal line (data output line) VSL2.

  The reset transistor TR3rst includes a gate, a channel formation region, and a source / drain region. The gate of the reset transistor TR3rst is connected to the reset line RST3, and one source / drain region constituting the reset transistor TR3rst is connected to the power supply VDD. The other source / drain region constituting the reset transistor TR3rst also serves as the floating diffusion FD3.

  The amplifier transistor TR3amp includes a gate, a channel formation region, and a source / drain region. The gate is connected to the other source / drain region (floating diffusion FD3) constituting the reset transistor TR3rst. Further, one source / drain region constituting the amplifier transistor TR3amp shares a region with one source / drain region constituting the reset transistor TR3rst, and is connected to the power supply VDD.

  The select transistor TR3sel includes a gate, a channel formation region, and a source / drain region. The gate is connected to the selection line SEL3. Further, one source / drain region constituting the selection transistor TR3sel shares a region with the other source / drain region constituting the amplifier transistor TR3amp. The other source / drain region constituting the selection transistor TR3sel is connected to a signal line (data output line) VSL3.

  The reset lines RST1, RST2, RST3, the selection lines SEL1, SEL2, SEL3, and the transfer gate lines TG2, TG3 are respectively connected to the vertical drive circuit 112 that constitutes the drive circuit. The signal lines (data output lines) VSL1, VSL2, and VSL3 are connected to a column signal processing circuit 113 that constitutes a drive circuit.

  The lower first contact 45, the lower second contact 46, the upper first contact 24A, and the upper second contact 24B are made of, for example, a doped silicon material such as PDAS (Phosphorus Doped Amorphous Silicon), or aluminum (Al), tungsten It is made of a metal material such as (W), titanium (Ti), cobalt (Co), hafnium (Hf), and tantalum (Ta).

(2-2. Manufacturing method of photoelectric conversion element)
The photoelectric conversion element 10B of the present embodiment can be manufactured, for example, as follows.

  8 to 13 show the manufacturing method of the photoelectric conversion element 10B in the order of steps. First, as shown in FIG. 8, for example, a p-well 31 is formed as a first conductivity type well in a semiconductor substrate 30, and a second conductivity type (for example, n-type) inorganic is formed in the p well 31. Photoelectric converters 32B and 32R are formed. A p + region is formed in the vicinity of the first surface 30 </ b> A of the semiconductor substrate 30.

  As shown in FIG. 8, for example, n + regions to be the floating diffusions FD <b> 1 to FD <b> 3 are formed on the second surface 30 </ b> B of the semiconductor substrate 30, and then the gate insulating layer 33, the transfer transistor Tr <b> 2, the transfer transistor Tr <b> 3 are selected. A gate wiring layer 47 including the gates of the transistor SEL, the amplifier transistor AMP, and the reset transistor RST is formed. Thereby, the transfer transistor Tr2, the transfer transistor Tr3, the selection transistor SEL, the amplifier transistor AMP, and the reset transistor RST are formed. Furthermore, the multilayer wiring 40 including the lower first contact 45, the lower second contact 46, the wiring layers 41 to 43 including the connection portion 41 </ b> A, and the insulating layer 44 is formed on the second surface 30 </ b> B of the semiconductor substrate 30.

  As the base of the semiconductor substrate 30, for example, an SOI (Silicon on Insulator) substrate in which a semiconductor substrate 30, a buried oxide film (not shown), and a holding substrate (not shown) are stacked is used. Although not shown in FIG. 8, the buried oxide film and the holding substrate are bonded to the first surface 30 </ b> A of the semiconductor substrate 30. After ion implantation, annealing is performed.

  Next, a support substrate (not shown) or another semiconductor substrate is joined to the second surface 30B side (multilayer wiring 40 side) of the semiconductor substrate 30 and turned upside down. Subsequently, the semiconductor substrate 30 is separated from the buried oxide film of the SOI substrate and the holding substrate, and the first surface 30A of the semiconductor substrate 30 is exposed. The above steps can be performed by techniques used in a normal CMOS process such as ion implantation and CVD (Chemical Vapor Deposition).

  Next, as shown in FIG. 9, the semiconductor substrate 30 is processed from the first surface 30A side, for example, by dry etching to form, for example, an annular opening 34H. As shown in FIG. 9, the depth of the opening 34H penetrates from the first surface 30A to the second surface 30B of the semiconductor substrate 30 and reaches, for example, the connection portion 41A.

  Subsequently, the negative fixed charge layer 12A, for example, is formed on the first surface 30A of the semiconductor substrate 30 and the side surface of the opening 34H. Two or more types of films may be stacked as the negative fixed charge layer 12A. Thereby, the function as a hole accumulation layer can be further enhanced. After forming the negative fixed charge layer 12A, the dielectric layer 12B is formed. Next, after the pad portions 39A and 39B are formed at predetermined positions on the dielectric layer 12B, the insulating layer 26 is formed on the dielectric layer 12B and the pad portions 39A and 39B, and then, for example, CMP (Chemical The surface of the insulating layer 26B is planarized using a mechanical polishing method.

  Subsequently, as shown in FIG. 10, openings 14H1 and 14H2 penetrating to the pad portions 39A and 39B are formed in the interlayer insulating layer 14. Next, a conductive material such as Al is embedded in the openings 14H1 and 14H2 to form the upper first contact 24A and the upper second contact 24B, respectively. Subsequently, as shown in FIG. 11, after a conductive film 21x is formed on the interlayer insulating layer 14, a photoresist is formed at a predetermined position (for example, between the pad portion 39A and the pad portion 39B) of the conductive film 21x. PR is formed. Thereafter, etching and photoresist PR are removed to pattern the read electrode 21A and the storage electrode 21B shown in FIG.

  Next, as shown in FIG. 13, after the insulating layer 22 is formed on the interlayer insulating layer 14, the readout electrode 21A, and the storage electrode 21B, an opening 22H is provided on the readout electrode 21A. Thereafter, the charge storage layer 23, the photoelectric conversion layer 17, the electron blocking layer 16, the upper electrode 18, the protective layer 19, and the light shielding film 51 are formed on the insulating layer 22. As described above, when another organic layer is formed on the upper layer or the lower layer of the photoelectric conversion layer 17, it is desirable to form the organic layer continuously (by a vacuum consistent process) in the vacuum process. Further, the method for forming the photoelectric conversion layer 17 is not necessarily limited to the method using the vacuum vapor deposition method, and other methods such as a spin coating technique and a printing technique may be used. Finally, an optical member such as a planarizing layer and the on-chip lens layer 50 are disposed. Thus, the photoelectric conversion element 10B illustrated in FIG. 5 is completed.

  In the photoelectric conversion element 10B, when light enters the organic photoelectric conversion unit 20 via the on-chip lens 50L, the light is emitted from the organic photoelectric conversion unit 20 in the same manner as the photoelectric conversion element 10A of the first embodiment. The inorganic photoelectric conversion units 32B and 32R pass through in order, and photoelectric conversion is performed for each of the green, blue, and red color lights in the passing process.

  FIG. 14 illustrates an operation example of the photoelectric conversion element 10B. (A) shows the potential at the storage electrode 21B, (B) shows the potential at the floating diffusion FD1 (readout electrode 21A), and (C) shows the potential at the gate (Gsel) of the reset transistor TR1rst. It is. In the photoelectric conversion element 10B, voltages are individually applied to the readout electrode 21A and the storage electrode 21B, respectively.

  In the photoelectric conversion element 10B, in the accumulation period, the potential V1 is applied from the drive circuit to the readout electrode 21A, and the potential V2 is applied to the storage electrode 21B. Here, the potentials V1 and V2 satisfy V2> V1. Thereby, charges (here, electrons) generated by the photoelectric conversion are attracted to the storage electrode 21B and stored in the region of the photoelectric conversion layer 17 facing the storage electrode 21B (storage period). Incidentally, the potential of the region of the photoelectric conversion layer 17 facing the storage electrode 21B becomes a more negative value as the photoelectric conversion time elapses. The holes are sent from the upper electrode 18 to the drive circuit.

  In the photoelectric conversion element 10B, a reset operation is performed in the later stage of the accumulation period. Specifically, at timing t1, the scanning unit changes the voltage of the reset signal RST from a low level to a high level. Thereby, in the unit pixel P, the reset transistor TR1rst is turned on. As a result, the voltage of the floating diffusion FD1 is set to the power supply voltage VDD, and the voltage of the floating diffusion FD1 is reset (reset period).

  After the reset operation is completed, charge is read out. Specifically, at timing t2, the potential V3 is applied from the drive circuit to the readout electrode 21A, and the potential V4 is applied to the storage electrode 21B. Here, the potentials V3 and V4 are set to V3 <V4. Thereby, the electric charge (here, electrons) accumulated in the region corresponding to the accumulation electrode 21B is read out from the readout electrode 21A to the floating diffusion FD1. That is, the charge accumulated in the photoelectric conversion layer 17 is read out to the control unit (transfer period).

  After the read operation is completed, the potential V1 is again applied from the drive circuit to the read electrode 21A, and the potential V2 is applied to the storage electrode 21B. Thereby, charges (here, electrons) generated by the photoelectric conversion are attracted to the storage electrode 21B and stored in the region of the photoelectric conversion layer 17 facing the storage electrode 21B (storage period).

(2-3. Action and effect)
As described above, in the photoelectric conversion element 10B of the present embodiment, the electronic block layer 16 including the benzodifuran derivative represented by the general formula (1) is provided between the anode (upper electrode 18) and the photoelectric conversion layer 17. In addition, the lower electrode 21 was divided into a read electrode 21A and a storage electrode 21B, and a voltage was applied independently. Thereby, in the photoelectric conversion element 10B, the charge generated in the photoelectric conversion layer 17 can be stored in the charge storage layer 23 disposed between the lower electrode 21 and the photoelectric conversion layer 17 and stored. It is possible to read out the charged charges to the floating diffusion FD1 through the readout electrode 21A as appropriate. Therefore, it is possible to completely deplete the charge storage portion at the start of exposure. That is, it is possible to provide the photoelectric conversion element 10B having high element characteristics and excellent heat resistance, and further improved in image quality, and the image pickup apparatus 1 including the photoelectric conversion element 10B.

<3. Application example>
(Application example 1)
FIG. 15 illustrates an entire configuration of the imaging apparatus 1 using, for example, the photoelectric conversion element 10A (or the photoelectric conversion element 10B) described in the first embodiment or the like for each pixel. The imaging device 1 is a CMOS image sensor, and has a pixel unit 1a as an imaging area on a semiconductor substrate 11, and a peripheral region of the pixel unit 1a includes, for example, a row scanning unit 131, a horizontal selection unit 133, A peripheral circuit unit 130 including a column scanning unit 134 and a system control unit 132 is provided.

  The pixel unit 1a includes, for example, a plurality of unit pixels P (for example, equivalent to the photoelectric conversion element 10A) that are two-dimensionally arranged in a matrix. In the unit pixel P, for example, 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 includes a shift register, an address decoder, and 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 each of the horizontal selection switches of 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 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.

(Application example 2)
The above-described imaging device 1 can be applied to all types of electronic devices having an imaging function, such as a camera system such as a digital still camera and a video camera, and a mobile phone having an imaging function. FIG. 16 shows a schematic configuration of the camera 2 as an example. The camera 2 is, for example, a video camera that can capture a still image or a moving image, and drives the imaging device 1, the optical system (optical lens) 310, the shutter device 311, the imaging device 1 and the shutter device 311. A unit 313 and a signal processing unit 312.

  The optical system 310 guides image light (incident light) from a subject to the pixel unit 1 a of the imaging device 1. The optical system 310 may be composed of a plurality of optical lenses. The shutter device 311 controls the light irradiation period and the light shielding period to the imaging apparatus 1. The drive unit 313 controls the transfer operation of the 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 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.

(Application example 3)
<Application example to in-vivo information acquisition system>
Furthermore, the technology (present technology) according to the present disclosure can be applied to various products. For example, the technology according to the present disclosure may be applied to an endoscopic surgery system.

  FIG. 17 is a block diagram illustrating an example of a schematic configuration of a patient in-vivo information acquisition system using a capsule endoscope to which the technique according to the present disclosure (present technique) can be applied.

  The in-vivo information acquisition system 10001 includes a capsule endoscope 10100 and an external control device 10200.

  The capsule endoscope 10100 is swallowed by a patient at the time of examination. The capsule endoscope 10100 has an imaging function and a wireless communication function, and moves inside the organ such as the stomach and the intestine by peristaltic motion or the like until it is spontaneously discharged from the patient. Images (hereinafter also referred to as in-vivo images) are sequentially captured at predetermined intervals, and information about the in-vivo images is sequentially wirelessly transmitted to the external control device 10200 outside the body.

  The external control device 10200 comprehensively controls the operation of the in-vivo information acquisition system 10001. Further, the external control device 10200 receives information about the in-vivo image transmitted from the capsule endoscope 10100 and, based on the received information about the in-vivo image, displays the in-vivo image on the display device (not shown). The image data for displaying is generated.

  In the in-vivo information acquisition system 10001, in this way, an in-vivo image obtained by imaging the state of the patient's body can be obtained at any time from when the capsule endoscope 10100 is swallowed until it is discharged.

  The configurations and functions of the capsule endoscope 10100 and the external control device 10200 will be described in more detail.

  The capsule endoscope 10100 includes a capsule-type casing 10101. In the casing 10101, a light source unit 10111, an imaging unit 10112, an image processing unit 10113, a wireless communication unit 10114, a power supply unit 10115, and a power supply unit 10116 and the control unit 10117 are stored.

  The light source unit 10111 is composed of a light source such as an LED (light emitting diode), for example, and irradiates the imaging field of the imaging unit 10112 with light.

  The imaging unit 10112 includes an imaging device and an optical system including a plurality of lenses provided in the preceding stage of the imaging device. Reflected light (hereinafter referred to as observation light) of light irradiated on the body tissue to be observed is collected by the optical system and enters the image sensor. In the imaging unit 10112, in the imaging element, the observation light incident thereon is photoelectrically converted, and an image signal corresponding to the observation light is generated. The image signal generated by the imaging unit 10112 is provided to the image processing unit 10113.

  The image processing unit 10113 is configured by a processor such as a CPU (Central Processing Unit) or a GPU (Graphics Processing Unit), and performs various signal processing on the image signal generated by the imaging unit 10112. The image processing unit 10113 provides the radio communication unit 10114 with the image signal subjected to signal processing as RAW data.

  The wireless communication unit 10114 performs predetermined processing such as modulation processing on the image signal subjected to signal processing by the image processing unit 10113, and transmits the image signal to the external control apparatus 10200 via the antenna 10114A. In addition, the wireless communication unit 10114 receives a control signal related to drive control of the capsule endoscope 10100 from the external control device 10200 via the antenna 10114A. The wireless communication unit 10114 provides a control signal received from the external control device 10200 to the control unit 10117.

  The power feeding unit 10115 includes a power receiving antenna coil, a power regeneration circuit that regenerates power from a current generated in the antenna coil, a booster circuit, and the like. In the power feeding unit 10115, electric power is generated using a so-called non-contact charging principle.

  The power supply unit 10116 is configured by a secondary battery and stores the electric power generated by the power supply unit 10115. In FIG. 17, in order to avoid complication of the drawing, illustration of an arrow or the like indicating a power supply destination from the power supply unit 10116 is omitted, but power stored in the power supply unit 10116 is stored in the light source unit 10111. The imaging unit 10112, the image processing unit 10113, the wireless communication unit 10114, and the control unit 10117 can be used for driving them.

  The control unit 10117 includes a processor such as a CPU, and a control signal transmitted from the external control device 10200 to drive the light source unit 10111, the imaging unit 10112, the image processing unit 10113, the wireless communication unit 10114, and the power feeding unit 10115. Control accordingly.

  The external control device 10200 is configured by a processor such as a CPU or GPU, or a microcomputer or a control board in which a processor and a storage element such as a memory are mounted. The external control device 10200 controls the operation of the capsule endoscope 10100 by transmitting a control signal to the control unit 10117 of the capsule endoscope 10100 via the antenna 10200A. In the capsule endoscope 10100, for example, the light irradiation condition for the observation target in the light source unit 10111 can be changed by a control signal from the external control device 10200. In addition, an imaging condition (for example, a frame rate or an exposure value in the imaging unit 10112) can be changed by a control signal from the external control device 10200. Further, the contents of processing in the image processing unit 10113 and the conditions (for example, the transmission interval, the number of transmission images, etc.) by which the wireless communication unit 10114 transmits an image signal may be changed by a control signal from the external control device 10200. .

  Further, the external control device 10200 performs various image processing on the image signal transmitted from the capsule endoscope 10100, and generates image data for displaying the captured in-vivo image on the display device. As the image processing, for example, development processing (demosaic processing), high image quality processing (band enhancement processing, super-resolution processing, NR (Noise reduction) processing and / or camera shake correction processing, etc.), and / or enlargement processing ( Various signal processing such as electronic zoom processing can be performed. The external control device 10200 controls driving of the display device to display an in-vivo image captured based on the generated image data. Alternatively, the external control device 10200 may cause the generated image data to be recorded on a recording device (not shown) or may be printed out on a printing device (not shown).

  Heretofore, an example of the in-vivo information acquisition system to which the technology according to the present disclosure can be applied has been described. The technology according to the present disclosure can be applied to, for example, the imaging unit 10112 among the configurations described above. Thereby, detection accuracy improves.

(Application example 4)
<4. Application example to endoscopic surgery system>
The technology according to the present disclosure (present technology) can be applied to various products. For example, the technology according to the present disclosure may be applied to an endoscopic surgery system.

  FIG. 18 is a diagram illustrating an example of a schematic configuration of an endoscopic surgery system to which the technology (present technology) according to the present disclosure can be applied.

  FIG. 18 shows a state where an operator (doctor) 11131 is performing surgery on a patient 11132 on a patient bed 11133 using an endoscopic surgery system 11000. As shown in the figure, an endoscopic surgery system 11000 includes an endoscope 11100, other surgical instruments 11110 such as an insufflation tube 11111 and an energy treatment instrument 11112, and a support arm device 11120 that supports the endoscope 11100. And a cart 11200 on which various devices for endoscopic surgery are mounted.

  The endoscope 11100 includes a lens barrel 11101 in which a region having a predetermined length from the distal end is inserted into the body cavity of the patient 11132, and a camera head 11102 connected to the proximal end of the lens barrel 11101. In the illustrated example, an endoscope 11100 configured as a so-called rigid mirror having a rigid lens barrel 11101 is illustrated, but the endoscope 11100 may be configured as a so-called flexible mirror having a flexible lens barrel. Good.

  An opening into which the objective lens is fitted is provided at the tip of the lens barrel 11101. A light source device 11203 is connected to the endoscope 11100, and light generated by the light source device 11203 is guided to the tip of the lens barrel by a light guide extending inside the lens barrel 11101. Irradiation is performed toward the observation target in the body cavity of the patient 11132 through the lens. Note that the endoscope 11100 may be a direct endoscope, a perspective mirror, or a side endoscope.

  An optical system and an imaging device are provided inside the camera head 11102, and reflected light (observation light) from the observation target is condensed on the imaging device by the optical system. Observation light is photoelectrically converted by the imaging element, and an electrical signal corresponding to the observation light, that is, an image signal corresponding to the observation image is generated. The image signal is transmitted to a camera control unit (CCU) 11201 as RAW data.

  The CCU 11201 is configured by a CPU (Central Processing Unit), a GPU (Graphics Processing Unit), and the like, and comprehensively controls operations of the endoscope 11100 and the display device 11202. Further, the CCU 11201 receives an image signal from the camera head 11102 and performs various kinds of image processing for displaying an image based on the image signal, such as development processing (demosaic processing), for example.

  The display device 11202 displays an image based on an image signal subjected to image processing by the CCU 11201 under the control of the CCU 11201.

  The light source device 11203 is composed of a light source such as an LED (light emitting diode), for example, and supplies irradiation light to the endoscope 11100 when photographing a surgical site or the like.

  The input device 11204 is an input interface for the endoscopic surgery system 11000. A user can input various information and instructions to the endoscopic surgery system 11000 via the input device 11204. For example, the user inputs an instruction to change the imaging conditions (type of irradiation light, magnification, focal length, etc.) by the endoscope 11100.

  The treatment instrument control device 11205 controls driving of the energy treatment instrument 11112 for tissue ablation, incision, blood vessel sealing, or the like. In order to inflate the body cavity of the patient 11132 for the purpose of securing the field of view by the endoscope 11100 and securing the operator's work space, the pneumoperitoneum device 11206 passes gas into the body cavity via the pneumoperitoneum tube 11111. Send in. The recorder 11207 is an apparatus capable of recording various types of information related to surgery. The printer 11208 is a device that can print various types of information related to surgery in various formats such as text, images, or graphs.

  Note that the light source device 11203 that supplies the irradiation light when imaging the surgical site to the endoscope 11100 can be configured by a white light source configured by, for example, an LED, a laser light source, or a combination thereof. When a white light source is configured by a combination of RGB laser light sources, the output intensity and output timing of each color (each wavelength) can be controlled with high accuracy. Therefore, the light source device 11203 adjusts the white balance of the captured image. It can be carried out. In this case, laser light from each of the RGB laser light sources is irradiated on the observation target in a time-sharing manner, and the drive of the image sensor of the camera head 11102 is controlled in synchronization with the irradiation timing, thereby corresponding to each RGB. It is also possible to take the images that have been taken in time division. According to this method, a color image can be obtained without providing a color filter in the image sensor.

  Further, the driving of the light source device 11203 may be controlled so as to change the intensity of light to be output every predetermined time. Synchronously with the timing of changing the intensity of the light, the drive of the image sensor of the camera head 11102 is controlled to acquire an image in a time-sharing manner, and the image is synthesized, so that high dynamic without so-called blackout and overexposure A range image can be generated.

  The light source device 11203 may be configured to be able to supply light of a predetermined wavelength band corresponding to special light observation. In special light observation, for example, by utilizing the wavelength dependence of light absorption in body tissue, the surface of the mucous membrane is irradiated by irradiating light in a narrow band compared to irradiation light (ie, white light) during normal observation. A so-called narrow band imaging is performed in which a predetermined tissue such as a blood vessel is imaged with high contrast. Alternatively, in special light observation, fluorescence observation may be performed in which an image is obtained by fluorescence generated by irradiating excitation light. In fluorescence observation, the body tissue is irradiated with excitation light to observe fluorescence from the body tissue (autofluorescence observation), or a reagent such as indocyanine green (ICG) is locally administered to the body tissue and applied to the body tissue. It is possible to obtain a fluorescence image by irradiating excitation light corresponding to the fluorescence wavelength of the reagent. The light source device 11203 can be configured to be able to supply narrowband light and / or excitation light corresponding to such special light observation.

  FIG. 19 is a block diagram illustrating an example of functional configurations of the camera head 11102 and the CCU 11201 illustrated in FIG.

  The camera head 11102 includes a lens unit 11401, an imaging unit 11402, a driving unit 11403, a communication unit 11404, and a camera head control unit 11405. The CCU 11201 includes a communication unit 11411, an image processing unit 11412, and a control unit 11413. The camera head 11102 and the CCU 11201 are connected to each other by a transmission cable 11400 so that they can communicate with each other.

  The lens unit 11401 is an optical system provided at a connection portion with the lens barrel 11101. Observation light taken from the tip of the lens barrel 11101 is guided to the camera head 11102 and enters the lens unit 11401. The lens unit 11401 is configured by combining a plurality of lenses including a zoom lens and a focus lens.

  One (so-called single plate type) image sensor may be included in the imaging unit 11402, or a plurality (so-called multi-plate type) may be used. In the case where the imaging unit 11402 is configured as a multi-plate type, for example, image signals corresponding to RGB may be generated by each imaging element, and a color image may be obtained by combining them. Alternatively, the imaging unit 11402 may be configured to include a pair of imaging elements for acquiring right-eye and left-eye image signals corresponding to 3D (dimensional) display. By performing the 3D display, the operator 11131 can more accurately grasp the depth of the living tissue in the surgical site. Note that in the case where the imaging unit 11402 is configured as a multi-plate type, a plurality of lens units 11401 can be provided corresponding to each imaging element.

  Further, the imaging unit 11402 is not necessarily provided in the camera head 11102. For example, the imaging unit 11402 may be provided inside the lens barrel 11101 immediately after the objective lens.

  The drive unit 11403 includes an actuator, and moves the zoom lens and focus lens of the lens unit 11401 by a predetermined distance along the optical axis under the control of the camera head control unit 11405. Thereby, the magnification and the focus of the image captured by the imaging unit 11402 can be adjusted as appropriate.

  The communication unit 11404 is configured by a communication device for transmitting / receiving various types of information to / from the CCU 11201. The communication unit 11404 transmits the image signal obtained from the imaging unit 11402 as RAW data to the CCU 11201 via the transmission cable 11400.

  In addition, the communication unit 11404 receives a control signal for controlling driving of the camera head 11102 from the CCU 11201 and supplies the control signal to the camera head control unit 11405. The control signal includes, for example, information for designating the frame rate of the captured image, information for designating the exposure value at the time of imaging, and / or information for designating the magnification and focus of the captured image. Contains information about the condition.

  Note that the imaging conditions such as the frame rate, exposure value, magnification, and focus may be appropriately specified by the user, or automatically set by the control unit 11413 of the CCU 11201 based on the acquired image signal. Good. In the latter case, the so-called AE (Auto Exposure) function, AF (Auto Focus) function, and AWB (Auto White Balance) function are mounted on the endoscope 11100.

  The camera head control unit 11405 controls driving of the camera head 11102 based on a control signal from the CCU 11201 received via the communication unit 11404.

  The communication unit 11411 is configured by a communication device for transmitting and receiving various types of information to and from the camera head 11102. The communication unit 11411 receives an image signal transmitted from the camera head 11102 via the transmission cable 11400.

  The communication unit 11411 transmits a control signal for controlling driving of the camera head 11102 to the camera head 11102. The image signal and the control signal can be transmitted by electrical communication, optical communication, or the like.

  The image processing unit 11412 performs various types of image processing on an image signal that is RAW data transmitted from the camera head 11102.

  The control unit 11413 performs various types of control related to imaging of the surgical site or the like by the endoscope 11100 and display of a captured image obtained by imaging of the surgical site or the like. For example, the control unit 11413 generates a control signal for controlling driving of the camera head 11102.

  In addition, the control unit 11413 causes the display device 11202 to display a captured image in which an operation part or the like is reflected based on the image signal subjected to image processing by the image processing unit 11412. At this time, the control unit 11413 may recognize various objects in the captured image using various image recognition techniques. For example, the control unit 11413 detects surgical tools such as forceps, specific biological parts, bleeding, mist when using the energy treatment tool 11112, and the like by detecting the shape and color of the edge of the object included in the captured image. Can be recognized. When displaying the captured image on the display device 11202, the control unit 11413 may display various types of surgery support information superimposed on the image of the surgical unit using the recognition result. Surgery support information is displayed in a superimposed manner and presented to the operator 11131, thereby reducing the burden on the operator 11131 and allowing the operator 11131 to proceed with surgery reliably.

  A transmission cable 11400 connecting the camera head 11102 and the CCU 11201 is an electric signal cable corresponding to electric signal communication, an optical fiber corresponding to optical communication, or a composite cable thereof.

  Here, in the illustrated example, communication is performed by wire using the transmission cable 11400, but communication between the camera head 11102 and the CCU 11201 may be performed wirelessly.

  Heretofore, an example of an endoscopic surgery system to which the technology according to the present disclosure can be applied has been described. The technology according to the present disclosure can be applied to the imaging unit 11402 among the configurations described above. By applying the technique according to the present disclosure to the imaging unit 11402, the detection accuracy is improved.

  Here, although an endoscopic surgery system has been described as an example, the technology according to the present disclosure may be applied to, for example, a microscope surgery system and the like.

(Application example 5)
<Application examples to mobile objects>
The technology according to the present disclosure can be applied to various products. For example, the technology according to the present disclosure may be any kind of movement such as an automobile, an electric vehicle, a hybrid electric vehicle, a motorcycle, a bicycle, personal mobility, an airplane, a drone, a ship, a robot, a construction machine, and an agricultural machine (tractor). You may implement | achieve as an apparatus mounted in a body.

  FIG. 20 is a block diagram illustrating a schematic configuration example of a vehicle control system that is an example of a mobile control system to which the technology according to the present disclosure can be applied.

  The vehicle control system 12000 includes a plurality of electronic control units connected via a communication network 12001. In the example illustrated in FIG. 20, the vehicle control system 12000 includes a drive system control unit 12010, a body system control unit 12020, a vehicle exterior information detection unit 12030, a vehicle interior information detection unit 12040, and an integrated control unit 12050. Further, as a functional configuration of the integrated control unit 12050, a microcomputer 12051, an audio image output unit 12052, and an in-vehicle network I / F (interface) 12053 are illustrated.

  The drive system control unit 12010 controls the operation of the device related to the drive system of the vehicle according to various programs. For example, the drive system control unit 12010 includes a driving force generator for generating a driving force of a vehicle such as an internal combustion engine or a driving motor, a driving force transmission mechanism for transmitting the driving force to wheels, and a steering angle of the vehicle. It functions as a control device such as a steering mechanism that adjusts and a braking device that generates a braking force of the vehicle.

  The body system control unit 12020 controls the operation of various devices mounted on the vehicle body according to various programs. For example, the body system control unit 12020 functions as a keyless entry system, a smart key system, a power window device, or a control device for various lamps such as a headlamp, a back lamp, a brake lamp, a blinker, or a fog lamp. In this case, the body control unit 12020 can be input with radio waves transmitted from a portable device that substitutes for a key or signals from various switches. The body system control unit 12020 receives input of these radio waves or signals, and controls a door lock device, a power window device, a lamp, and the like of the vehicle.

  The vehicle outside information detection unit 12030 detects information outside the vehicle on which the vehicle control system 12000 is mounted. For example, the imaging unit 12031 is connected to the vehicle exterior information detection unit 12030. The vehicle exterior information detection unit 12030 causes the imaging unit 12031 to capture an image outside the vehicle and receives the captured image. The vehicle outside information detection unit 12030 may perform an object detection process or a distance detection process such as a person, a car, an obstacle, a sign, or a character on a road surface based on the received image.

  The imaging unit 12031 is an optical sensor that receives light and outputs an electrical signal corresponding to the amount of received light. The imaging unit 12031 can output an electrical signal as an image, or can output it as distance measurement information. Further, the light received by the imaging unit 12031 may be visible light or invisible light such as infrared rays.

  The vehicle interior information detection unit 12040 detects vehicle interior information. For example, a driver state detection unit 12041 that detects a driver's state is connected to the in-vehicle information detection unit 12040. The driver state detection unit 12041 includes, for example, a camera that images the driver, and the vehicle interior information detection unit 12040 determines the degree of fatigue or concentration of the driver based on the detection information input from the driver state detection unit 12041. It may be calculated or it may be determined whether the driver is asleep.

  The microcomputer 12051 calculates a control target value of the driving force generator, the steering mechanism, or the braking device based on the information inside / outside the vehicle acquired by the vehicle outside information detection unit 12030 or the vehicle interior information detection unit 12040, and the drive system control unit A control command can be output to 12010. For example, the microcomputer 12051 realizes ADAS (Advanced Driver Assistance System) functions including vehicle collision avoidance or impact mitigation, tracking based on inter-vehicle distance, vehicle speed maintenance, vehicle collision warning, or vehicle lane departure warning. It is possible to perform cooperative control for the purpose.

  Further, the microcomputer 12051 controls the driving force generator, the steering mechanism, the braking device, and the like based on the information around the vehicle acquired by the vehicle exterior information detection unit 12030 or the vehicle interior information detection unit 12040. It is possible to perform cooperative control for the purpose of automatic driving that autonomously travels without depending on the operation.

  Further, the microcomputer 12051 can output a control command to the body system control unit 12020 based on information outside the vehicle acquired by the vehicle outside information detection unit 12030. For example, the microcomputer 12051 controls the headlamp according to the position of the preceding vehicle or the oncoming vehicle detected by the outside information detection unit 12030, and performs cooperative control for the purpose of anti-glare, such as switching from a high beam to a low beam. It can be carried out.

  The sound image output unit 12052 transmits an output signal of at least one of sound and image to an output device capable of visually or audibly notifying information to a vehicle occupant or the outside of the vehicle. In the example of FIG. 20, an audio speaker 12061, a display unit 12062, and an instrument panel 12063 are illustrated as output devices. The display unit 12062 may include at least one of an on-board display and a head-up display, for example.

  FIG. 21 is a diagram illustrating an example of the installation position of the imaging unit 12031.

  In FIG. 21, the imaging unit 12031 includes imaging units 12101, 12102, 12103, 12104, and 12105.

  The imaging units 12101, 12102, 12103, 12104, and 12105 are provided, for example, at positions such as a front nose, a side mirror, a rear bumper, a back door, and an upper part of a windshield in the vehicle interior of the vehicle 12100. The imaging unit 12101 provided in the front nose and the imaging unit 12105 provided in the upper part of the windshield in the vehicle interior mainly acquire an image in front of the vehicle 12100. The imaging units 12102 and 12103 provided in the side mirror mainly acquire an image of the side of the vehicle 12100. The imaging unit 12104 provided in the rear bumper or the back door mainly acquires an image behind the vehicle 12100. The imaging unit 12105 provided on the upper part of the windshield in the passenger compartment is mainly used for detecting a preceding vehicle or a pedestrian, an obstacle, a traffic light, a traffic sign, a lane, or the like.

  FIG. 21 shows an example of the imaging range of the imaging units 12101 to 12104. The imaging range 12111 indicates the imaging range of the imaging unit 12101 provided in the front nose, the imaging ranges 12112 and 12113 indicate the imaging ranges of the imaging units 12102 and 12103 provided in the side mirrors, respectively, and the imaging range 12114 The imaging range of the imaging part 12104 provided in the rear bumper or the back door is shown. For example, by superimposing the image data captured by the imaging units 12101 to 12104, an overhead image when the vehicle 12100 is viewed from above is obtained.

  At least one of the imaging units 12101 to 12104 may have a function of acquiring distance information. For example, at least one of the imaging units 12101 to 12104 may be a stereo camera including a plurality of imaging elements, or may be an imaging element having pixels for phase difference detection.

  For example, the microcomputer 12051, based on the distance information obtained from the imaging units 12101 to 12104, the distance to each three-dimensional object in the imaging range 12111 to 12114 and the temporal change in this distance (relative speed with respect to the vehicle 12100). In particular, it is possible to extract, as a preceding vehicle, a three-dimensional object that travels at a predetermined speed (for example, 0 km / h or more) in the same direction as the vehicle 12100, particularly the closest three-dimensional object on the traveling path of the vehicle 12100. it can. Further, the microcomputer 12051 can set an inter-vehicle distance to be secured in advance before the preceding vehicle, and can perform automatic brake control (including follow-up stop control), automatic acceleration control (including follow-up start control), and the like. Thus, cooperative control for the purpose of autonomous driving or the like autonomously traveling without depending on the operation of the driver can be performed.

  For example, the microcomputer 12051 converts the three-dimensional object data related to the three-dimensional object to other three-dimensional objects such as a two-wheeled vehicle, a normal vehicle, a large vehicle, a pedestrian, and a utility pole based on the distance information obtained from the imaging units 12101 to 12104. It can be classified and extracted and used for automatic avoidance of obstacles. For example, the microcomputer 12051 identifies obstacles around the vehicle 12100 as obstacles that are visible to the driver of the vehicle 12100 and obstacles that are difficult to see. The microcomputer 12051 determines the collision risk indicating the risk of collision with each obstacle, and when the collision risk is equal to or higher than the set value and there is a possibility of collision, the microcomputer 12051 is connected via the audio speaker 12061 or the display unit 12062. By outputting an alarm to the driver and performing forced deceleration or avoidance steering via the drive system control unit 12010, driving assistance for collision avoidance can be performed.

  At least one of the imaging units 12101 to 12104 may be an infrared camera that detects infrared rays. For example, the microcomputer 12051 can recognize a pedestrian by determining whether a pedestrian is present in the captured images of the imaging units 12101 to 12104. Such pedestrian recognition is, for example, whether or not the user is a pedestrian by performing a pattern matching process on a sequence of feature points indicating the outline of an object and a procedure for extracting feature points in the captured images of the imaging units 12101 to 12104 as infrared cameras. It is carried out by the procedure for determining. When the microcomputer 12051 determines that there is a pedestrian in the captured images of the imaging units 12101 to 12104 and recognizes the pedestrian, the audio image output unit 12052 has a rectangular contour line for emphasizing the recognized pedestrian. The display unit 12062 is controlled so as to be superimposed and displayed. Moreover, the audio | voice image output part 12052 may control the display part 12062 so that the icon etc. which show a pedestrian may be displayed on a desired position.

<4. Example>
Next, examples of the present disclosure will be described in detail. In Experiment 1, the characteristics of each single layer composed of a benzodifuran derivative (CZBDF) and tBPA-IC used as an electron blocking layer were evaluated. In Experiment 2, a photoelectric conversion element including an electron block layer made of CZBDF and tBPA-IC was produced, and its characteristics were evaluated.

[Experiment 1]
As Experiment 1, each characteristic (hole mobility) of the electron block layer which consists of CZBDF represented by said Formula (1-1), and the electron block layer single layer which consists of tBPA-IC represented by following formula (6) , Ionization potential, electron affinity, crystallinity, arithmetic average roughness, and glass transition point).

The hole mobility was calculated from a measurement result obtained by preparing a hole mobility evaluation element. The hole transfer evaluation element was produced using the following method. First, after cleaning a substrate provided with an electrode having a thickness of 50 nm, molybdenum oxide (MoO ₃ ) was formed to a thickness of 0.8 nm on the substrate. Subsequently, CZBDF was deposited to a thickness of 150 nm at a substrate temperature of 0 ° C. and a deposition rate of 0.3 Å / sec. Next, after depositing molybdenum oxide (MoO ₃ ) with a thickness of 3 nm on the CZBDF film, a gold (Au) film with a thickness of 100 nm is formed on the molybdenum oxide (MoO ₃ ) as an electrode, and made of CZBDF. A hole transfer evaluation element provided with an electron blocking layer was produced. A hole transfer evaluation element provided with an electron block layer made of tBPA-IC was also produced using the same method as described above. The hole mobility is obtained by obtaining a current-voltage curve obtained by sweeping the bias voltage applied between the electrodes from 0 V to 10 V using a semiconductor parameter analyzer, and then fitting the curve according to the space charge limited current model. The relationship between the voltage and the voltage was obtained. The hole mobility value obtained here is at 1V.

  The ionization potential and electron affinity were calculated using the following methods. First, CZBDF (or tBPA-IC) was deposited on a glass substrate to a thickness of 35 nm at a substrate temperature of 0 ° C. and a deposition rate of 1.0 kg / sec. Subsequently, UV-Vis spectra of the obtained single film of CZBDF and single film of tBPA-IC were measured, and the energy gap was determined from the wavelength of the absorption edge. Moreover, the same film | membrane was each formed on the ITO substrate, and each ionization potential was calculated | required by the ultraviolet photoelectron spectroscopy (UPS). The electron affinity was determined by subtracting the energy gap from the ionization potential.

  The crystallinity was evaluated using each single film of CZBDF and tBPA-IC formed on the glass substrate when the ionization potential was measured. Specifically, using an X-ray diffractometer (RINT-TTRII manufactured by Rigaku Corporation), the diffraction pattern when each single film was irradiated with copper Kα rays was measured. It was judged whether the single film was composed of crystals or amorphous.

  For the surface roughness, the arithmetic average roughness Ra was calculated using an atomic force microscope. Specifically, using an atomic force microscope AFM (VN-8010 manufactured by Keyence Corporation), the surface shape of each single film of CZBDF and tBPA-IC formed on the glass substrate at the time of measuring the ionization potential was 10 μm × Measurement was performed in a 10 μm square area, and an arithmetic average roughness Ra was calculated for any two line segments based on JIS B 601: 2001.

  The glass transition point was measured using differential scanning calorimetry. Specifically, using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.), 5 mg to 10 mg of CZBDF and tBPA-IC powders were weighed and placed in aluminum (Al) pans, respectively, in a nitrogen atmosphere. It heated to the temperature which each powder fuse | melts with the temperature increase rate of (degreeC / min). Thereafter, the Al pan was taken out from the differential scanning calorimeter, placed on an Al block and rapidly cooled, and this was the first measurement. Subsequently, heating was performed from 30 ° C. to the melting points of CZBDF and tBPA-IC at a rate of temperature increase of 20 ° C./min, and the temperature at which the secondary phase transition appears was measured as the glass transition temperature. Measurement was taken.

From the above experiment, the following values were obtained as physical properties of the electron block layer composed of CZBDF and tBPA-IC. First, the hole mobility of CZBDF is 1E-6 cm ² / Vs, the ionization potential is 6.0 eV, the electron affinity is 2.9 eV, the arithmetic average roughness Ra is 1.0 nm, and the glass transition point is 162 ° C. From the XRD measurement, the crystallinity was found to be amorphous. The hole mobility of tBPA-IC is 1E-5 cm ² / Vs, the ionization potential is 5.5 eV, the electron affinity is 2.4 eV, the arithmetic average roughness (Ra) is 1.1 nm, and the glass transition point is 171 ° C. From the XRD measurement, it was found that the crystallinity was amorphous. Table 1 summarizes the characteristics of the electron block layer made of CZBDF and the electron block layer made of tBPA-IC.

  The ionization potential of the photoelectric conversion layer used in Experiment 2 described later was 5.6 eV to 5.8 eV. The work function of the ITO electrode was 5.0 eV. From this, it was found that both CZBDF and tBPA-IC have the necessary characteristics as the above-described electron blocking layer. That is, in order to efficiently and quickly transport holes generated by the charge separation process in the photoelectric conversion layer to the anode, it has high hole transportability and ionization potential at the same level as the ionization potential of the hole transport material of the photoelectric conversion layer It was found to have potential. Moreover, it turned out that the single layer which consists of each material has an electron affinity lower 1 eV or more than the work function of an adjacent anode (ITO electrode), respectively. Furthermore, it has been found that both CZBDF and tBPA-IC form a uniform amorphous layer having high smoothness and few defects. Furthermore, both CZBDF and tBPA-IC had a high glass transition point of 140 ° C. or higher.

[Experiment 2]
Next, as Experiment 2, photoelectric conversion elements (Experimental Examples 1 to 5) each including an electron block layer made of CZBDF and tBPA-IC were prepared, and the element characteristics (dark current characteristics, external quantum efficiency (EQE) and (Response speed) was evaluated.

(Experimental example 1)
First, a glass substrate with an ITO electrode (lower electrode) was washed by UV / ozone treatment, the substrate was moved to a vacuum deposition machine, and the interior of the chamber was decompressed to 1 × 10 ⁻⁵ Pa or less. Subsequently, while rotating the substrate holder, CZBDF was deposited to a thickness of 10 nm at a deposition rate of 0.3 Å / sec at a substrate temperature of 0 ° C. to form an electronic block layer. Next, DP-BTBT represented by the following formula (7), F ₆ -SubPc-OC ₆ F ₅ and fullerene C ₆₀ represented by the following formula (9) were formed as an electronic block layer as a photoelectric conversion layer, respectively. Vapor deposition was performed at a film rate of 0.75 Å / sec, 0.75 Å / sec, and 0.50 、 / sec. Subsequently, as a buffer layer, B4PyMPM represented by the following formula (8) was formed to a thickness of 5 nm at a film formation rate of 0.3 l / sec. Finally, an AlSiCu alloy was deposited as an upper electrode so as to have a thickness of 100 nm. After that, under a nitrogen atmosphere, heat treatment was performed on the upper electrode at 150 ° C. for 3.5 hours assuming a heating process such as soldering of the color filter, the protective layer, and the photoelectric conversion element. A photoelectric conversion element (Experimental Example 1) having a 1 mm × 1 mm photoelectric conversion region was manufactured by the above manufacturing method.

As fullerene C ₆₀ , nano purple SUH (HPLC purity:> 99.9%, sublimation purified product) manufactured by Frontier Carbon Co., Ltd. was used. F ₆ -SubPc-OC ₆ F ₅ (formula (9)) was synthesized using the following scheme, and the resulting product was purified by sublimation purification and used.

(Experimental example 2)
A photoelectric conversion element (Experimental Example 2) was produced using the same method as in Experimental Example 1 except that the thickness of the electron blocking layer was changed to 5 nm.

(Experimental example 3)
A photoelectric conversion element (Experimental Example 3) was produced using the same method as in Experimental Example 1 except that tBPA-IC shown in the above formula (6) was used as the material of the electron blocking layer.

(Experimental example 4)
A photoelectric conversion element (Experimental Example 4) was produced using the same method as in Experimental Example 3 except that the thickness of the electron blocking layer was changed to 5 nm.

(Experimental example 5)
A photoelectric conversion element (Experimental Example 5) was produced using the same method as in Experimental Example 1 except that no electron blocking layer was formed.

The dark current characteristics and external quantum efficiency (EQE) of Experimental Examples 1 to 5 were evaluated using a semiconductor parameter analyzer. Moreover, the response speed was evaluated. Regarding the dark current characteristics, the current value was measured when the bias voltage applied between the electrodes of the photoelectric conversion element was set to −1 V in the dark state. Regarding the external quantum efficiency, the amount of light (LED light with a wavelength of 560 nm) irradiated from the light source to the photoelectric conversion element through the filter is 1.62 μW / cm ^2, and the bias voltage applied between the electrodes is the semiconductor parameter analyzer. The effective number of carriers is obtained by subtracting the dark current value from the bright current value when the voltage applied to the lower electrode with respect to the upper electrode is set to -1 V with respect to the upper electrode. Calculated by dividing. Regarding the response speed, the light applied when the voltage applied to the lower electrode with respect to the upper electrode is set to -1 V, the light having a wavelength of 560 nm and the light amount of 1.62 μW / cm ² is irradiated, and then the light irradiation is stopped. Immediately after stopping, the time until the current flowing between the upper electrode and the lower electrode became 3% was measured.

  Table 1 summarizes the material and film thickness, dark current, external quantum efficiency, and normalized response speed of the electron block layers of Experimental Examples 1 to 5. The normalized response speed is a relative value when the result of Experimental Example 1 is 1.

  CZBDF is used as the material of the electron blocking layer and the thickness thereof is 10 nm in Experimental Example 1, compared with Experimental Example 3 where tBPA-IC is used as the material of the electron blocking layer and the film thickness is 10 nm. Equivalent external electronic efficiency and fast response speed are shown. In Experimental Example 2, the thickness of the electron blocking layer is halved (5 nm) compared to Experimental Example 1, and similarly, in comparison with Experimental Example 4 in which the thickness of the electron blocking layer is 5 nm. High external electron efficiency and fast response speed. The results of Experimental Examples 1 and 2 showed lower dark current, equivalent external quantum efficiency, and faster normalized response speed compared with Experimental Example 5 in which no electron blocking layer was provided.

  In Experimental Example 5, the reason for the high dark current is presumed to be that electrons from the adjacent lower electrode were injected because there was no electron blocking layer. In Experimental Example 5, a low response speed was shown. This is presumably because the extraction of holes into the lower electrode was delayed. The latter mechanism is considered to be caused by aggregation or segregation of components other than the hole transport material in the photoelectric conversion layer at the interface of the lower electrode after annealing. The external quantum efficiency is the same value as in Experimental Example 1 and the like, but since it is actually influenced by the photo-induced injection current, it seems to be overestimated.

  The reason why the device characteristics of Experimental Examples 1 and 2 were superior to that of Experimental Examples 3 and 4 was that the glass transition point (Tg) of tBPA-IC was higher than that of CZBDF. However, it is considered that the photoelectric conversion elements of Experimental Examples 1 and 2 have higher adhesiveness with the ITO of the lower electrode as another reason. In Experimental Examples 3 and 4, when the thickness of the electron block layer made of tBPA-IC was 5 nm, the external quantum efficiency was particularly lower than that of 10 nm. This is presumably because in Experimental Example 4 having a film thickness of 5 nm, tBPA-IC diffused into an adjacent layer after annealing. On the other hand, in Experimental Examples 1 and 2 using CZBDF, since CZBDF has oxygen atoms in the molecule, intermolecular force works between the oxygen atoms of ITO constituting the lower electrode and does not have oxygen. It is considered that the adhesiveness was improved as compared with tBPA-IC, and as a result, an electron block layer having high heat resistance was formed. Compared with Experimental Examples 3 and 4, Experimental Examples 1 and 2 showed a higher response speed because the electron block layers of Experimental Examples 1 and 2 with higher adhesion showed smoother carrier movement at the interface. This is probably because of As described above, it is considered that the electron blocking layer using the benzodifuran derivative functions as an excellent electron blocking layer even after annealing, and exhibits a low dark current, a high external quantum efficiency, and a high standardized response speed.

  The first and second embodiments and examples have been described above, but the present disclosure is not limited to the above-described embodiments and the like, and various modifications are possible. For example, in the photoelectric conversion element described above, the lower electrode 15 is used as an anode and the upper electrode 18 is used as a cathode. However, the present invention is not limited thereto, and the lower electrode 15 is used as a cathode and the upper electrode 18 is used as an anode. Also good. In that case, the electron block layer 16 is provided between the photoelectric conversion layer 17 and the upper electrode 18.

  Moreover, in the said embodiment, the organic photoelectric conversion part 11G which detects green light, the inorganic photoelectric conversion part 11B and the inorganic photoelectric conversion part 11R which each detect blue light and red light were laminated | stacked as a photoelectric conversion element. Although configured, the present disclosure is not limited to such a structure. That is, the organic photoelectric conversion unit may detect red light or blue light, or the inorganic photoelectric conversion unit may detect green light.

  Furthermore, 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. Furthermore, the organic photoelectric conversion unit and the inorganic photoelectric conversion unit are not limited to a structure in which the organic photoelectric conversion unit and the inorganic photoelectric conversion unit are stacked in the vertical direction, and may be arranged in parallel along the substrate surface.

  Further, in the above-described embodiments and the like, the configuration of the backside illumination type solid-state imaging device is illustrated, but the present disclosure can be applied to a front-side illumination type solid-state imaging device. Furthermore, the photoelectric conversion element of the present disclosure does not need to include all the components described in the above embodiments, and may include other layers.

  Furthermore, in the said embodiment etc., although the example using the photoelectric conversion element 10A as an image pick-up element which comprises the imaging device 1 was shown, you may apply the photoelectric conversion element 10A of this indication to a solar cell.

  In addition, the effect described in this specification is an illustration to the last, and is not limited, Moreover, there may exist another effect.

（Ｒ１，Ｒ２，Ｒ３，Ｒ４は、各々独立して、水素原子または炭素数４以上４０以下のアリール基、ヘテロアリール基、カルバゾール基、ジフェニルアミノ基あるいはそれらの誘導体であり、Ｒ１，Ｒ２，Ｒ３，Ｒ４のうちの少なくとも１つは、炭素数１２以上４０以下のカルバゾール基またはジフェニルアミノ基あるいはそれらの誘導体である。）
［２］
前記光電変換層は、正孔輸送性材料を１種以上含む、前記［１］に記載の光電変換素子。
［３］
前記光電変換層は、波長４００ｎｍ以上７５０ｎｍ以下の可視光領域における極大吸収係数が５００００ｃｍ^-1以上の色材を含む、前記［１］または［２］に記載の光電変換素子。
［４］
前記色材は、下記一般式（２）で表されるサブフタロシアニンまたはその誘導体である、前記［３］に記載の光電変換素子。

（Ｒ５〜Ｒ１６は、各々独立して、水素原子、ハロゲン原子、直鎖，分岐，または環状アルキル基、チオアルキル基、チオアリール基、アリールスルホニル基、アルキルスルホニル基、アミノ基、アルキルアミノ基、アリールアミノ基、ヒドロキシ基、アルコキシ基、アシルアミノ基、アシルオキシ基、フェニル基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、アシル基、スルホニル基、シアノ基およびニトロ基からなる群から選択され、且つ、隣接した任意のＲ５〜Ｒ１６は縮合脂肪族環または縮合芳香環の一部であってもよい。前記縮合脂肪族環または縮合芳香環は、炭素以外の1または複数の原子を含んでいてもよい。Ｍはホウ素または２価あるいは３価の金属である。Ｘは、ハロゲン、ヒドロキシ基、チオール基、イミド基、置換もしくは未置換のアルコキシ基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアルキル基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基からなる群より選択されるいずれかの置換基である。）
［５］
前記光電変換層は、電子輸送性材料としてフラーレンまたはその誘導体を１種以上含む、前記［１］乃至［４］のうちのいずれかに記載の光電変換素子。
［６］
前記フラーレンまたはその誘導体は、下記一般式（３）または一般式（４）で表される、前記［５］に記載の光電変換素子。

（Ｒ１７，Ｒ１８は、水素原子、ハロゲン原子、直鎖，分岐または環状のアルキル基、フェニル基、直鎖または縮環した芳香族化合物を有する基、ハロゲン化物を有する基、パーシャルフルオロアルキル基、パーフルオロアルキル基、シリルアルキル基、シリルアルコキシ基、アリールシリル基、アリールスルファニル基、アルキルスルファニル基、アリールスルホニル基、アルキルスルホニル基、アリールスルフィド基、アルキルスルフィド基、アミノ基、アルキルアミノ基、アリールアミノ基、ヒドロキシ基、アルコキシ基、アシルアミノ基、アシルオキシ基、カルボニル基、カルボキシ基、カルボキソアミド基、カルボアルコキシ基、アシル基、スルホニル基、シアノ基、ニトロ基、カルコゲン化物を有する基、ホスフィン基、ホスホン基あるいはそれらの誘導体である。ｎ，ｍは２以上の整数である。）
［７］
前記陽極は金属酸化物によって形成され、前記金属酸化物を構成する金属原子としてスズ（Ｓｎ）、亜鉛（Ｚｎ）、インジウム（Ｉｎ）、ケイ素（Ｓｉ）、ジルコニウム（Ｚｒ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、タングステン（Ｗ）、クロム（Ｃｒ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、タンタル（Ｔａ）、ニオブ（Ｎｂ）およびモリブデン（Ｍｏ）のうちのいずれか１種以上を含む、前記［１］乃至［６］のうちのいずれかに記載の光電変換素子。
［８］
前記陽極および前記陰極の一方は複数の電極からなる、前記［１］乃至［７］のうちのいずれかに記載の光電変換素子。
［９］
前記複数の電極として電荷読み出し電極および電荷蓄積電極を有する、前記［８］に記載の光電変換素子。
［１０］
各画素が１または複数の有機光電変換部を有し、
前記有機光電変換部は、
陽極と、
前記陽極と対向配置された陰極と、
前記陽極と前記陰極との間に設けられた光電変換層と、
前記陽極と前記光電変換層との間に設けられると共に、下記一般式（１）で表される有機半導体材料を含む電子ブロック層と
を備えた撮像装置。

（Ｒ１，Ｒ２，Ｒ３，Ｒ４は、各々独立して、水素原子または炭素数４以上４０以下のアリール基、ヘテロアリール基、カルバゾール基、ジフェニルアミノ基あるいはそれらの誘導体であり、Ｒ１，Ｒ２，Ｒ３，Ｒ４のうちの少なくとも１つは、炭素数１２以上４０以下のカルバゾール基またはジフェニルアミノ基あるいはそれらの誘導体である。）
［１１］
各画素では、１または複数の前記有機光電変換部と、前記有機光電変換部とは異なる波長域の光電変換を行う１または複数の無機光電変換部とが積層されている、前記［１０］に記載の撮像装置。
［１２］
前記無機光電変換部は、半導体基板内に埋め込み形成され、
前記有機光電変換部は、前記半導体基板の第１面側に形成されている、前記［１１］に記載の撮像装置。
［１３］
前記半導体基板の、前記第１面に対向する第２面側に多層配線層が形成されている、前記［１２］に記載の撮像装置。
［１４］
前記有機光電変換部が緑色光の光電変換を行い、
前記半導体基板内に、青色光の光電変換を行う無機光電変換部と、赤色光の光電変換を行う無機光電変換部とが積層されている、前記［１２］または［１３］に記載の撮像装置。 The present disclosure may be configured as follows.
[1]
The anode,
A cathode disposed opposite to the anode;
A photoelectric conversion layer provided between the anode and the cathode;
The photoelectric conversion element provided with the electronic block layer containing the organic-semiconductor material represented by following General formula (1) while being provided between the said anode and the said photoelectric converting layer.

(R1, R2, R3 and R4 are each independently a hydrogen atom or an aryl group, heteroaryl group, carbazole group, diphenylamino group or derivatives thereof having 4 to 40 carbon atoms, and R1, R2, R3 , R4 is a carbazole group having 12 to 40 carbon atoms, a diphenylamino group, or a derivative thereof.)
[2]
The photoelectric conversion layer according to [1], wherein the photoelectric conversion layer includes at least one hole transporting material.
[3]
The photoelectric conversion layer according to [1] or [2], wherein the photoelectric conversion layer includes a colorant having a maximum absorption coefficient in a visible light region having a wavelength of 400 nm or more and 750 nm or less of 50000 cm ⁻¹ or more.
[4]
The photoelectric conversion element according to [3], wherein the colorant is subphthalocyanine represented by the following general formula (2) or a derivative thereof.

(R5 to R16 are each independently a hydrogen atom, a halogen atom, a linear, branched, or cyclic alkyl group, a thioalkyl group, a thioaryl group, an arylsulfonyl group, an alkylsulfonyl group, an amino group, an alkylamino group, an arylamino group. Selected from the group consisting of a group, hydroxy group, alkoxy group, acylamino group, acyloxy group, phenyl group, carboxy group, carboxamide group, carboalkoxy group, acyl group, sulfonyl group, cyano group and nitro group, and adjacent R5 to R16 may be a part of a condensed aliphatic ring or a condensed aromatic ring, and the condensed aliphatic ring or the condensed aromatic ring may contain one or more atoms other than carbon. M is boron or a divalent or trivalent metal, X is halogen, hydroxy group, thiol group, imi Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group Any substituent.)
[5]
The photoelectric conversion layer according to any one of [1] to [4], wherein the photoelectric conversion layer includes at least one fullerene or a derivative thereof as an electron transporting material.
[6]
The fullerene or a derivative thereof is the photoelectric conversion element according to the above [5], which is represented by the following general formula (3) or general formula (4).

(R17 and R18 are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a phenyl group, a group having a linear or condensed aromatic compound, a group having a halide, a partial fluoroalkyl group, a perfluoroalkyl group, Fluoroalkyl group, silylalkyl group, silylalkoxy group, arylsilyl group, arylsulfanyl group, alkylsulfanyl group, arylsulfonyl group, alkylsulfonyl group, arylsulfide group, alkylsulfide group, amino group, alkylamino group, arylamino group Hydroxy group, alkoxy group, acylamino group, acyloxy group, carbonyl group, carboxy group, carboxamide group, carboalkoxy group, acyl group, sulfonyl group, cyano group, nitro group, chalcogenated group, phosphine group, phospho group Is a group, or a derivative thereof .n, m is an integer of 2 or more.)
[7]
The anode is formed of a metal oxide, and tin (Sn), zinc (Zn), indium (In), silicon (Si), zirconium (Zr), aluminum (Al) as metal atoms constituting the metal oxide, Including one or more of gallium (Ga), tungsten (W), chromium (Cr), cobalt (Co), nickel (Ni), tantalum (Ta), niobium (Nb) and molybdenum (Mo), The photoelectric conversion element according to any one of [1] to [6].
[8]
One of the said anode and the said cathode consists of a several electrode, The photoelectric conversion element in any one of said [1] thru | or [7].
[9]
The photoelectric conversion element according to [8], wherein the plurality of electrodes include a charge readout electrode and a charge storage electrode.
[10]
Each pixel has one or more organic photoelectric conversion units,
The organic photoelectric conversion unit is
The anode,
A cathode disposed opposite to the anode;
A photoelectric conversion layer provided between the anode and the cathode;
An imaging device comprising: an electronic block layer that is provided between the anode and the photoelectric conversion layer and includes an organic semiconductor material represented by the following general formula (1).

(R1, R2, R3 and R4 are each independently a hydrogen atom or an aryl group, heteroaryl group, carbazole group, diphenylamino group or derivatives thereof having 4 to 40 carbon atoms, and R1, R2, R3 , R4 is a carbazole group having 12 to 40 carbon atoms, a diphenylamino group, or a derivative thereof.)
[11]
In each pixel, the one or more organic photoelectric conversion units 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. The imaging device described.
[12]
The inorganic photoelectric conversion part is embedded in a semiconductor substrate,
The said photoelectric conversion part is an imaging device as described in said [11] currently formed in the 1st surface side of the said semiconductor substrate.
[13]
The imaging device according to [12], wherein a multilayer wiring layer is formed on a second surface side of the semiconductor substrate facing the first surface.
[14]
The organic photoelectric conversion unit performs green light photoelectric conversion,
The imaging device 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. .

  DESCRIPTION OF SYMBOLS 1 ... Imaging device, 2 ... Electronic device (camera), 10A, 10B ... Photoelectric conversion element, 11 ... Semiconductor substrate, 11G ... Organic photoelectric conversion part, 11R, 11B ... Inorganic photoelectric conversion part, 12, 14 ... Interlayer insulation layer, 12A ... Fixed charge layer, 12B ... Dielectric layer, 13A, 13C ... Pad part, 13B ... Upper contact, 15 ... Lower electrode, 16 ... Electron blocking layer, 17 ... Photoelectric conversion layer, 18 ... Upper electrode, 19 ... Protective layer 50: On-chip lens layer, 50L: On-chip lens.

Claims (14)

The anode,
A cathode disposed opposite to the anode;
A photoelectric conversion layer provided between the anode and the cathode;
The photoelectric conversion element provided with the electronic block layer containing the organic-semiconductor material represented by following General formula (1) while being provided between the said anode and the said photoelectric converting layer.

(R1, R2, R3 and R4 are each independently a hydrogen atom or an aryl group, heteroaryl group, carbazole group, diphenylamino group or derivatives thereof having 4 to 40 carbon atoms, and R1, R2, R3 , R4 is a carbazole group having 12 to 40 carbon atoms, a diphenylamino group, or a derivative thereof.)   The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer includes at least one hole transporting material. The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer includes a colorant having a maximum absorption coefficient in a visible light region having a wavelength of 400 nm or more and 750 nm or less of 50000 cm ⁻¹ or more. The photoelectric conversion element according to claim 3, wherein the coloring material is subphthalocyanine represented by the following general formula (2) or a derivative thereof.

(R5 to R16 are each independently a hydrogen atom, a halogen atom, a linear, branched, or cyclic alkyl group, a thioalkyl group, a thioaryl group, an arylsulfonyl group, an alkylsulfonyl group, an amino group, an alkylamino group, an arylamino group. Selected from the group consisting of a group, hydroxy group, alkoxy group, acylamino group, acyloxy group, phenyl group, carboxy group, carboxamide group, carboalkoxy group, acyl group, sulfonyl group, cyano group and nitro group, and adjacent R5 to R16 may be a part of a condensed aliphatic ring or a condensed aromatic ring, and the condensed aliphatic ring or the condensed aromatic ring may contain one or more atoms other than carbon. M is boron or a divalent or trivalent metal, X is halogen, hydroxy group, thiol group, imi Group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group Any substituent.)   The photoelectric conversion element according to claim 1, wherein the photoelectric conversion layer contains at least one fullerene or a derivative thereof as an electron transporting material. The photoelectric conversion device according to claim 5, wherein the fullerene or a derivative thereof is represented by the following general formula (3) or general formula (4).

(R17 and R18 are a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, a phenyl group, a group having a linear or condensed aromatic compound, a group having a halide, a partial fluoroalkyl group, a perfluoroalkyl group, Fluoroalkyl group, silylalkyl group, silylalkoxy group, arylsilyl group, arylsulfanyl group, alkylsulfanyl group, arylsulfonyl group, alkylsulfonyl group, arylsulfide group, alkylsulfide group, amino group, alkylamino group, arylamino group Hydroxy group, alkoxy group, acylamino group, acyloxy group, carbonyl group, carboxy group, carboxamide group, carboalkoxy group, acyl group, sulfonyl group, cyano group, nitro group, chalcogenated group, phosphine group, phospho group Is a group, or a derivative thereof .n, m is an integer of 2 or more.)   The anode is formed of a metal oxide, and tin (Sn), zinc (Zn), indium (In), silicon (Si), zirconium (Zr), aluminum (Al) as metal atoms constituting the metal oxide, Including one or more of gallium (Ga), tungsten (W), chromium (Cr), cobalt (Co), nickel (Ni), tantalum (Ta), niobium (Nb) and molybdenum (Mo), The photoelectric conversion element according to claim 1.   The photoelectric conversion element according to claim 1, wherein one of the anode and the cathode includes a plurality of electrodes.   The photoelectric conversion element according to claim 8, comprising a charge readout electrode and a charge storage electrode as the plurality of electrodes. Each pixel has one or more organic photoelectric conversion units,
The organic photoelectric conversion unit is
The anode,
A cathode disposed opposite to the anode;
A photoelectric conversion layer provided between the anode and the cathode;
An imaging device comprising: an electronic block layer that is provided between the anode and the photoelectric conversion layer and includes an organic semiconductor material represented by the following general formula (1).

(R1, R2, R3 and R4 are each independently a hydrogen atom or an aryl group, heteroaryl group, carbazole group, diphenylamino group or derivatives thereof having 4 to 40 carbon atoms, and R1, R2, R3 , R4 is a carbazole group having 12 to 40 carbon atoms, a diphenylamino group, or a derivative thereof.)   11. Each pixel includes one or more organic photoelectric conversion units and one or more inorganic photoelectric conversion units that perform photoelectric conversion in a wavelength region different from that of the organic photoelectric conversion unit. Imaging device. The inorganic photoelectric conversion part is embedded in a semiconductor substrate,
The imaging device according to claim 11, wherein the organic photoelectric conversion unit is formed on a first surface side of the semiconductor substrate.   The imaging device according to claim 12, wherein a multilayer wiring layer is formed on a second surface side of the semiconductor substrate facing the first surface. The organic photoelectric conversion unit performs green light photoelectric conversion,
The imaging apparatus according to claim 12, wherein an inorganic photoelectric conversion unit that performs blue light photoelectric conversion and an inorganic photoelectric conversion unit that performs red light photoelectric conversion are stacked in the semiconductor substrate.

Images