PHOTOELECTRIC CONVERSION ELEMENT AND SOLID-BODY IMAGE DEVICE

Abstract

Photoelectric conversion element (10) comprising: a first electrode (15); a second electrode (17) arranged opposite the first electrode; and an organic photoelectric conversion layer (16) provided between the first electrode and the second electrode, wherein the organic photoelectric conversion layer comprises a domain of an organic semiconductor material, wherein the domain of the organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in a film thickness direction and has a smaller domain length in a plane direction of the organic photoelectric conversion layer than a domain length in the film thickness direction of the organic photoelectric conversion layer, wherein the organic photoelectric conversion layer (16) comprises p-type semiconductor molecules that are periodically stacked.such that an interference pattern is obtained in a cross-sectional photograph in the direction of the film thickness when the cross-sectional photograph is taken with a transmission electron microscope under defocusing conditions, wherein the interference pattern comprises two or more lines, and wherein an interval between the two or more lines belonging to the interference pattern lies within an interval of 50% and 150% of the molecular length of the p-type semiconductor molecules.

Description

Technical area

[0001] The present disclosure relates to a photoelectric conversion element and a solid-state image acquisition device including the latter. Background technology

[0002] In recent years, devices with organic thin films have been developed. One such device is an organic photoelectric conversion element. An organic thin-film solar cell, an organic imaging element, or similar device incorporating this organic photoelectric conversion element has been proposed. A bulk heterostructure is incorporated into the organic photoelectric conversion element to increase the external quantum yield. This bulk heterostructure consists of a mixture of an organic p-type semiconductor and an organic n-type semiconductor. However, the organic photoelectric conversion element suffers from the problem that, due to the low conductivity properties of organic semiconductors, it is not possible to achieve a sufficient external quantum yield. Furthermore, the organic imaging element has the problem that its electrical output signal is slightly delayed relative to the incident light.

[0003] It has generally been found that the molecular orientation is important for the conductivity of an organic semiconductor. The same applies to an organic photoelectric conversion element with a bulk heterostructure. For this reason, in an organic photoelectric conversion element where a conduction direction is perpendicular to a substrate, it is preferable for the organic semiconductor to be oriented parallel to the substrate. In contrast, for example, PTL 1 reveals a photoelectric conversion element containing an organic semiconductor compound with a horizontal orientation. PTL 2 shows, for example, an organic thin-film solar cell in which an orientation control layer is provided in a lower layer of an i-layer.PTL 3, for example, shows a method for producing an organic photoelectric conversion element that controls the orientation of a photoelectric conversion layer by controlling the substrate temperature to form a film. List of citations from patent literature PTL 1: Japanese unexamined patent application, publication number 2009-60053 PTL 2: Japanese unexamined patent application, publication number 2007-59457 PTL 3: Japanese unexamined patent application, publication number 2008-258421 Summary of the invention Problems to be solved by the invention

[0004] As described above, the photoelectric conversion element, which contains an organic semiconductor material, is requested to increase the external quantum yield and response speed.

[0005] It is desirable to provide a photoelectric conversion element and a solid-state imaging device, each of which will enable the external quantum yield and reaction rate to be increased.

[0006] A photoelectric conversion element according to one embodiment of the present disclosure comprises: a first electrode; a second electrode arranged opposite the first electrode; and an organic photoelectric conversion layer provided between the first and second electrodes. The organic photoelectric conversion layer contains a domain of an organic semiconductor material. The domain of the organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in a film thickness direction and has a shorter domain length in a plane direction of the organic photoelectric conversion layer than a domain length in the film thickness direction of the organic photoelectric conversion layer.

[0007] A solid-state image acquisition device according to an embodiment of the present disclosure includes pixels, each containing one or more organic photoelectric conversion sections, and includes the photoelectric conversion element described above according to the embodiment of the present disclosure as the organic photoelectric conversion section.

[0008] In each of the photoelectric conversion elements according to the embodiment of the present disclosure and the solid-state imaging device according to the embodiment of the present disclosure, the organic photoelectric conversion layer provided between the first electrode and the second electrode contains the single organic semiconductor material that forms the domain with the predetermined shape in the layer. The domain of this single organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in the film thickness direction and has a shorter domain length in the plane direction of the organic photoelectric conversion layer than the domain length in the film thickness direction. This makes it possible to appropriately control a mixture state of organic semiconductor materials contained in the organic photoelectric conversion layer.

[0009] The photoelectric conversion element according to the embodiment of the present disclosure and the solid-state imaging device according to the embodiment of the present disclosure each contain the organic semiconductor material that forms the domain described above in the layer, and the organic semiconductor materials contained in the organic photoelectric conversion layer are thus controlled in a suitable mixing state. This makes it possible to increase the external quantum yield and the reaction rate.

[0010] It should be noted that the effects described here are not necessarily limited, but all effects described in the present disclosure may be included. List of characters [ Fig. 1] Fig.Figure 1 is a schematic cross-sectional view of a configuration of a photoelectric conversion element according to an embodiment of the present disclosure. [ Fig. 2] Fig. Figure 2 is a schematic diagram illustrating an example of a mixing state of the respective organic semiconductor materials in an organic photoelectric conversion layer, as shown in Fig. 1 is shown. [ Fig. 3] Fig. Figure 3 is a TEM image used to describe an interference pattern. [ Fig. 4] Fig. 4 is a schematic top view of a configuration of a unit pixel of the in Fig. 1 photoelectric conversion element shown. [ Fig. 5] Fig. 5 is a schematic cross-sectional view to describe a method for producing the in Fig. 1 photoelectric conversion element shown. [ Fig. 6] Fig.6 is a schematic cross-sectional view showing a process according to Fig. 5 illustrates. [ Fig. 7] Fig. Figure 7 is a schematic cross-sectional view of a configuration of a photoelectric conversion element according to a modification example of the present disclosure. [ Fig. 8] Fig. Figure 8 is a block diagram showing the overall configuration of a solid-state image capture element, including the one shown in Fig. 1 illustrates the photoelectric conversion element shown. [ Fig. 9] Fig. Figure 9 is a functional block diagram that shows an example of a solid-state image acquisition device (camera) with the one described in Figure 9. Fig. 8 illustrated solid-state image capture element. [ Fig. 10] Fig. Figure 10 is a block diagram that shows an example of a schematic configuration of an in-vivo information acquisition system. [ Fig. 11] Fig. Figure 11 is a view showing an example of a schematic configuration of an endoscopic surgical system. [ Fig. 12] Fig. Figure 12 is a block diagram showing an example of a functional configuration of a camera head and a camera control unit (CCU). [ Fig. 13] Fig. Figure 13 is a block diagram that shows an example of the schematic structure of a vehicle control system. [ Fig. 14] Fig. Figure 14 is an auxiliary diagram to illustrate an example of the installation positions of an outside vehicle information acquisition section and an imaging section. [ Fig. 15] Fig. Figure 15 is a diagram illustrating a TEM image (A) of experimental example 1 and its signal intensity (B). [ Fig. 16] Fig. Figure 16 contains TEM images of experiment examples 1 and 4. [ Fig. 17] Fig.Figure 17 contains TEM images of experimental examples 6 and 8. Modes for carrying out the invention

[0011] In the following, embodiments of the present disclosure are described in detail with reference to the drawings. The following description is a specific example of the present disclosure, but the present disclosure is not limited to the following embodiment. Furthermore, the present disclosure is not limited to the arrangement, dimensions, ratios, and the like of the respective components shown in the accompanying diagrams. It should be noted that the description is given in the following order. 1. Embodiment (A photoelectric conversion element in which an organic photoelectric conversion layer contains an organic semiconductor material forming a domain with a predetermined shape) 1-1. Configuration of the photoelectric conversion element 1-2. Method for producing a photoelectric conversion element 1-3. Function and effects 2. Modification example (A photoelectric conversion element in which a multitude of organic photoelectric conversion sections are stacked) 3. Application examples 4. Work examples <Ausführungsform>

[0012] Fig. Figure 1 illustrates a cross-sectional configuration of a photoelectric conversion element (photoelectric conversion element). 10 ) according to an embodiment of the present disclosure. The photoelectric conversion element 10 is, for example, in a pixel (unit pixel P) in a solid-state imaging device (solid-state imaging device). 1) include, for example, a CCD image sensor (CCD = Charge Coupled Device) or a CMOS image sensor (CMOS = Complementary Metal Oxide Semiconductor) of the back-illumination type (backside light reception type) (see Fig. 8) The photoelectric conversion element 10 is of a so-called vertical spectroscopic type, in which an organic photoelectric conversion section 11G and two inorganic photoelectric conversion sections 11B and 11R are arranged vertically, one above the other. The organic photoelectric conversion section 11G and the two inorganic photoelectric conversion sections 11B and 11R They selectively detect corresponding light components in different wavelength ranges to perform the photoelectric conversion. In the present embodiment, an organic photoelectric conversion layer is used. 16, which are in the organic photoelectric conversion section 11G It includes a configuration in which the organic photoelectric conversion layer 16 It is formed using an organic semiconductor material. The organic semiconductor material forms a domain with a predetermined shape within the layer. (Configuration of the photoelectric conversion element)

[0013] In the photoelectric conversion element 10 are one organic photoelectric conversion section for each unit pixel P 11G and two inorganic photoelectric conversion sections 11B and 11R Stacked vertically. The inorganic photoelectric conversion sections 11B and 11R are embedded in the semiconductor substrate 11embedded and formed therein and in the direction of the thickness of the semiconductor substrate 11 stacked. The organic photoelectric conversion section 11G contains the organic photoelectric conversion layer 16 , which contains a p-type semiconductor and an n-type semiconductor and exhibits a bulk heterojunction structure in a single layer. The bulk heterojunction structure is a p / n junction surface formed by a mixture of a p-type semiconductor and an n-type semiconductor.

[0014] The organic photoelectric conversion section 11G and the inorganic photoelectric conversion sections 11B and 11R They carry out the photoelectric conversion by selectively capturing corresponding light components with different wavelengths. In particular, the organic photoelectric conversion section 11Ga green (G) color signal appears. The inorganic photoelectric conversion sections 11B and 11R Each detects a blue (B) and a red (R) color signal using the difference in absorption coefficients. This makes the photoelectric conversion element 10 able to capture multiple types of color signals in one pixel without using a color filter.

[0015] It should be noted that the present embodiment describes a case in which an electron is read as the signal charge (case in which the n-type semiconductor region is used as the photoelectric conversion layer) of an electron-hole pair generated by photoelectric conversion. Furthermore, in the drawings, “+” for “p” and “n” indicates that the concentration of p-type or n-type impurities is high, and “++” indicates that the concentration of p-type or n-type impurities is even higher than “+”.

[0016] The semiconductor substrate 11 It contains, for example, an n-type silicon (Si) substrate and has a p-well 61 in a predetermined area. A second surface (front surface of the semiconductor substrate) 11 ) 11S2 the p-tub 61is, for example, with various floating or potential-free diffusions (floating or potential-free diffusion layers) FD (e.g. FD1 , FD2 and FD3 ), various transistors Tr (e.g. vertical transistor (transfer transistor) Tr1 , transfer transistor Tr2 , amplifier transistor (modulation element) AMP and reset transistor RST) and a multilayer wiring line 70 equipped. The multi-layered wiring cable 70 has a configuration where, for example, the wiring levels 71 , 72 and 73 in an insulating layer 74 are stacked. In addition, a peripheral part of the semiconductor substrate is 11 equipped with a peripheral circuit (not shown) which includes a logic circuit or similar.

[0017] It should be noted that Fig. 1 the first side of the surface 11S1 of the semiconductor substrate11 as a surface for light incidence S1 and the second side of surface 11S2 as the wiring layer side S2 represents.

[0018] The inorganic photoelectric conversion sections 11B and 11R Each contains, for example, a PIN-type (Positive Intrinsic Negative) photodiode and each has a pn junction in a predetermined area of ​​the semiconductor substrate. 11 The inorganic photoelectric conversion sections 11B and 11R They enable the scattering of light in a vertical direction by using the wavelength bands of the absorbed light, which differ depending on the depth of incidence on the silicon substrate.

[0019] The inorganic photoelectric conversion section 11BIt selectively detects blue light to accumulate the signal charge corresponding to blue and is positioned at a depth that allows for efficient photoelectric conversion of the blue light. The inorganic photoelectric conversion section 11R It selectively detects red light to accumulate the signal charge corresponding to red and is positioned at a depth that allows for efficient photoelectric conversion of the red light. It should be noted that blue (B) is a color corresponding, for example, to a wavelength range of 450 nm to 495 nm, and red (R) is a color corresponding, for example, to a wavelength range of 620 nm to 750 nm. It is sufficient if the inorganic photoelectric conversion sections 11B and 11R are able to detect light components of a part or all of the respective wavelength bands.

[0020] Specifically included, as in Fig.Figure 1 shows the inorganic photoelectric conversion section 11B and the inorganic photoelectric conversion section 11R Each has, for example, a p+ region that serves as a hole accumulation layer and an n region that serves as an electron accumulation layer (they each have a pnp stack structure). The n region of the inorganic photoelectric conversion section 11B is with the vertical transistor Tr1 coupled. The p+ region of the inorganic photoelectric conversion section 11B bends along the vertical transistor Tr1 and is associated with the p+ region of the inorganic photoelectric conversion section 11R tied together.

[0021] As described above, the second surface is 11S2 of the semiconductor substrate. 11 for example with floating or potential-free diffusions (floating or potential-free diffusion layers) FD1 , FD2 and FD3 , the vertical transistor (transfer transistor) Tr1 , the transfer transistor Tr2 , equipped with the amplifier transistor (modulation element) AMP and the reset transistor RST.

[0022] The vertical transistor Tr1 is a transfer transistor that converts the energy in the inorganic photoelectric conversion section 11B generated and accumulated signal charges (here electrons) on the floating or potential-free diffusion FD1 transmits. The signal charges correspond to blue. The inorganic photoelectric conversion section. 11B is located at a deep point on the second surface 11S2 of the semiconductor substrate 11 formed, and therefore it is preferable that the transfer transistors of the inorganic photoelectric conversion section 11B the vertical transistor Tr1 contain.

[0023] The transfer transistorTr2 transfers the energy in the inorganic photoelectric conversion section 11R generated and accumulated signal charges (electrons, here) on the floating or potential-free diffusion FD2 The signal charges correspond to red. The transfer transistor Tr2 It contains, for example, a MOS transistor.

[0024] The amplifier transistor AMP is a modulation element that incorporates a number of components from the organic photoelectric conversion section. 11G The generated charges are modulated into a voltage and contain, for example, a MOS transistor.

[0025] The reset transistor RST resets the charges that were generated by the organic photoelectric conversion section. 11G to the FD3 were transmitted via floating or potential-free diffusion, and contains, for example, a MOS transistor.

[0026] A lower first contact 75 , a lower second contact 76and an upper contact 13B Each contains, for example, a doped silicon material such as PDAS (phosphorus-doped amorphous silicon) or a metallic material such as aluminum (Al), tungsten (W), titanium (Ti), cobalt (Co), hafnium (Hf) or tantalum (Ta).

[0027] The organic photoelectric conversion section 11G is on the first surface side 11S1 of the semiconductor substrate 11 planned. The organic photoelectric conversion section 11G has a configuration where, for example, a lower electrode 15 , the organic photoelectric conversion layer 16 and an upper electrode 17 in this order from the side of the first surface 11S1 of the semiconductor substrate 11 They are stacked. The lower electrode 15 is e.g. for every photoelectric conversion element 10separately formed. The organic photoelectric conversion layer 16 and the upper electrode 17 are designed as successive layers that accommodate the multitude of photoelectric conversion elements 10 are common. The organic photoelectric conversion section 11G is an organic photoelectric conversion element that absorbs green light according to part or all of the selective wavelength bands (e.g., 450 nm or more and 650 nm or less) to generate an electron-hole pair.

[0028] Between the first surface 11S1 of the semiconductor substrate 11 and the lower electrode 15 are e.g. from the side of the semiconductor substrate 11 here the intermediate layer insulating layers 12 and 14stacked in this order. The intermediate insulation layers each have a configuration in which, for example, one layer (solid charge layer) 12A with a fixed charge and a dielectric layer 12B are stacked with insulating properties. On the upper electrode 17 is a protective layer 18 planned. An on-chip lens layer. 19 , which are in an on-chip lens 19L which is contained and also serves as a planarizing layer, is above the protective layer 18 arranged.

[0029] A through-electrode 63 is between the first surface 11S1 and the second surface 11S2 of the semiconductor substrate 11 planned. The organic photoelectric conversion section 11G is via this through-electrode 63 with a gate Gamp of the amplifier transistor AMP and the floating or potential-free diffusion FD3coupled. This means the photoelectric conversion element is 10 able to transfer charges that are in the organic photoelectric conversion section 11G on the first surface 11S1 of the semiconductor substrate 11 are generated via the through-electrode 63 to the second surface 11S2 of the semiconductor substrate 11 to transfer in a cost-effective manner, thereby improving the properties.

[0030] The through-electrode 63 is e.g. for every organic photoelectric conversion section 11G of the photoelectric conversion element 10 provided. The through-electrode 63 It functions as a connector for the organic photoelectric conversion section. 11G and the gate Gamp of the amplifier transistor AMP and the floating or potential-free diffusion FD3and serves as a transmission path for the substances in the organic photoelectric conversion section 11G generated charges.

[0031] The lower end of the through-electrode 63 is e.g. with a coupled section 71A in the wiring layer 71 coupled, and the coupled section 71A and the gate Gamp of the amplifier transistor AMP are connected via the lower first contact 75 coupled. The coupled section 71 and floating or potential-free diffusion FD3 are via the lower second contact 76 with the lower electrode 15 coupled. It should be noted that Fig. 1 the through-electrode 63 It is represented in the form of a cylinder, but this is not a limiting factor. The through-electrode 63 It can, for example, have a conical shape.

[0032] As in Fig.As shown in Figure 1, a reset gate Grst of the reset transistor RST is preferably located next to the floating or potential-free diffusion. FD3 arranged. This makes it possible to cause the reset transistor RST to be activated, which is located in the floating or potential-free diffusion. FD3 to reset accumulated charges.

[0033] In the photoelectric conversion element 10 According to the present explanation, light coming from the side of the upper electrode 17 into the organic photoelectric conversion section 11G is fed in by the organic photoelectric conversion layer 16 absorbed. The excitons thus generated move towards an interface between an electron donor and an electron acceptor, located in the organic photoelectric conversion layer. 16are contained within and undergo exciton separation, i.e., they dissociate into electrons and holes. The charges generated here (electrons and holes) are transferred by diffusion due to a difference in charge carrier concentration or by an internal electric field due to a difference in work function between an anode (here the upper electrode) and the anode (here the upper electrode). 17 ) and a cathode (here the lower electrode) 15 The energy is transported to various electrodes and detected as a photocurrent. Furthermore, applying an electrical potential between the lower electrode enables... 15 and the upper electrode 17 the control of the directions in which electrons and holes are transported.

[0034] The following describes the configurations, materials, or similar aspects of the respective sections.

[0035] The organic photoelectric conversion section 11Gis an organic photoelectric conversion element that absorbs green light according to part or all of the selective wavelength bands (e.g., 450 nm or more and 650 nm or less) to generate an electron-hole pair.

[0036] The lower electrode 15 is provided in an area that directly corresponds to the light-receiving surfaces of the semiconductor substrate 11 formed inorganic photoelectric conversion sections 11B and 11R is facing towards and covers these light-receiving surfaces. The lower electrode 15 It contains an electrically conductive, translucent layer, which, for example, contains ITO (indium tin oxide). This material is used in the lower electrode. 15However, in addition to this ITO, a tin oxide (SnO2)-based material obtained by adding a dopant, or a zinc oxide-based material formed by adding a dopant to zinc oxide (ZnO), can be used. Examples of zinc oxide-based materials are aluminum zinc oxide (AZO), obtained by adding aluminum (Al) as a dopant; gallium zinc oxide (GZO), obtained by adding gallium (Ga); and indium zinc oxide (IZO), obtained by adding indium (In). Furthermore, CuI, InSbO4, ZnMgO, CuInO2, Mg1N2O4, CdO, ZnSnO3, or similar materials can also be used.

[0037] The organic photoelectric conversion layer 16 Converts optical energy into electrical energy. The organic photoelectric conversion layer 16It comprises, for example, two or more types of organic semiconductor materials and preferably, for example, one or both of a p-type semiconductor and an n-type semiconductor. For example, in a case where the organic photoelectric conversion layer 16 The composition comprises two types of organic semiconductor materials, including a p-type semiconductor and an n-type semiconductor. One of the p-type and n-type semiconductors is preferably a material transmitting visible light, and the other is preferably a material that photoelectrically converts light in a selective wavelength range (e.g., 450 nm or more and 650 nm or less). Alternatively, the organic photoelectric conversion layer contains 16Preferably three types of organic semiconductor materials, including a material (light absorber), an n-type semiconductor, and a p-type semiconductor. The material (light absorber) photoelectrically converts light in a selective wavelength range. The n-type semiconductor and the p-type semiconductor each have a transmittance for visible light. The organic photoelectric conversion layer 16 It has a bulk heterostructure in which the multitude of these organic semiconductor materials are randomly mixed in the layer.

[0038] Fig. Figure 2 schematically shows an example of a mixing state of the respective organic semiconductor materials in the organic photoelectric conversion layer. 16 according to the present embodiment. In the organic photoelectric conversion layer 16 , as in Fig.Figure 2 shows, for example, the three types of organic semiconductor materials described above (light absorbers, p-type semiconductors, and n-type semiconductors) randomly mixed. In the organic photoelectric conversion layer 16 The respective organic semiconductor materials form grains (e.g., a grain Gc of the light absorber and a grain Gn of the n-type semiconductor). In the present embodiment, the layer contains a domain (e.g., domain Dp) of at least one (e.g., a p-type semiconductor (an organic semiconductor material)) of a plurality of types of organic semiconductor materials. It should be noted that the domain is, for example, a region containing a continuous array of an organic semiconductor material. Furthermore, the organic photoelectric conversion layer can contain... 16In addition to the domain of a p-type semiconductor, a second domain (e.g., an n-type semiconductor or light absorber) can be formed. Furthermore, a single domain can comprise two or more types of organic semiconductor materials.

[0039] The domain Dp of the p-type semiconductor according to the present embodiment preferably has a percolation structure in which the domain Dp is located in the organic photoelectric conversion layer. 16 The domain Dp of the p-type semiconductor preferably extends vertically in the direction of the film thickness (Y-axis direction). Furthermore, the domain Dp of the p-type semiconductor preferably has a shape in which the length (domain length) of the domain in the plane direction (e.g., X-axis direction) is smaller than the domain length in the film thickness direction. That is, the p-type semiconductor preferably forms the domain Dp, which extends vertically in the p-film thickness direction of the organic photoelectric conversion layer. 16 extends.

[0040] Fig.Figure 3 is an enlarged view of a section of the image (TEM image) obtained by photographing the organic photoelectric conversion layer. 16 (Experimental example) 1 (described below) was obtained using a transmission electron microscope under defocused conditions. The organic photoelectric conversion layer 16 It is fabricated using a p-type semiconductor that forms the domain as described above. In the organic photoelectric conversion layer... 16 According to the present explanation, an interference pattern with two or more lines, as shown by dashed lines in Fig. Figure 3 is shown, confirmed in the area corresponding to the domain Dp. An interference pattern preferably comprises fewer than ten lines.

[0041] This interference pattern is observed because the period of p-type semiconductor molecules, which form a domain in the principal axis direction, and electronic waves cause a phase contrast. That is, paired lines lying adjacent to each other between the two or more lines enclosed in the interference pattern each correspond to the molecular period of the p-type semiconductor molecules in the principal axis direction. The interference pattern extends into the organic photoelectric conversion layer. 16 essentially in the direction of the layer thickness and preferably has a length of 20 nm or more. Furthermore, the angle between the interference pattern and the electrode surface of the lower electrode is 15The interference pattern is formed at angles greater than 45° and 90° or smaller, since the propagation direction of the interference pattern is specific. The distance between these two lines is preferably within ±50% of the molecular length of the p-type semiconductor, for example. Even more preferred is a distance between these two lines within ±30%. That is, p-type semiconductors are periodically stacked in the same direction between the two lines enclosed in the interference pattern. It should be noted that the molecular length of a p-type semiconductor is the length of the molecules of the p-type semiconductor in the principal axis direction.

[0042] As described above, the organic photoelectric conversion layer contains 16Preferably two types of organic semiconductor materials, including an n-type semiconductor and a p-type semiconductor, or three types of organic semiconductor materials, including a light absorber, an n-type semiconductor, and a p-type semiconductor. The layer contains a transition surface (p / n junction) between the p-type semiconductor and the n-type semiconductor. The light absorber has its maximum absorption wavelength in a range of, for example, 450 nm or more and 650 nm or less. The p-type semiconductor acts relatively as an electron donor, and the use of a material with hole transport properties is, for example, preferable. The n-type semiconductor acts relatively as an electron acceptor, and the use of a material with electron transport properties is, for example, preferable. The organic photoelectric conversion layer 16It provides a field in which the excitons generated during light absorption are separated into electrons and holes. Specifically, excitons are separated into electrons and holes at the interface (p / n junction) between the electron donor and the electron acceptor. The thickness of the organic photoelectric conversion layer 16 For example, it is 50 nm to 500 nm. The interface between the organic photoelectric conversion layer 16 and the upper electrode 17 preferably has a surface roughness of 10 nm or less.

[0043] It should be noted that an example in which a p-type semiconductor forms the Dp domain has been described in the present embodiment, but this is not limiting. For example, an n-type semiconductor could form the domain.

[0044] The upper electrode 17contains an electrically conductive film with a light transmittance that is comparable to that of the lower electrode 15 similar. In the solid-state imaging device 1 , which is the photoelectric conversion element 10 as a pixel, this upper electrode can 17 The electrode can be separate for each pixel or configured as a single electrode common to all pixels. The thickness of the upper electrode 17 For example, it is 10 nm to 200 nm.

[0045] It should be noted that between the organic photoelectric conversion layer 16 and the lower electrode 15 and between the organic photoelectric conversion layer 16 and the upper electrode 17 Further layers may be provided. Specifically, for example, an underlying film, a hole transport layer, an electron barrier film, or an organic photoelectric conversion layer. 16, a hole-blocking film, a buffer film, an electron transport layer, a film for adjusting the working function and similar from the side of the lower electrode 15 to be stacked one after the other.

[0046] The solid charge layer 12A The film can be either positively charged or negatively charged. Materials used in negatively charged films include hafnium oxide, aluminum oxide, zirconium oxide, tantalum oxide, titanium oxide, and similar substances. In addition, materials other than those described above may include lanthanum oxide, praseodymium oxide, cerium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, lochmium oxide, thulium oxide, ytterbium oxide, lutetium oxide, yttrium oxide, aluminum nitride film, hafnium oxynitride film, aluminum oxynitride film, or similar substances.

[0047] The solid charge layer 12AIt can also have a configuration in which two or more film types are stacked. This makes it possible to further improve the function of a hole accumulation layer, e.g., in the case of a film with a negative fixed charge.

[0048] Although the materials of the dielectric layer 12B are not particularly limited, the dielectric layer contains 12B e.g. a silicon oxide film, TEOS, a silicon nitride film, a silicon oxynitride film or similar.

[0049] The intermediate layer insulating layer 14 This includes, for example, a single-layer film containing one type of silicon oxide, silicon nitride, silicon oxynitride (SiON) and the like, or a stacked film containing two or more types of these.

[0050] The protective layer 18It contains a material with light transmission and includes, for example, a single-layer film containing silicon oxide, silicon nitride, silicon oxynitride, and similar materials, or a stacked film containing two or more of these. The thickness of the protective layer 18 For example, it ranges from 100 nm to 30000 nm.

[0051] The on-chip lens layer 19 is applied to the protective layer 18 formed and covering their entire surface. The multitude of on-chip lenses (microlenses) 19L is located on the front surface of the on-chip lens layer 19 planned. The on-chip lenses 19L Each light source from above the on-chip lens condenses. 19L The light is applied to the respective light-receiving surfaces of the organic photoelectric conversion section. 11G and the inorganic photoelectric conversion sections 11B and 11RIn the present version, the multilayer wiring cable 70 on the second surface 11S2 side of the semiconductor substrate 11 This allows the respective light-receiving surfaces of the organic photoelectric conversion section to be formed. 11G and the inorganic photoelectric conversion sections 11B and 11R They are arranged close together, making it possible to adjust sensitivity variations between the respective colors produced depending on the F-value of the on-chip lens. 19L to reduce.

[0052] Fig. Figure 4 is a top view of a configuration example of a photoelectric conversion element with one pixel, in which a variety of photoelectric conversion sections (e.g., the inorganic photoelectric conversion sections described above) are located. 11B and 11R and the organic photoelectric conversion section11G ) are stacked, to which the technology according to the present disclosure is applicable. That is to say, Fig. Figure 4 shows an example of a planar configuration of the unit pixel P, located in a pixel section 1a is contained, which e.g. in Fig. 8 is shown.

[0053] The unit pixel P comprises a photoelectric conversion area. 1100 , in which a red photoelectric conversion section (inorganic photoelectric conversion section) 11R in Fig. 1) a blue photoelectric conversion section (inorganic photoelectric conversion section) 11B in Fig. 3) and a green photoelectric conversion section (organic photoelectric conversion section) 11G in Fig. 1) are present (neither of them is in Fig.4), which each photoelectrically convert light components of wavelengths R (red), G (green) and B (blue), are stacked in three layers in the order of the green photoelectric conversion section, the blue photoelectric conversion section and the red photoelectric conversion section, for example from the side of the light receiving surface (light incidence surface). S1 in Fig. 1) Furthermore, the unit pixel P contains a Tr group 1110 , a Tr group 1120 and a Tr group 1130 as charge readout sections that read out charges corresponding to the respective light components of wavelengths R, G, and B from the red photoelectric conversion section, the green photoelectric conversion section, and the blue photoelectric conversion section. The solid-state imaging device 1scatters light in a vertical direction in a unit pixel P, i.e., it scatters the respective light components of R, G, and B in the respective layers that serve as the red photoelectric conversion section, the green photoelectric conversion section, and the blue photoelectric conversion section, which are located in the photoelectric conversion area. 1100 are stacked.

[0054] The Tr Group 1110 , the Tr group 1120 and the Tr group 1130 are located at the periphery of the photoelectric conversion area 1100 formed. The Tr group 1110 The Tr group outputs a signal charge as a pixel signal, corresponding to the light generated and accumulated in the red photoelectric conversion region of R. 1110 contains a transfer transformer (MOS-FET) 1111 , a reset tool 1112 , a reinforcement train 1113 and a selection 1114 The Tr Group 1120The Tr group outputs a signal charge as a pixel signal, corresponding to the light generated and accumulated in the blue photoelectric conversion section of B. 1120 contains a transfer Tr 1121 , a reset Tr 1122 , a reinforcement train 1123 and a selection 1124 The Tr Group 1130 The pixel signal outputs a signal charge corresponding to the light from G, which is generated and accumulated in the green photoelectric conversion section. The Tr group 1130 contains a transfer Tr 1131 , a reset tool 1132 , a reinforcement train 1133 and a selection 1134 .

[0055] The transfer Tr 1111 includes (source / drain region, which is considered) a gate G, a source / drain region S / D and FD (floating or potential-free diffusion) 1115. The transfer Tr 1121 includes a gate G, a source / drain area S / D and FD 1125 The transfer Tr1131 contains a gate G, (source / drain area S / D coupled to) the green photoelectric conversion section of the photoelectric conversion area 1100 and FD 1135 It should be noted that the source / drain area of ​​the transfer tr 1111 with the red photoelectric conversion section of the photoelectric conversion area 1100 is coupled and the source / drain area S / D of the transfer tr 1121 with the blue photoelectric conversion section of the photoelectric conversion area 1100 is coupled.

[0056] The reset trip 1112 , 1132 and 1122 , the reinforcement trains 1113 , 1133 and 1123 as well as the selection trips 1114 , 1134 and 1124 Each contains a gate G and a pair of source / drain areas S / D, which are arranged above the gate G.

[0057] The FDs 1115 , 1135 and1125 are coupled to the respective source / drain areas S / D, which serve as sources of the reset channels 1112 , 1132 and 1122 serve, and are connected to the respective Gates G of the amplification trains 1113 , 1133 and 1123 coupled. Each power supply Vdd is connected to the common source / drain area S / D in the reset circuit. 1112 and the reinforcement train 1113 , the reset-Tr 1132 and the reinforcement train 1133 as well as the reset button 1122 and the reinforcement train 1123 coupled. VSL (vertical signal line) is coupled to each of the source / drain areas S / D, which are the respective sources of the selection trains. 1114 , 1134 and 1124 serve.

[0058] The technology according to the present disclosure is applicable to the photoelectric conversion element as described above. (Method for manufacturing a photoelectric conversion element)

[0059] It is possible to use the photoelectric conversion element 10 According to the present embodiment, it can be produced, for example, in the following manner.

[0060] Fig. 5 and Fig. Figure 6 each illustrates a method for manufacturing the photoelectric conversion element. 10 in the order of the processes. First, as in Fig. 5 shown, e.g. the p-tub 61 as the first electrically conductive well in the semiconductor substrate 11 formed. In this p-tub 61 The second electrically conductive (e.g., n-type) inorganic photoelectric conversion sections will be used. 11B and 11R A p+ region is formed near the first surface. 11S1 of the semiconductor substrate 11 educated.

[0061] As in Fig.5 are shown on the second surface 11S2 of the semiconductor substrate 11 after the formation of n+ areas, which are known as the floating or potential-free diffusions FD1 until FD3 serve as a gate insulating layer 62 and a gate wiring layer 64 including the respective gates of the vertical transistor Tr1 , of the transfer transistor Tr2 , of the amplifier transistor AMP and the reset transistor RST. This forms the vertical transistor Tr1 , the transfer transistor Tr2 The amplifier transistor AMP and the reset transistor RST are formed. Furthermore, the multilayer wiring harness is... 70 on the second surface 11S2 of the semiconductor substrate 11 formed. The multilayer wiring cable 70 includes the wiring levels 71 until 73 and the insulating layer 74 The wiring levels71 until 73 include the lower first contact 75 , the lower second contact 76 and the coupled section 71A .

[0062] As the basis of the semiconductor substrate 11 For example, an SOI (Silicon on Insulator) substrate is used, in which the semiconductor substrate 11 , an embedded oxide film (not shown) and a holding substrate (not shown) are stacked. Although not in Fig. Figure 5 shows the embedded oxide film and the holding substrate with the first substrate surface. 11S1 of the semiconductor substrate 11 connected. After ion implantation, an annealing process is carried out.

[0063] Then a support substrate (not shown), another semiconductor substrate, or similar is bonded to the second surface. 11 S2 side (side of the multilayer wiring cable) 70 ) of the semiconductor substrate 11connected and turned vertically. The semiconductor substrate is then... 11 separated from the embedded oxide film and the holding substrate of the SOI substrate to form the first surface 11S1 of the semiconductor substrate 11 to expose. It is possible to carry out these processes using technologies employed in a normal CMOS process, such as ion implantation and CVD (Chemical Vapor Deposition).

[0064] Then, as in Fig. 6 shows the semiconductor substrate 11 from the first side of the surface 11S1 processed with dry etching to, for example, create a ring-shaped opening 63H to form. The opening 63H has a depth that extends from the first surface 11S1 up to the second surface 11S2 of the semiconductor substrate 11 penetrates, as in Fig. 6 shown, and e.g. the coupled section 71A reached.

[0065] Then, for example, as in Fig. 6 shows the negative fixed charge layer 12A on the first surface 11S1 of the semiconductor substrate 11 and a side surface of the opening 63H formed. Two or more types of films can be used as the negative fixed charge layer. 12A They can be stacked. This makes it possible to further improve the function of the hole accumulation layer. The dielectric layer 12B after the formation of the negative fixed charge layer 12A educated.

[0066] Next, an electrical conductor is inserted into the opening. 63H embedded to form the through-electrode 63 to form. As an electrical conductor, for example, a metallic material such as aluminum (Al), tungsten (W), titanium (Ti), cobalt (Co), hafnium (Hf) and tantalum (Ta) can be used alongside a doped silicon material such as PDAS (phosphorus-doped amorphous silicon).

[0067] Then, after a pad section 13A on the through-electrode 63 Once formed, the intermediate layer insulation layer 14 on the dielectric layer 12B and the pad section 13 formed. In the intermediate layer-insulating layer 14 will the upper contact 13B and a pad section 13C on the pad section 13A provided. The upper contact 13B and the pad section 13C electrically couple the lower electrode 15 and the through-electrode 63 (more precisely, the pad section) 13A on the through-electrode 63 ).

[0068] Next, the lower electrode will be 15 , the organic photoelectric conversion layer 16 , the upper electrode 17 and the protective layer 18 in this order on the intermediate layer insulating layer 14formed. Such as the organic photoelectric conversion layer. 16 Films of the three types of organic semiconductor materials described above are formed, for example, using a vacuum deposition process. Finally, the on-chip lens layer is created. 19 arranged on their surface the multitude of on-chip lenses 19L contains. This means that the in Fig. 1 photoelectric conversion element shown 10 completed.

[0069] It should be noted that in a case where another organic layer (e.g. electron blocking layer, etc.) is on or under the organic photoelectric conversion layer 16 As described above, it is desirable to continuously form the other organic layer (through a vacuum-constant process) in a vacuum process. Furthermore, the method for forming the organic photoelectric conversion layer is 16not necessarily limited to the vacuum coating process, but another process, e.g. a spin coating technique, a printing process or similar, can also be used.

[0070] When light passes through the on-chip lens 19L in the photoelectric conversion element 10 into the organic photoelectric conversion section 11G Upon entering, the light passes through the organic photoelectric conversion section. 11G , the inorganic photoelectric conversion sections 11B and the 11R In this order, the respective components of green, blue, and red light are photoelectrically converted during the process. The following describes a procedure for detecting signals of the respective colors. (Detection of the green color signal by the organic photoelectric conversion section) 11G )

[0071] First, the green light from the light parts that enter the photoelectric conversion element is 10 are fed in, selectively detected (absorbed) and by the organic photoelectric conversion section 11G converted photoelectrically.

[0072] The organic photoelectric conversion section 11G is via the through-electrode 63 with a gate Gamp of the amplifier transistor AMP and the floating or potential-free diffusion FD3 coupled. This couples the electron of the organic photoelectric conversion section. 11G generated electron-hole pair from the side of the lower electrode 15 taken via the through-electrode 63 to the second surface 11S2 of the semiconductor substrate 11 transferred and in the floating or potential-free diffusion FD3accumulated. Simultaneously, the amplifier transistor AMP modulates the amount in the organic photoelectric conversion section. 11G generated charges into a voltage.

[0073] Furthermore, the reset gate Grst of the reset transistor RST is in addition to the floating or potential-free diffusion. FD3 arranged. This causes the reset transistor RST to reset the floating or potential-free diffusion. FD3 resets accumulated charges.

[0074] Here is the organic photoelectric conversion section. 11G not only with the amplifier transistor AMP, but also via the through-electrode 63 also with floating or potential-free diffusion FD3 coupled, which allows the reset transistor RST to operate in the floating or potential-free diffusion. FD3 Simply reset accumulated charges.

[0075] In contrast, in a case where the through-electrode 63 and floating or potential-free diffusion FD3 are not coupled, making it difficult to understand the floating or potential-free diffusion. FD3 to reset accumulated charges, which leads to the application of a high voltage to move the charges to the side of the upper electrode. 17 to extract. Accordingly, there is a possibility that the organic photoelectric conversion layer 16 It is damaged. Furthermore, a structure that allows for rapid reset leads to increased dark-time noise and results in a compromise. This structure is therefore difficult. (Detection of the blue and red color signals by inorganic photoelectric conversion sections) 11B and 11R )

[0076] Subsequently, the blue light and the red light of the light parts, which are the organic photoelectric conversion section, are 11G pass through, are absorbed one after the other, and are processed in the inorganic photoelectric conversion section. 11B and the inorganic photoelectric conversion section 11R photoelectrically converted. In the inorganic photoelectric conversion section 11B Electrons corresponding to the input blue light are generated in the n-region of the inorganic photoelectric conversion section. 11B accumulated, and the accumulated electrons are passed through the vertical transistor Tr1 on floating or potential-free diffusion FD1 transferred. Similarly, in the inorganic photoelectric conversion section, 11R Electrons corresponding to the input red light in the n-region of the inorganic photoelectric conversion section 11Raccumulated, and the accumulated electrons are passed through the transfer transistor Tr2 on floating or potential-free diffusion FD2 transmitted. (How it works and its effects)

[0077] As described above, an organic photoelectric conversion element used in an organic thin-film solar cell, an organic imaging element, or similar application adopts a bulk heterostructure in which an organic p-type semiconductor and an organic n-type semiconductor are mixed. However, organic semiconductors have low conductivity properties, so the organic photoelectric conversion element cannot achieve sufficient quantum efficiency. Therefore, the problem arises that the electrical output signal is slightly delayed relative to the incident light.

[0078] It is generally accepted that the molecular orientation is important for the conductivity of organic semiconductors. The same applies to organic photoelectric conversion devices with a bulk heterostructure. It is known that for an organic photoelectric conversion device where the conduction direction is perpendicular to a substrate, it is generally preferable for the organic semiconductor to be oriented parallel to the substrate. Therefore, as described above, various measures are taken to improve the horizontal orientation of an organic semiconductor contained in an organic photoelectric conversion layer.

[0079] Simply aligning the organic molecules parallel to the substrate does not sufficiently improve the conductivity properties of the organic photoelectric conversion element, so in some cases, an adequate improvement in quantum yield and response is not achieved. In a photoelectric conversion element with a bulk heterostructure, each material contained within the bulk heterostructure in the layer is encouraged to form a suitable grain. In a case where, for example, a large defect is present at the grain boundary, the conductivity is significantly degraded. One reason for this is that charge is trapped at a trap level of the defect, or the defect acts as an energy barrier to prevent charge transfer between the grains when the charge at the grain boundary is conductive.This is assumed to lead to a deterioration in quantum yield and reaction rate.

[0080] In contrast, the organic photoelectric conversion layer contains 16 In the present embodiment, an organic semiconductor material (an organic semiconductor material) forms a domain (e.g., domain Dp) with a predetermined shape within the layer. In particular, the organic photoelectric conversion layer 16 The resulting structure comprises an organic semiconductor material containing a domain with a percolation structure and a shape where the domain's length in the plane direction is smaller than its length in the layer thickness direction. In the percolation structure, the domain extends vertically within the organic photoelectric conversion layer. 16in the direction of the film thickness. This makes it possible to appropriately control the mixing state of organic semiconductor materials in the organic photoelectric conversion layer.

[0081] As described above, the photoelectric conversion element contains 10 According to the present embodiment, an organic semiconductor material (e.g., p-type semiconductor) is used in the organic photoelectric conversion layer. 16 The organic semiconductor material (e.g., p-type semiconductor) forms the domain described above in the organic photoelectric conversion layer. 16 This results in organic semiconductor materials (e.g., an n-type semiconductor and a light absorber in addition to the p-type semiconductor described above) being used in the organic photoelectric conversion layer. 16The components are contained within a controlled mixture state. This makes it possible to increase the external quantum yield and reaction rate.

[0082] Next, a modification example of the present disclosure is described. It should be noted that the components are similar to those of the photoelectric conversion element. 10 according to the embodiment described above, are designated with the same reference numerals and their description is omitted. <Beispiel einer Modifikation>

[0083] Fig. Figure 7 illustrates a cross-sectional configuration of a photoelectric conversion element (photoelectric conversion element). 20 ) using a modification example of the present disclosure. The photoelectric conversion element 20 is, for example, in a unit pixel P in the solid-state image capture element (solid-state image capture device). 1) such as a CCD image sensor or CMOS image sensor with backlighting, similar to the photoelectric conversion element 10 according to the embodiment described above, etc. The photoelectric conversion element 20 According to the present modification example, a configuration has a red photoelectric conversion section. 40R , a green photoelectric conversion section 40G and a blue photoelectric conversion section 40B in this order on a silicon substrate 81 with the insulating layer in between 82 are stacked.

[0084] The red photoelectric conversion section 40R , the green photoelectric conversion section 40G and the blue photoelectric conversion section 40B Each contains organic photoelectric conversion layers 42R , 42G and 42Bbetween the respective electrode pairs. In particular, the red photoelectric conversion section contains 40R , the green photoelectric conversion section 40G and the blue photoelectric conversion section 40B each of the organic photoelectric conversion layers 42R , 42G and 42B between a first electrode 41R and a second electrode 43R , between a first electrode 41G and a second electrode 43G and between a first electrode 41B and a second electrode 43B The organic photoelectric conversion layers 42R , 42G and 42B Each contains a ChDT derivative, making it possible to achieve similar effects to the version described above.

[0085] As described above, the photoelectric conversion element 20a configuration in which the red photoelectric conversion section 40R , the green photoelectric conversion section 40G and the blue photoelectric conversion section 40B in this order on the silicon substrate 81 with the insulating layer in between 82 are stacked. The on-chip lens 19L is located on the blue photoelectric conversion section 40B , whereby the protective layer 18 and the on-chip lens layer 19 are arranged in between. A red energy storage layer 210R , a green energy storage layer 210G and a blue energy storage layer 210B are in the silicon substrate 81 provided for. The one integrated into the on-chip lens. 19L The injected light components are converted by the red photoelectric conversion section. 40R , the green photoelectric conversion section 40Gand the blue photoelectric conversion section 40B photoelectrically converted. The respective signal charges are converted by the red photoelectric conversion section. 40R to the red energy storage layer 210R , from the green photoelectric conversion section 40G to the green energy storage layer 210G and from the blue photoelectric conversion section 40B to the blue energy storage layer 210B transferred. Although the signal charges can be either electrons or holes generated by photoelectric conversion, the following description uses the example of a case where electrons are read as signal charges.

[0086] The silicon substrate 81 It contains, for example, a p-type silicon substrate. The red energy storage layer 210R , the green energy storage layer 210G and the blue energy storage layer 210B, which are in this silicon substrate 81 The components provided each contain an n-type semiconductor region. The respective signal charges (electrons) originate from the red photoelectric conversion section. 40R , the green photoelectric conversion section 40G and the blue photoelectric conversion section 40B The energy supplied is accumulated in the n-type semiconductor regions. The n-type semiconductor regions of the red energy storage layer 210R , the green energy storage layer 210G and the blue energy storage layer 210B for example, by doping the silicon substrate 81 formed with n-type impurities such as phosphorus (P) or arsenic (As). It should be noted that the silicon substrate 81 can be provided on a support substrate (not shown) made of glass or similar material.

[0087] The silicon substrate 81contains a pixel transistor to extract the respective electrons from the red power storage layer 210R , the green energy storage layer 210G and the blue energy storage layer 210B to read out and direct the read-out electrons, e.g., onto a vertical signal line (vertical signal line Lsig in Fig. (described below in section 8). A floating or potential-free diffusion of this pixel transistor is possible in the silicon substrate. 81 provided for, and this floating or potential-free diffusion is connected to the red energy storage layer. 210R , the green energy storage layer 210G and the blue energy storage layer 210B coupled. The floating or potential-free diffusion encloses an n-type semiconductor region.

[0088] The insulating layer 82 This includes, for example, silicon oxide, silicon nitride, silicon oxynitride, hafnium oxide, or similar materials. The insulating layer 82It can contain a variety of types of insulating films that are stacked. The insulating layer 82 may contain an organic insulating material. This insulating layer 82 includes appropriate connectors and electrodes for coupling the red energy storage layer 210R and the red photoelectric conversion section 40R , the green energy storage layer 210G and the green photoelectric conversion section 40G as well as the blue energy storage layer 210B and the blue photoelectric conversion section 40B .

[0089] The red photoelectric conversion section 40R The first electrode contains 41R , an organic photoelectric conversion layer 42R and the second electrode 43R in this order from a position near the silicon substrate 81 out. The green photoelectric conversion section 40GThe first electrode contains 41G , an organic photoelectric conversion layer 42G and the second electrode 43G in this order from a position near the red photoelectric conversion section 40R out. The blue photoelectric conversion section 40B The first electrode contains 41B , an organic photoelectric conversion layer 42B and the second electrode 43B in this order from a position near the green photoelectric conversion section 40G out. An insulating layer 44 is between the red photoelectric conversion section 40R and the green photoelectric conversion section 40G provided, and an insulating layer 45 is between the green photoelectric conversion section 40G and the blue photoelectric conversion section 40BProvided. Red light (e.g., wavelength of 600 nm or more and less than 700 nm) is selectively absorbed in the red photoelectric conversion section. 40R absorbed; green light (e.g. wavelength of 480 nm or more and less than 600 nm) is selectively absorbed in the green photoelectric conversion section. 40G absorbed; and blue light (e.g. wavelength of 400 nm or more and less than 480 nm) is selectively absorbed in the blue photoelectric conversion section. 40B absorbed, generating electron-hole pairs.

[0090] The first electrode 41R extracts signal charges that are located in the organic photoelectric conversion layer 42R are generated; the first electrode 41G extracts signal charges that are located in the organic photoelectric conversion layer 42G be generated; and the first electrode 41Bextracts signal charges that are located in the organic photoelectric conversion layer 42B to be generated. The first electrodes 41R , 41G and 41B These first electrodes are, for example, intended for each pixel. 41R , 41G and 41B They each contain, for example, a translucent, electrically conductive material, in particular ITO. The first electrodes 41R , 41G and 41BThey can, for example, each contain a tin oxide-based or zinc oxide-based material. The tin oxide-based material is obtained by doping tin oxide with a dopant. Examples of zinc oxide-based materials include aluminum zinc oxide, where aluminum is added to zinc oxide as a dopant; gallium zinc oxide, where gallium is added to zinc oxide as a dopant; indium zinc oxide, where indium is added to zinc oxide as a dopant; and the like. Alternatively, it is also possible to use IGZO, CuI, InSbO4, ZnMgO, CuInO2, MgIn2O4, CdO, ZnSnO3, and the like. The thickness of each of the first electrodes 41R , 41Gund 41B For example, it is 50 nm to 500 nm.

[0091] For example, appropriate electron transport layers can be placed between the first electrode. 41R and the organic photoelectric conversion layer 42R , between the first electrode 41Gand the organic photoelectric conversion layer 42G and between the first electrode 41B and the organic photoelectric conversion layer 42B The electron transport layers serve to ensure that the electrons in the organic photoelectric conversion layers are transferred to the electron transport layers. 42R , 42G and 42B generated electrons to the first electrodes 41R , 41G and 41B The electron transport layers can be supplied with materials such as titanium oxide, zinc oxide, or similar substances. Each layer contains titanium oxide and zinc oxide stacked together. The thickness of each electron transport layer is, for example, 0.1 nm to 1000 nm, preferably 0.5 nm to 300 nm.

[0092] The organic photoelectric conversion layers 42R , 42G and 42BEach layer absorbs light in a selective wavelength range for photoelectric conversion and transmits light in a different wavelength range. The light in the selective wavelength range is, for example, light with a wavelength of 600 nm or more and less than 700 nm in the organic photoelectric conversion layer. 42R , light in a wavelength range with a wavelength of 480 nm or more and less than 600 nm, e.g. in the organic photoelectric conversion layer 42G , and light in a wavelength range with a wavelength of 400 nm or more and less than 480 nm, e.g. in the organic photoelectric conversion layer 42B The thickness of each of the organic photoelectric conversion layers 42R , 42G and 42B For example, it is 50 nm or more and less than 500 nm.

[0093] The organic photoelectric conversion layers 42R , 42G and 42B each contain, for example, two or more types of organic semiconductor materials and preferably, for example, one or both of a p-type semiconductor and an n-type semiconductor, similar to the organic photoelectric conversion layer. 16 in the configuration described above. For example, in a case where each of the organic photoelectric conversion layers 42R , 42G and 42BThe composition comprises two types of organic semiconductor materials, including a p-type semiconductor and an n-type semiconductor. One of the p-type semiconductors and the n-type semiconductor are preferably materials transmitting visible light, and the other is preferably a material that photoelectrically converts light in a selective wavelength range (e.g., 450 nm or more and 650 nm or less). Alternatively, each of the organic photoelectric conversion layers contains 42R , 42G and 42B Preferably three types of organic semiconductor materials, including a material (light absorber), an n-type semiconductor, and a p-type semiconductor. The material (light absorber) photoelectrically converts light in a selective wavelength range corresponding to each layer. The n-type semiconductor and the p-type semiconductor each have a transmittance for visible light.

[0094] Each of the organic photoelectric conversion layers 42R , 42G and 42B It has a bulk heterostructure in which the multitude of these organic semiconductor materials are randomly mixed within the layer. In the present modification example, at least one of the organic photoelectric conversion layers has 42R , 42G and 42B a configuration in which one domain (e.g., domain Dp) has a configuration similar to the organic photoelectric conversion layer 16 according to the embodiment described above in the layer.

[0095] For example, appropriate hole transport layers can be placed between the organic photoelectric conversion layer. 42R and the second electrode 43R , between the organic photoelectric conversion layer 42G and the second electrode 43G and between the organic photoelectric conversion layer42B and the second electrode 43B The hole transport layers serve to fill holes that are present in the organic photoelectric conversion layers. 42R , 42G and 42B to be generated, the second electrodes 43R , 43G and 43B to be supplied, and each comprises, for example, molybdenum oxide, nickel oxide, vanadium oxide, or similar materials. The hole transport layers can each contain an organic material such as PEDOT (poly(3,4-ethylenedioxythiophene)) and TPD (N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine). The thickness of each of the hole transport layers is, for example, 0.5 nm or more and 100 nm or less.

[0096] The second electrode 43R It serves to extract holes that are present in the organic photoelectric conversion layer. 42R were produced; the second electrode 43GIt serves to extract holes that are present in the organic photoelectric conversion layer. 42G were produced; and the second electrode 43B It serves to extract holes that are present in the organic photoelectric conversion layer. 42G were generated. The ones from the second electrodes 43R , 43G and 43B The extracted holes are transferred via appropriate transmission pathways (not shown) to, for example, a p-type semiconductor region (not shown) in the silicon substrate. 81 discharged. The second electrodes 43R , 43G and 43B They each contain, for example, an electrically conductive material such as gold, silver, copper, and aluminum. Similar to the first electrodes. 41R , 41G and 41B can the second electrodes 43R , 43G and 43B Each contains a transparent, electrically conductive material. In the photoelectric conversion element20 will the electrodes from these second electrodes 43R , 43G and 43B extracted holes discharged. For example, if the multitude of photoelectric conversion elements 20 in the solid-state imaging device described below 1 is arranged 43R , 43G and 43B common for each of the photoelectric conversion elements 20 (Unit pixel P) are provided. The thickness of each of the second electrodes 43R , 43G and 43B For example, 0.5 nm or more and 100 nm or less.

[0097] The insulating layer 44 serves to connect the second electrode 43R and the first electrode 41G to isolate each other, and the insulating layer 45 serves to connect the second electrode 43G and the first electrode 41B to isolate each other. The insulating layers 44and 45 Each layer contains, for example, a metal oxide, a metal sulfide, or an organic material. Examples of metal oxides include silicon dioxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, tungsten oxide, magnesium oxide, niobium oxide, tin oxide, gallium oxide, and the like. Examples of metal sulfides include zinc sulfide, magnesium sulfide, and the like. The band gap of a material present in each of the insulating layers 44 and 45 The contained value is preferably 3.0 eV or more. The thickness of each of the insulating layers 44 and 45 For example, 2 nm or more and 100 nm or less.

[0098] As described above, an organic semiconductor material is used, which is incorporated into at least one of the organic photoelectric conversion layers. 42R , 42G and 42BA domain with a percolation structure and a shape is formed in which the length of the domain in the plane direction is less than the length of the domain in the layer thickness direction. In the percolation structure, the domain extends vertically in the organic photoelectric conversion layer (e.g., organic photoelectric conversion layer). 42R ) in the direction of the film thickness. This results in organic semiconductor materials (e.g., an n-type semiconductor and a light absorber in addition to the p-type semiconductor described above) embedded in an organic photoelectric conversion layer (e.g., organic photoelectric conversion layer). 42R ) are contained in a suitable mixing state and controlled. This makes it possible to increase the external quantum yield and response speed. <anwendungsbeispiele>(Application example 1)

[0099] Fig. Figure 8 illustrates, for example, an overall configuration of the solid-state imaging device. 1 including the photoelectric conversion element 10 , which is described for each pixel in the embodiment described above. This solid-state image capture device 1 is a CMOS image sensor. The solid-state image acquisition device 1 contained on the semiconductor substrate 11 the pixel section 1a as an imaging area and a peripheral circuit unit 130 in a peripheral area of ​​this pixel section 1a The peripheral circuit unit 130 contains, for example, a line sampling section 131 , a horizontal selection section 133 , a column sampling section 134 and a control panel section 132 .

[0100] The pixel section 1a contains, for example, a large number of unit pixels P (corresponding, for example, to the photoelectric conversion element). 10 ), which are arranged two-dimensionally in a matrix. In these unit pixels P, for example, the pixel driver lines Lread (in particular, row select lines and reset control lines) are located at each of the pixel rows, and the vertical signal lines Lsig are located at each of the pixel columns. The pixel driver lines Lread are each used to transmit driver signals for reading signals from pixels. One end of each of the pixel driver lines Lread is connected to the output end of the row scanning section. 131 coupled, corresponding to each line.

[0101] The line sampling section 131 is a pixel control section that contains a shift register, an address decoder, and similar components, and, for example, controls each of the unit pixels P of the pixel section. 1a It is controlled line by line. A signal is generated by each of the unit pixels P of the selected line and by the line sampling section. 131 The sampled pixel rows are output to the horizontal selection section. 133 Lsig is fed in via each of the vertical signal lines. The horizontal selection section 133 contains an amplifier, a horizontal selector switch and the like, which is used for each of the vertical signal lines.

[0102] The column sampling section 134 It contains a shift register, an address decoder, and similar components, and sequentially controls each of the horizontal selector switches of the horizontal selector device. 133 on, while the horizontal selection switches are being scanned. The selection and scanning by this column scanning section. 134 outputs signals from the respective pixels sequentially, which are sent via each of the vertical signal lines Lsig to a horizontal signal line. 135 are transmitted, and transmits the signals via the horizontal signal line. 135 to the outside of the semiconductor substrate 11 .

[0103] Circuit components including the line scanning section 131 , of the horizontal selection section 133 , of the column sampling section 134 and the horizontal signal line 135 can be placed directly on the semiconductor substrate 11 These circuit components can be built on a physical substrate or mounted on an external control IC. Furthermore, they can be formed on a different substrate coupled by a cable or similar device.

[0104] The Control Panel section 132 For example, it receives data for a clock, instructions regarding an operating mode, and similar information. The clock signal and the data are generated on the outside of the semiconductor substrate. 11 supplied. In addition, the system control section 132 Data such as internal information of the solid-state imaging device 1 off. The system control section 132 It also includes a timing generator that produces various timing signals and controls the peripheral circuitry, such as the line scanning section. 131 , of the horizontal selection section 133 and the column sampling section 134 It controls based on the various timing signals generated by the timing generator. (Application example 2)

[0105] The solid-state imaging device described above 1 This is applicable, for example, to any type of electronic device (solid-state image-capturing device) with an imaging function. The electronic device (solid-state image-capturing device) includes a camera system, such as a digital still camera and a video camera, a mobile phone with an imaging function, and the like. Fig. Figure 9 illustrates a schematic configuration of a camera. 2 as an example. This camera 2 For example, a video camera is capable of recording a still image or a moving image. The camera 2 includes the solid-state imaging device 1 , an optical system (optical lens) 310, a shutter device 311 , a drive section 313 , which is the solid-state imaging device 1 and the locking device 311 drives, and a signal processing section 312 .

[0106] The optical system 310 guides image light (incident light) from an object to the pixel section 1a the solid-state imaging device 1 This optical system 310 It can contain a variety of optical lenses. The shutter device 311 controls a time period during which the solid-state imaging device 1 is illuminated with light, and a period of time during which the light is blocked. The drive section 313 controls a transmission process of the solid-state image acquisition device 1 and a closing process of the closing device 311 The signal processing section 312 performs various types of signal processing of signals received from the solid-state image acquisition device 1 A processed image signal (Dout) is stored in a storage medium such as memory or output to a monitor or similar device. (Application example 3)<Beispiel für die Anwendung auf ein In-Vivo-Informationserfassungssystem>

[0107] Furthermore, the technology (present technology) according to the present disclosure is applicable to various products. For example, the technology according to the present disclosure can be applied to an endoscopic surgical system.

[0108] Fig. Figure 10 is a block diagram that provides an example of a schematic configuration of an in vivo information acquisition system for a patient using a capsule-type endoscope, for which the technology according to an embodiment of the present disclosure (present technology) can be used.

[0109] The in vivo information acquisition system 10001 includes an endoscope. 10100 of capsule type and an external control device 10200 .

[0110] The endoscope 10100 The capsule-type endoscope is swallowed by the patient during the examination. 10100 The capsule-type endoscope has an image acquisition function and a wireless communication function. It sequentially captures an image from inside an organ, such as the stomach or intestine (hereinafter also referred to as an in vivo image), at predetermined intervals as it moves within the organ via peristaltic movement for a period of time until it is naturally expelled by the patient. 10100 The capsule type then wirelessly transmits information from the in-vivo image successively to the external control unit. 10200 outside the body.

[0111] The external control device 10200 Integrally controls the operation of the in-vivo information acquisition system 10001. Furthermore, the external control unit receives 10200 information from an endoscope 10100 from the capsule type transmitted there in vivo image and generates image data for displaying the in vivo image on a (not shown) display device based on the received information of the in vivo image.

[0112] In the in-vivo information acquisition system 10001 In this way, an in-vivo image that captures the condition of a patient's inside body can be acquired at any time during a period of time until the endoscope 10100 It is excreted of the capsule type after being swallowed.

[0113] Configuration and functions of the endoscope 10100 of the capsule type and the external control device 10200 will be described in more detail below.

[0114] The endoscope 10100 The capsule type has a housing 10101 of the capsule type, containing a light source unit 10111 , an image capture unit 10112 , an image processing unit 10113 , a unit 10114 for wireless communication, a power supply unit 10115 , a power supply unit 10116 and a control unit 10117 are housed.

[0115] The light source unit 10111 contains a light source, such as a light-emitting diode (LED), and emits light onto an image capture field of view of the image capture unit. 10112 .

[0116] The image acquisition unit 10112 It contains an image-taking element and an optical system comprising a plurality of lenses provided at a stage preceding the image-taking element. Reflected light (hereafter referred to as observation light) from light directed onto body tissue that is the observation target is collected by the optical system and introduced into the image-taking element. In the image-taking unit 10112 The incident observation light is photoelectrically converted by the image acquisition element, thereby generating an image signal corresponding to the observation light. The image is then processed by the image acquisition unit. 10112 The generated image signal is sent to the image processing unit. 10113 provided.

[0117] The image processing unit 10113 It contains a processor such as a central processing unit (CPU) or a graphics processing unit (GPU) and performs various signal processing for an image from the image acquisition unit. 10112 generated image signal. The image processing unit 10113 represents the image signal for which the signal processing was carried out, so that the unit 10114 Available as raw data for wireless communication.

[0118] The unit 10114 For wireless communication, a predetermined process such as a modulation process for the image signal is carried out, for which the signal processes are performed by the image processing unit. 10113 The process was carried out, and the resulting image signal is transmitted via an antenna. 10114A to the external control unit 10200 Furthermore, the unit receives 10114 for wireless communication, a drive control system for the endoscope. 10100 Control signal related to the capsule type from the external control device 10200 via the antenna 10114A The unit 10114 For wireless communication, the external control unit provides 10200 received control signal to the control unit 10117 .

[0119] The power supply unit 10115 It contains an antenna coil for power input, a power recovery circuit for recovering electrical power from current generated in the antenna coil, a voltage amplifier circuit, and the like. The power supply unit 10115 generates electrical power using a principle of so-called contactless charging.

[0120] The power supply unit 10116 It contains a secondary battery and stores the power supplied by the power supply unit. 10115 generated electrical power. In Fig. To avoid a complicated illustration, 10 represents an arrow marking indicating a supply destination for electrical energy from the power supply unit. 10116 Specifies, etc. omitted. The power supply unit 10116 However, the stored electrical power is transferred to the light source unit. 10111 , the image acquisition unit 10112 , the image processing unit 10113 , the unit 10114 for wireless communication and the control unit 10117 provided and can be used to control them.

[0121] The control unit 10117 It contains a processor such as a CPU and appropriately controls the control of the light source unit. 10111 , the image acquisition unit 10112 , the image processing unit 10113 , the unit 10114 for wireless communication and the power supply unit 10115 according to a control device 10200 control signal transmitted there.

[0122] The external control device 10200 It contains a processor such as a CPU or GPU, a microcomputer, a control board, or the like, in which a processor and a memory element such as a memory are integrated. The external control device 10200 transmits via an antenna 10200A a control signal to the control unit 10117 of the endoscope 10100 of capsule type, to facilitate the operation of the endoscope 10100 to control the capsule type. In the endoscope 10100 The capsule type can, for example, provide an irradiation condition of light onto an observation target of the light source unit. 10111 for example, according to a control signal from the external control device 10200 can be changed. Furthermore, an image capture condition (for example, a frame rate, an exposure value, or the like) can be set in the image capture unit. 10112 ) according to a control signal from the external control device 10200 can be changed. Furthermore, the content of a processing operation can be modified by the image processing unit. 10113 or a condition for transmitting an image signal from the unit 10114 for wireless communication (for example, a transmission interval, the number of transmission images, and the like) according to a control signal from the external control device 10200 will be changed.

[0123] Furthermore, the external control device 10200 various image processing techniques are used to generate an image signal from the endoscope 10100 The signal was transferred from the capsule type to generate image data for displaying a captured in-vivo image on the display device. Various signal processing can be performed as image processing, such as a development process (demosaicing process), an image quality improvement process (bandwidth expansion process, super-resolution process, noise reduction (NR) process, and / or image stabilization process), and / or a magnification process (electronic zoom process). The external control device 10200 It controls a signal from the display unit to cause the display unit to show in-vivo images captured based on generated image data. Alternatively, the external control unit can be used. 10200 also control a (not illustrated) recording device to record generated image data, or control a (not illustrated) printing device to print generated image data.

[0124] An example of the in-vivo information acquisition system to which the technology according to the present disclosure can be applied has been described above. The technology according to the present disclosure can, for example, be applied to the image acquisition unit. 10112 These components can be used in conjunction with those described above. This makes it possible to increase the detection accuracy. (Application example 4)<Beispiel für die Anwendung des Systems für endoskopische Chirurgie>

[0125] The technology (present technology) is applicable to various products according to the present disclosure. For example, the technology can be applied to an endoscopic surgical system according to the present disclosure.

[0126] Fig. Figure 11 is a view that represents an example of a schematic configuration of a system for endoscopic surgery for which the technology according to an embodiment of the present disclosure (present technology) can be used.

[0127] In Fig. 11 illustrates a condition in which a surgeon (doctor) 11131 just a system 11000 Used for endoscopic surgery to perform a surgical procedure on a patient 11132 on a patient bed 11133 to be carried out. As shown, the system includes 11000 for endoscopic surgery an endoscope 11100 , other surgical instruments 11110 such as a pneumoperitoneum tube 11111 and an energy treatment device 11112 , a carrier arm device 11120 , which the endoscope 11100 it carries, and a trolley 11200 , on which various devices for endoscopic surgery are mounted.

[0128] The endoscope 11100 includes a lens tube 11101 , with a predetermined length from its distal end to enter a body cavity of the patient 11132 to be introduced, and a camera head 11102 , which is connected to a proximal end of the lens tube 11101 is connected. In the example shown, the endoscope 11100 The image shows a rigid endoscope with the lens tube. 11101 of the hard type. The endoscope 11100 However, it can otherwise be used as a flexible or bendable endoscope with the lens tube. 11101 be of the flexible type.

[0129] At its distal end, the lens tube points 11101 An opening into which an objective lens is fitted. A light source arrangement. 11203 is with the endoscope 11100 connected in such a way that from the light source device 11203 generated light into a distal end of the lens tube 11101 is introduced by a light guide that is located inside the lens tube 11101 extends, and in the direction of an observation target in a body cavity of the patient 11132 The light is projected through the objective lens. It is particularly worth mentioning that the endoscope 11100 It can be an endoscope for straight-through viewing, or an endoscope for oblique viewing, or an endoscope for side-viewing.

[0130] An optical system and an image capture element are located inside the camera head. 11102 The system is designed so that reflected light (observation light) from the observation target is focused or collected by the optical system on the image acquisition element. The observation light is photoelectrically converted by the image acquisition element to generate an electrical signal corresponding to the observation light, namely an image signal corresponding to an observation image. The image signal is transmitted as raw data to a CCU (Control Unit). 11201 transmitted.

[0131] The CCU 11201 It contains a central processing unit (CPU), a graphics processing unit (GPU) or the like, and controls an operation of the endoscope in a comprehensive or integral way. 11100 and a display device 11202 Furthermore, the CCU receives 11201 an image signal from the camera head 11102 and performs various image processing operations for the image signal to display an image based on the image signal, such as a development process (demosaicing process).

[0132] The display device 11202 It shows an image based on an image signal provided by the CCU 11201 the image processes were carried out under the control of the CCU 11201 to.

[0133] The light source setup 11203 It contains a light source, such as a light-emitting diode (LED), and directs irradiated light to the endoscope when imaging an area of ​​a surgical procedure. 11100 to.

[0134] An input device 11204 is an input interface for the system 11000 for endoscopic surgery. A user can use the input device. 11204 Enter various types of information or instructions into the system 11000 for endoscopic surgery. For example, the user gives an instruction or the like to specify an image acquisition condition (a type of illumination, magnification, focal length, or the like) through the endoscope. 11100 to change, one.

[0135] An institution 11205 To control a treatment instrument, a control system for the energy treatment device is used. 11112 For cauterization or burning, or cutting of tissue, occlusion of a blood vessel, or the like. To improve the field of view of the endoscope. 11100 To ensure and provide a working space for the surgeon, a pneumoperitoneum device is used. 11206 through the pneumoperitoneum tube 11111 Gas into a body cavity of the patient 11132 one, to expand the body cavity. A recording device 11207 is a device that can record various types of information related to a surgical procedure. A printer 11208 is a facility that can print various types of information relating to a surgical procedure in different forms such as text, image or graphic representation.

[0136] It is particularly worth mentioning that the light source setup 11203 , the irradiation light, when an area of ​​a surgical procedure is to be imaged, the endoscope 11100 The supplied light source can be a white light source, which may include, for example, an LED, a laser light source, or a combination of both. If a white light source contains a combination of red, green, and blue (RGB) laser light sources, the output intensity and timing for each color (each wavelength) can be controlled with a high degree of accuracy, allowing the white balance of a captured image to be adjusted by the light source setup. 11203 This will be carried out. Furthermore, in this case, if laser beams from the respective RGB laser light sources are directed at an observation target in time-division multiplexing, the image acquisition elements of the camera head will be controlled. 11102 The process is synchronized with the irradiation times. This allows for the individual acquisition of images corresponding to the R, G, and B colors, also using time-division multiplexing. This method makes it possible to obtain a color image even without color filters for the image acquisition element.

[0137] Furthermore, the light source setup 11203 It can be controlled so that the intensity of the emitted light is changed for each predetermined time. This is achieved by controlling the image capture element of the camera head. 11102 By controlling the system synchronously with the timing of changes in light intensity to capture images in time-division multiplexing mode, and combining or synthesizing the images, an image with a high dynamic range can be produced without underdeveloped blocked shadows and overexposed highlights.

[0138] Furthermore, the light source setup 11203 It must be configured to provide light of a predetermined wavelength band suitable for special-light observation. In special-light observation, for example, by exploiting the wavelength dependence of light absorption in body tissue to emit light of a narrow band, a narrowband observation (narrowband imaging) is performed to image a predetermined tissue, such as a blood vessel or a surface area of ​​the mucosal membrane, in high contrast compared to the irradiation light used in ordinary observation (namely white light). Alternatively, special-light observation can be used for fluorescence observation to obtain an image from fluorescent light generated by irradiation with excitation light.Fluorescence observation can be performed by observing fluorescence light emitted from body tissue by shining excitation light onto the tissue (autofluorescence observation), or by obtaining a fluorescence image by locally injecting a reagent such as indocyanine green (ICG) into body tissue and shining excitation light corresponding to a fluorescence wavelength of the reagent onto the tissue. The light source setup... 11203 can be configured to provide such narrowband light and / or excitation light suitable for special light observation as described above.

[0139] Fig. Figure 12 is a block diagram that shows an example of a functional configuration of the camera head. 11102 and the CCU 11201 shows that in Fig. 11 are shown.

[0140] The camera head 11102 contains a lens unit 11401 , an image capture unit 11402 , a control unit 11403 , a communication unit 11404 and a camera head control unit 11405 The CCU 11201 contains a communication unit 11411 , an image processing unit 11412 and a control unit 11413 The camera head 11102 and the CCU 11201 are used for communication with each other via a transmission cable 11400 tied together.

[0141] The lens unit 11401 is an optical system that connects to the lens tube at a junction point. 11101 is provided for. From a distal end of the lens tube 11101 The received observation light is directed to the camera head. 11102 guided and into the lens unit 11401 introduced. The lens unit 11401 It contains a combination of a variety of lenses, including a zoom lens and a focusing lens.

[0142] The number of image acquisition units in the image acquisition unit 11402 The number of plates included can be one (single-plate type) or multiple (multi-plate type). If the image acquisition unit 11402 For example, depending on how the multi-plate type is configured, the respective R, G, and B image signals are generated by the image acquisition elements, and these image signals can be synthesized to obtain a color image. The image acquisition unit 11402 It can also be configured to include a pair of image capture elements to obtain separate image signals for the right and left eye, suitable for a three-dimensional (3D) display. If a 3D display is performed, the depth of tissue in a living body within a surgical area can then be determined by the surgeon. 11131 more accurately detected. It is particularly worth mentioning that when the image capture unit 11402 how one of a stereoscopic type is configured, a variety of systems of lens units 11401 is provided for according to the individual image capture elements.

[0143] Furthermore, the image capture unit 11402 not necessarily on the camera head 11102 be provided. For example, the image acquisition unit 11402 immediately behind the objective lens inside the lens tube 11101 be planned.

[0144] The control unit 11403 It contains an actuator and moves under the control of the camera head control unit. 11405 the zoom lens and the focus lens of the lens unit 11401 by a predetermined distance along an optical axis. Consequently, the magnification and focus of a captured image can be adjusted by the image acquisition unit. 11402 be adjusted appropriately.

[0145] The communication unit 11404 It contains a communication device for transmitting and receiving various types of information to and from the CCU. 11201 The communication unit 11404 transmits a signal from the image capture unit 11402 image signal obtained via the transmission cable 11400 as raw data for the CCU 11201 .

[0146] Furthermore, the communication unit receives 11404 a control signal for controlling the camera head 11102 from the CCU 11201 and provides the control signal for the camera head control unit 11405 ready. The control signal contains information regarding image capture conditions, such as information that a frame rate of a captured image is determined, information that an exposure value is determined for an image capture, and / or information that a magnification and focus of a captured image are determined.

[0147] It is particularly worth mentioning that the image capture conditions, such as the frame rate, exposure value, magnification, or focus, can be determined by the user or by the control unit. 11413 the CCU 11201 They can be automatically adjusted based on the captured image signal. In the latter case, the endoscope 11100 It integrates an automatic exposure (AE) function, an autofocus (AF) function and an automatic white balance (AWB) function.

[0148] The camera head control unit 11405 controls the camera head 11102 based on a communication unit 11404 from the CCU 11201 received control signal.

[0149] The communication unit 11411 It includes a communication device to send various types of information to the camera head. 11102 to transmit and receive from it. The communication unit 11411 receives via the transmission cable 11400 from the camera head 11102 Image signal transmitted there.

[0150] Furthermore, the communication unit transmits 11411 a control signal for controlling the camera head 11102 to the camera head 11102 The image signal and the control signal can be transmitted via electrical communication, optical communication, or the like.

[0151] The image processing unit 11412 Performs various image processing for an image signal in the form of the camera head 11102 raw data transferred there.

[0152] The control unit 11413 It enables various types of control regarding image acquisition of an area of ​​a surgical procedure or the like through the endoscope. 11100 and a display of a captured image obtained by means of an image capture of the area of ​​a surgical procedure or the like. For example, the control unit generates 11413 a control signal to control the camera head 11102 to control.

[0153] Furthermore, the control unit controls 11413 based on an image signal, for which image processes are carried out by means of the image processing unit 11412 were carried out, the display device 11202 , to display a recorded image depicting the area of ​​a surgical procedure or similar. The control unit can then 11413 Using various image recognition technologies, different objects can be identified in the captured image. For example, the control unit can 11413 a surgical instrument such as tweezers or forceps, a specific area of ​​a living body, bleeding, mist, when the energy treatment device 11112 It is used to recognize objects by detecting the shape, color, and so on of the edges of objects contained in a captured image. The control unit 11413 can, if they have the display device 11202 To display a captured image, various types of surgical-supporting information are displayed overlapping with an image of the surgical area using a recognition result. When the surgical-supporting information is displayed overlapping and presented to the surgeon... 11131 The burden on the surgeon can be increased. 11131 be reduced, and the surgeon 11131 can safely continue the surgical procedure.

[0154] The transmission cable 11400 , which the camera head 11102 and the CCU 11201 The cable that connects them is an electrical signal cable suitable for communication of electrical signals, an optical fiber suitable for optical communication, or a composite cable suitable for both electrical and optical communication.

[0155] While in the illustrated example using the transmission cable 11400 If communication is carried out via a wired connection, the communication between the camera head can be used here. 11102 and the CCU 11201 this will be carried out using wireless communication.

[0156] An example of the endoscopic surgical system to which the technology according to the present disclosure can be applied has been described above. The technology according to the present disclosure can be applied to the image acquisition unit among the components described above. 11402 The application of the technology according to one embodiment of the present disclosure to the image acquisition unit. 11402 Increases detection accuracy.

[0157] It should be noted that the endoscopic surgical system has been described here as an example, but the technology according to the present disclosure can also be applied, for example, to a microscopic surgical system or similar. (Application example) 5 )<Beispiel für die Anwendung am mobilen Körper>

[0158] The technology according to the present disclosure is applicable to various products. For example, the technology according to the present disclosure can be achieved as a device mounted on any type of mobile body, such as a vehicle, an electric vehicle, a hybrid electric vehicle, a motorcycle, a bicycle, personal mobility equipment, an aircraft, a drone, a ship, a robot, a construction machine, or an agricultural machine (tractor).

[0159] Fig. Figure 13 is a block diagram illustrating an example of a schematic configuration of a vehicle control system as an example of a system for controlling moving bodies for which the technology according to an embodiment of the present disclosure can be used.

[0160] The vehicle control system 12000 includes a variety of electronic control units that are connected via a communication network 12001 are interconnected. In the Fig. The example shown in section 13 includes the vehicle control system. 12000 a drive system control unit 12010 , a body control system control unit 12020 , a unit 12030 for detecting information from outside the vehicle, a unit 12040 for detecting information in the vehicle and an integrated control unit 12050 Furthermore, they are a functional configuration of the integrated control unit. 12050 a microcomputer 12051 , an audio / video output section 12052 and illustrates an interface (I / F) 12053 of the network installed in the vehicle.

[0161] The drive system control unit 12010 According to various types of programs, it controls the operation of devices related to the vehicle's drive system. For example, the drive system control unit serves to... 12010 as a control device for a drive force generating device for generating a drive force of the vehicle such as an internal combustion engine, a drive motor or the like, a drive force transmission mechanism to transmit the drive force to wheels, a steering mechanism to adjust the steering angle of the vehicle, a braking device to generate the braking force of the vehicle, and the like.

[0162] The body control system 12020 It controls the operation of various types of devices installed on a vehicle body, according to different types of programs. For example, the body system control unit serves this purpose. 12020 as a control device for a keyless entry system, a smart key system, an automatic window device, or various types of lights such as a headlight, a taillight, a brake light, a turn signal, a fog light, or the like. In this case, radio waves transmitted by a mobile device as an alternative to a key, or signals from various types of switches, can be received by the body control unit. 12020 be fed in. The body control system control unit 12020 It receives these injected radio waves or signals and controls a door locking device, the automatic window device, the lights or the like of the vehicle.

[0163] The unit 12030 For the detection of information from outside the vehicle, the vehicle control system detects information about the external environment. 12000 containing vehicle. For example, the unit 12030 for detecting information from outside the vehicle using an imaging section 12031 connected. The unit 12030 The imaging section is used to detect information from outside the vehicle. 12031 , takes an image of the vehicle's external surroundings, and receives the captured image. The unit 12030 To detect information from outside the vehicle, processing can be performed on the basis of the received image to detect an object such as a person, a car, an obstacle, a traffic sign, a mark on a road surface or the like, or processing to detect a distance to it.

[0164] The imaging section 12031 It is an optical sensor that receives light and emits an electrical signal according to the amount of light received. The imaging section 12031 It can also output the electrical signal as an image or provide information about a measured distance. Furthermore, this can be done by the imaging section. 12031 The received light can be visible light or invisible light such as infrared rays or the like.

[0165] The unit 12040 For detecting information within the vehicle, the unit detects information about or from the interior of the vehicle. 12040 For example, information detection in the vehicle is achieved with a section 12041 connected to the detection of a driver's condition, which detects the condition of a driver. The section 12041 The system for detecting a driver's condition includes, for example, a camera that records the driver. The unit 12040 Information detection in the vehicle can be based on a system developed by the section 12041 The system can use the detection information entered to detect a driver's condition to calculate a driver fatigue level or driver concentration level, or can determine whether the driver is dozing off.

[0166] The microcomputer 12051 can calculate a control target value for the drive force generation device, the steering mechanism or the braking device based on information about the interior or external environment of the vehicle, which information is provided by the unit 12030 for detecting information from outside the vehicle or unit 12040 Information is received for the detection of data within the vehicle and can send a control command to the drive system control unit. 12010 output. For example, the microcomputer can 12051 to perform cooperative control intended to implement functions of an Advanced Driver Assistance System (ADAS), the functions of which include collision avoidance or impact mitigation for the vehicle, following based on a following distance, driving at a constant speed, warning of vehicle collision, warning of vehicle lane deviation, or the like.

[0167] Furthermore, the microcomputer can 12051 to perform a cooperative control system intended for automated driving, which allows the vehicle to drive autonomously without dependence on driver intervention or the like, by controlling the drive force generation device, steering mechanism, braking device, or the like, based on information about the external environment or the interior of the vehicle, which information is provided by the unit 12030 for detecting information from outside the vehicle or unit 12040 for the detection of information within the vehicle.

[0168] The microcomputer 12051 It can also send a control command to the body system control unit. 12020 Based on information about the vehicle's external environment, output which information is provided by the unit 12030 for detecting information received from outside the vehicle. For example, the microcomputer 12051 to execute a cooperative control designed to prevent glare by adjusting the front light according to the position of a vehicle ahead or an oncoming vehicle, as determined by the unit 12030 The system detects information from outside the vehicle and controls the system to switch from high beam to low beam.

[0169] The audio / video output section 12052 It transmits an output signal of sound and / or image to an output device that can convey information visually or audibly to an occupant of the vehicle or the vehicle's external environment. For example, Fig. 13 are the output device, a loudspeaker 12061 , an ad section 12062 and a dashboard 12063 specified. The display section 12062 This could include, for example, an on-board display and / or a head-up display.

[0170] Fig. Figure 14 is a diagram showing an example of an installation position for the imaging section. 12031 illustrated.

[0171] In Fig. 14 comprises the imaging section 12031 Imaging sections 12101 , 12102 , 12103 , 12104 and 12105 .

[0172] The imaging sections 12101 , 12102 , 12103 , 12104 and 12105 These are, for example, positions on the front of the vehicle, on side mirrors, a rear bumper and a tailgate. 12100 as well as a position on the upper part of a windshield inside the vehicle. The imaging section provided at the front. 12101 and the imaging section provided at the top of the windshield inside the vehicle 12105 They primarily receive an image from in front of the vehicle. 12100 The imaging sections provided on the side mirrors 12102 and 12103 We primarily receive an image of the sides of the vehicle. 12100 The imaging section provided on the rear bumper or tailgate 12104 The image is primarily taken from behind the vehicle. 12100 The imaging section located on the inside of the upper part of the windshield 12105 It is primarily used to detect a vehicle ahead, a pedestrian, an obstacle, a traffic light, a traffic sign, a lane or the like.

[0173] Furthermore, Fig. 14 an example of photography areas of the imaging sections 12101 until 12104 This represents an imaging area. 12111 represents the imaging area of ​​the imaging section provided at the front. 12101 . Image areas 12112 and 12113 represent the imaging areas of the imaging sections provided on the side mirrors 12102 or 12103 A mapping area 12114 represents the imaging area of ​​the imaging section provided on the rear bumper or tailgate 12104 For example, an image from the vehicle's bird's-eye view is taken. 12100 , as seen from above, obtained, for example, through the imaging sections 12101 until 12104 The displayed image data is superimposed.

[0174] At least one of the imaging sections 12101 until 12104 It may have a function for obtaining distance information. For example, at least one of the imaging sections may 12101 until 12104 It could be a stereo camera composed of a variety of imaging elements, or it could be an imaging element containing pixels for phase difference detection.

[0175] The microcomputer 12051 For example, it can determine the distance to each three-dimensional object within the imaging areas. 12111 until 12114 and a change in distance over time (relative speed in relation to the vehicle) 12100 ) based on the findings from the imaging sections 12101 until 12104 Determine the received distance information and thereby, in particular, extract the nearest three-dimensional object, such as a vehicle traveling ahead, that is located on the vehicle's path. 12100 is located and is moving at a predetermined speed (for example, 0 km / h or higher) in essentially the same direction as the vehicle 12100 drives. Furthermore, the microcomputer can 12051 Predefine a following distance to a vehicle ahead and implement automatic braking control (including follow-stop control), automatic acceleration control (including follow-start control), or similar functions. Consequently, it is possible to implement cooperative control intended for automated driving, allowing the vehicle to drive autonomously without driver intervention.

[0176] The microcomputer 12051 For example, it can classify three-dimensional object data into three-dimensional object data of a two-wheeled vehicle, a vehicle of usual size, a large vehicle, a pedestrian, a telephone pole and other three-dimensional objects based on the distance information provided by the imaging sections. 12101 until 12104 The system obtains the classified three-dimensional object data, extracts it, and uses the extracted three-dimensional objects for automatic obstacle avoidance. For example, the microcomputer identifies... 12051 obstacles around the vehicle 12100 as obstacles that the driver of the vehicle 12100 can be visually recognized, and obstacles that are visible to the driver of the vehicle. 12100 are difficult to detect visually. The microcomputer 12051 It then determines a collision risk, which indicates the likelihood of a collision with any obstacle. In a situation where the collision risk is equal to or higher than a set value, and thus a collision is possible, the microcomputer outputs a warning. 12051 over the loudspeaker 12061 or the display section 12062 a warning to the driver and is executed via the drive system control unit 12010 a forced braking or evasive steering maneuver. The microcomputer 12051 This can help with driving to avoid a collision.

[0177] At least one of the imaging sections 12101 until 12104 It could be an infrared camera that detects infrared rays. For example, the microcomputer 12051 Identifying a pedestrian by determining whether there is a pedestrian in the images captured by the imaging sections. 12101 until 12104 Whether or not a pedestrian is present. Such pedestrian detection is achieved, for example, by means of a procedure for extracting characteristic points from the images acquired by the imaging sections. 12101 until 12104 as infrared cameras and a procedure to determine whether it is the pedestrian or not by performing pattern matching processing at a series of characteristic points that define the object's contour. If the microcomputer 12051 determined that it is in the recorded images of the imaging sections 12101 until 12104 When a pedestrian is detected, and thus the pedestrian is recognized, the audio / video output section is controlled. 12052 the display section 12062 , so that a square outline is displayed for highlighting, superimposed on the detected pedestrian. The audio / video output section 12052 The display section can also be used. 12062 control it so that a symbol or the like representing the pedestrian is displayed at a desired position. <arbeitsbeispiele>

[0178] Next, working examples for the present revelation will be described. (Evaluation of electrical characteristics)

[0179] After a Si substrate with a 50 nm thick ITO electrode (bottom electrode) was purified in a UV / ozone process, an organic photoelectric conversion layer was first deposited at a substrate temperature of 40°C using a resistance heating process, while a substrate holder was heated in a vacuum of 1 × 10 -5 Pa or less was rotated. For an organic photoelectric conversion layer material, 3,6BP-BBTN in expression (1) below was used as the hole transport material (P-material), a subphthalocyanine derivative (F6-SubPc-OPh). 26 F2) as light absorbers and fullerenes C60 The electron transport material (N-material) was used and deposited simultaneously. The deposition rate ratio was 3.6BP-BBTN F6-SubPc-OPh. 26 F2 : C60 = 4:4:2. The layer formation was carried out such that the total layer thickness was 230 nm. Subsequently, B4PyPMP with a thickness of 5 nm was deposited as a buffer layer on the photoelectric conversion layer using a vacuum deposition process at a substrate temperature of 0°C. Then, the upper electrode was applied. 17 An ITO layer with a thickness of 100 nm was formed by sputtering and then subjected to heat treatment below 160°C. This resulted in the fabrication of a photoelectric conversion element (Experimental Example 1) with a photoelectric conversion area of ​​1 mm × 1 mm.

[0180] Additionally, photoelectric conversion elements were fabricated, serving as Experimental Examples 2 to 8. In Experimental Examples 2 and 3, photoelectric conversion elements were fabricated using a similar method to Experimental Example 1, except that the organic photoelectric conversion layers were formed at substrate temperatures of 25°C (Experimental Example 2) and 0°C (Experimental Example 3). In Experimental Example 4, a photoelectric conversion element was fabricated using a similar procedure to that in Experimental Example 3, except that no heat treatment was performed after the formation of the organic film (after the formation of the buffer layer). In Experimental Example 5, a photoelectric conversion element was fabricated using a similar procedure to that in Experimental Example 3, except that BP-ChDT (expression (2)) was used as the P-material.In experimental examples 6, 7 and 8, photoelectric conversion elements were produced by using DBPA (printout (3)) as the P material and the settings -10°C and ANL 160°C (experiment 6), -10°C and As depo (experiment 7) and 40°C and ANL 160°C (experiment 8) as the respective substrate temperatures during the formation of the organic photoelectric conversion layers and the respective heat treatment conditions after the formation of the organic films.

[0181] The responsiveness (afterimage characteristics) of experimental examples 1 to 8 were evaluated. The afterimage characteristics were assessed by measuring the rate at which the value of the luminous current, observed at the time of light irradiation, decreased after the light irradiation was stopped using the semiconductor parameter analyzer. Specifically, the amount of light irradiating the photoelectric conversion element from the light source via the filter was reduced to 1.62 µW / cm². 2 The bias voltage applied between the electrodes was set to -2.6 V. After observing a constant current in this state, the light irradiation was stopped and the decay of the current was observed. Subsequently, with the area surrounded by a current-time curve and the dark current set to 100%, the time elapsed before the area reached 3% was considered an index of the response sensitivity. All evaluations were performed at room temperature.

[0182] Additionally, the quantum efficiency (external quantum efficiency; EQE) of experimental examples 1 to 8 was evaluated using a semiconductor parameter analyzer. Specifically, the external photoelectric conversion efficiency was calculated from a luminous current value and a dark current value in a case where the amount of light (LED light with a wavelength of 560 nm) irradiated by the light source via the filter onto the photoelectric conversion element was 1.62 µW / cm². 2 and the preload to be applied between the electrodes was set to -2.6 V. (Analysis using the transmission electron microscope (TEM))

[0183] Furthermore, TEM observation samples of the cross-sections of the organic photoelectric conversion layers were prepared according to experimental examples 1 to 8, and the P-material domains in the organic photoelectric conversion layers were observed. The domains of the P-materials (organic semiconductor materials, each possessing the property of hole transport) were confirmed by observation of transmission images with a transmission electron microscope.

[0184] First, a thin sample from the area of ​​the organic photoelectric conversion layer of the sample from experimental example 1 above was treated using a focused ion beam (FIB, HELIOS NANOLAB). 400S , manufactured by FEI), and then a damaged layer of an FIB-machined end surface was milled using an ion milling machine (model 1040 , manufactured by Fischione). TEM (JEM-300F, manufactured by JEOL) observed a transmission image at an accelerating voltage of 300 kV in the low-radiation electron beam state. The transmission image was observed with a blurred transmission pattern, i.e., with a deviation of approximately 1500 nm from the pure focus position to the underside as a defocusing condition for observing a domain. Additionally, similar methods were used to perform the transmission microscope analyses of the above experimental examples. 2 until 8 to carry out. [Table 1] P-Material Substrate temperature during layer formation (°C) Heat treatment conditions Electrical characteristics Interference patterns Afterimage characteristics (ms) EQE (%) Length (ms) Angle (*) Number of lines Experiment 1 3, 6BP-BBTN 40 ALN 160°C 1,3 80,4 117,9 87,1 4 Experiment 2 3.6BP-BBTN 25 ALN 160°C 3,5 79,8 61,4 86,6 2 Experiment 3 3.6BP-BBTN 0 ALN 160°C 7,8 62,3 31,5 49,7 2 Experiment 4 3.6BP-BBTN 0 As depo 8,1 61,8 — — — Experiment 5 BP-ChDT 0 ALN 160°C 0,16 85,1 90,0 83,1 2 Experiment 6 DBPA -10 ALN 160°C 3,5 88% 101,2 82,1 3 Experiment 7 DBPA -10 As depo 4,1 72,8 45,8 63,7 2 Experiment 8 DBPA 40 ALN 160°C >100 significantly worsened 107,7 71,9 10

[0185] Fig. Figure 15 contains a TEM image (A) in which the interference pattern component from Experiment 1 is magnified, and (B) obtained by measuring the signal intensity of the TEM image using TEM imaging software (digital micrograph). The interference pattern of the TEM image appears as a series of peaks and troughs in signal intensity, depending on the contrast strength. As described above, paired adjacent lines contained in the interference pattern represent the molecular period of the P material along the principal axis. While the P material used in Experiment 1 had a molecular length of approximately 3 nm, the P material used in Experiment 1 had a molecular length of approximately 3 nm. Fig. 15(B) The line pairs enclosed in the interference pattern have an interval of 2.2 nm. This allows the interference pattern to be described using an interference pattern that has the period of the P material in the principal axis direction.

[0186] Fig. Figure 16 shows the respective TEM images of Experiment 1 (A) and Experiment 4 (B). Fig. Figure 17 shows the corresponding TEM images of Experiment 6 (A) and Experiment 8 (B). Table 1 lists the P-materials used in Experiments 1 to 8, the conditions for the formation of the organic photoelectric conversion layers, their respective electrical properties, and the results of the transmission microscopy analysis. In Experiments 1 and 4, where 3, 6BP-BBTN was used as the P-material. In Experiment 1, where a heat treatment at 160°C was performed after an organic film had formed, an interference pattern was observed indicating a domain extending along the film thickness (e.g., in the circle in Figure 3). Fig. 16(A)). In Experiment 4, where no heat treatment was performed (As depo) after an organic film had formed, no interference pattern was observed. Experiment 1 exhibited better replication features than Experiment 4 and a further improved quantum yield. This demonstrated the effectiveness of a domain in an organic photoelectric conversion layer. Furthermore, in Experiment 3, which used BP-ChDT as the P material and exhibited excellent replication features and quantum yield, a domain extending towards the layer thickness was also confirmed. This suggested that the formation of a domain extending towards the layer thickness was significant for improving an electrical property.

[0187] In contrast, in Experiment 6, where DBPA was used as the P-material and an organic photoelectric conversion layer was formed at 40°C, a domain in the organic photoelectric conversion layer was certainly confirmed, but afterimage features and quantum yield were both significantly degraded. In Experiment 8, a large number (ten or more) of interference patterns were confirmed. This suggested that an excessively large domain led to a degradation of an electrical property.

[0188] It should be noted that in the embodiment described above, the angle between an interference pattern and the electrode surface of the lower electrode was described. 15 The angle formed is preferably greater than 45° and less than 90°, for the following reason: In a case where a domain is formed in an organic photoelectric conversion layer, this domain serves as a charge transport pathway. To transport holes or electrons more efficiently towards the upper and lower electrodes, it is desirable to configure a domain that extends perpendicular to the electrode surface. For example, a domain containing a P-material contributes to the hole transport efficiency, and this increases the response speed to provide favorable replication features. Relatively favorable replication features are achieved in the present working example even when the angle formed between an interference pattern and the electrode surface is 49.7° (Experimental Example 3).As described above, it is preferable for the angle formed between an interference pattern and the electrode surface to be greater than 45° and less than 90° as the direction of propagation of the interference pattern. Furthermore, an angle of 63° or greater and 90° or less is preferable, and an angle of 82° or greater and 90° or less is still preferable.

[0189] Furthermore, in the embodiment described above, the distance between two adjacent lines contained in an interference pattern is preferably within ±50% of the molecular length of a p-type semiconductor. The reason for this is as follows: While the molecular length of the 3,6BP-BBTN used in Experimental Example 1 is approximately 3 nm along the principal axis, the interval of the interference pattern is 2.2 nm, resulting in a difference of approximately 27%. A key factor in this difference is a molecular axis that is not perpendicular to the direction of propagation of the interference pattern or the direction of electron transfer, but is inclined. In a case where the molecular axis is inclined with respect to the electrode surface, the distance between the pairs of lines included in the interference pattern is shorter than the molecular length.Furthermore, the possible variable factors caused by the focus amount of a transmission electron microscope are as follows. Firstly, the image of the transmission electron microscope is variably blurred according to the amount of defocus, and a greater amount of defocus increases the interval between the line pairs included in the interference pattern. Secondly, the amount of defocus varies in accordance with the error of a position without defocus. As a guideline, a defocus amount of 0 is determined from the position of weakest contrast by visually confirming the contrast at one end of the sample while changing the sample height. Thirdly, the amount of focus depends on the position of a p-type semiconductor in a sample, which varies the distance between paired lines.As described above, it is preferable that the distance between two adjacent lines contained in an interference pattern lies within ±50% of the molecular length of the p-type semiconductor.

[0190] The description above was given with reference to the embodiment, the modification example, and the working examples, but the content of the present disclosure is not limited to the embodiment described above and similar embodiments, and various modifications are possible. For example, in the embodiment described above, the photoelectric conversion element has a configuration in which the organic photoelectric conversion section 11G , which detects green light, and the inorganic photoelectric conversion section 11B and the inorganic photoelectric conversion section 11R The components, which detect blue light and red light respectively, are stacked. However, the content of the present disclosure is not limited to such a structure. That is to say, the organic photoelectric conversion section can detect red light or blue light, or the inorganic photoelectric conversion section can detect green light.

[0191] Furthermore, the number of these organic photoelectric conversion sections and inorganic photoelectric conversion sections, or a portion thereof, is not limited. Two or more organic photoelectric conversion sections can be provided, or color signals of a variety of colors can be obtained using only the organic photoelectric conversion section. Moreover, the structure is not limited to one in which the organic photoelectric conversion section and the inorganic photoelectric conversion sections are stacked vertically; rather, the organic photoelectric conversion section and the inorganic photoelectric conversion sections can be arranged side by side along a substrate surface.

[0192] Furthermore, the embodiment described above illustrates the configuration of a solid-state image acquisition device with back illumination, but the content of this disclosure also applies to a solid-state image acquisition device with front-surface illumination. Moreover, the photoelectric conversion element of this disclosure need not necessarily include all the components described in the embodiment above and may, conversely, include an additional layer.

[0193] It should be noted that the effects described here are merely examples and not exhaustive. Other effects may also occur.

[0194] It should be noted that the present disclosure may have the following configurations. (1) A photoelectric conversion element comprising: a first electrode; a second electrode positioned opposite the first electrode; and an organic photoelectric conversion layer provided between the first electrode and the second electrode, wherein the organic photoelectric conversion layer has a domain made of an organic semiconductor material therein, wherein the domain of one organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in a film thickness direction, and has a smaller domain length in a plane direction of the organic photoelectric conversion layer than a domain length in the film thickness direction of the organic photoelectric conversion layer. (2) The photoelectric conversion element according to (1), in which the organic photoelectric conversion layer exhibits an interference pattern in a cross-sectional photograph in the direction of the film thickness, wherein the cross-sectional photograph was taken with a transmission electron microscope under defocused conditions, wherein the interference pattern comprises two or more lines, and an interval between the two or more lines enclosed in the interference pattern lies within ±50% of a molecular length of the one organic semiconductor material. (3) The photoelectric conversion element according to (2) wherein the interference pattern has a length of 20 nm or more. (4) The photoelectric conversion element according to (2) or (3) wherein an angle formed between the interference pattern and an electrode surface of the first electrode is greater than 45° and 90° or less. (5) The photoelectric conversion element according to one of the points (2) to (4) where the interference pattern comprises fewer than ten lines. (6) The photoelectric conversion element according to any of (1) to (5) wherein an interface between the organic photoelectric conversion layer and the second electrode has a surface roughness of 10 nm or less. (7) The photoelectric conversion element according to one of (1) to (6) in which the organic semiconductor material has a hole transport property. (8) A solid-state imaging device comprising Pixels, each comprising one or more organic photoelectric conversion sections, The organic photoelectric conversion sections each comprise a first electrode, a second electrode arranged opposite the first electrode and an organic photoelectric conversion layer provided between the first electrode and the second electrode, wherein the organic photoelectric conversion layer has a domain of an organic semiconductor material therein, wherein the domain of one organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in a film thickness direction, and has a smaller domain length in a plane direction of the organic photoelectric conversion layer than a domain length in the film thickness direction of the organic photoelectric conversion layer. (9) Solid-state imaging device according to (8) in which one or more organic photoelectric conversion sections and one or more inorganic photoelectric conversion sections are stacked in each pixel, wherein the one or more inorganic photoelectric conversion sections each perform a photoelectric conversion in a wavelength range that differs from wavelength ranges of the organic photoelectric conversion sections. (10) The solid-state imaging device according to (9), in which the inorganic photoelectric conversion sections are each embedded in and formed within a semiconductor substrate, and the organic photoelectric conversion sections are each formed on a first surface side of the semiconductor substrate. (11) The solid-state imaging device according to (10) wherein a multilayer wiring layer is formed on a second surface side of the semiconductor substrate. (12) The solid-state imaging device according to (10) or (11), wherein The organic photoelectric conversion sections each convert green light photoelectrically, and an inorganic photoelectric conversion section that photoelectrically converts blue light, and an inorganic photoelectric conversion section that photoelectrically converts red light, in which semiconductor substrates are stacked. (13) Solid-state imaging device according to any of (8) to (12) wherein a plurality of organic photoelectric conversion sections are stacked in each pixel, the plurality of organic photoelectric conversion sections performing the photoelectric conversion in respective wavelength ranges which differ from each other.

[0195] This application claims priority on the basis of Japanese patent application No. 2017-222977, filed with the Japan Patent Office on November 20, 2017, the entire contents of which are incorporated into this application by reference.

[0196] It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and changes may occur depending on design requirements and other factors, insofar as they fall within the scope of the attached claims or their equivalents. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2017222977

[0195] < / arbeitsbeispiele> < / anwendungsbeispiele>

Claims

[1] Photoelectric conversion element comprising: a first electrode; a second electrode positioned opposite the first electrode; and an organic photoelectric conversion layer provided between the first electrode and the second electrode, wherein the organic photoelectric conversion layer has a domain made of an organic semiconductor material therein, wherein the domain of one organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in a film thickness direction, and has a smaller domain length in a plane direction of the organic photoelectric conversion layer than a domain length in the film thickness direction of the organic photoelectric conversion layer. [2] Photoelectric conversion element according to claim 1, wherein the organic photoelectric conversion layer exhibits an interference pattern in a cross-sectional photograph in the direction of the film thickness, wherein the cross-sectional photograph was taken with a transmission electron microscope under defocusing conditions and the interference pattern includes two or more lines, and an interval between the two or more lines enclosed in the interference pattern lies within ±50% of a molecular length of the one organic semiconductor material. [3] Photoelectric conversion element according to claim 2, wherein the interference pattern has a length of 20 nm or more. [4] Photoelectric conversion element according to claim 2, wherein an angle formed between the interference pattern and an electrode surface of the first electrode is greater than 45° and 90° or less. [5] Photoelectric conversion element according to claim 2, wherein the interference pattern comprises fewer than ten lines. [6] Photoelectric conversion element according to claim 1, wherein an interface between the organic photoelectric conversion layer and the second electrode has a surface roughness of 10 nm or less. [7] Photoelectric conversion element according to claim 1, wherein one organic semiconductor material has a hole transport property. [8] Solid-state imaging device comprising: Pixels, each comprising one or more organic photoelectric conversion sections, The organic photoelectric conversion sections each comprise a first electrode, a second electrode positioned opposite the first electrode, and an organic photoelectric conversion layer provided between the first electrode and the second electrode, wherein the organic photoelectric conversion layer has a domain made of an organic semiconductor material therein, wherein the domain of one organic semiconductor material has a percolation structure in which the domain extends vertically in the organic photoelectric conversion layer in a film thickness direction, and has a smaller domain length in a plane direction of the organic photoelectric conversion layer than a domain length in the film thickness direction of the organic photoelectric conversion layer. [9] Solid-state imaging device according to claim 8, wherein one or more organic photoelectric conversion sections and one or more inorganic photoelectric conversion sections are stacked in each pixel, the one or more inorganic photoelectric conversion sections each performing a photoelectric conversion in a wavelength range that differs from the wavelength ranges of the organic photoelectric conversion sections. [10] Solid-state imaging device according to claim 9, wherein the inorganic photoelectric conversion sections are each embedded in and formed in a semiconductor substrate, and the organic photoelectric conversion sections are each formed on a first surface side of the semiconductor substrate. [11] Solid-state imaging device according to claim 10, wherein a multilayer wiring layer is formed on a second surface side of the semiconductor substrate. [12] Solid-state imaging device according to claim 10, wherein the organic photoelectric conversion sections each photoelectrically convert green light, and an inorganic photoelectric conversion section that photoelectrically converts blue light, and an inorganic photoelectric conversion section that photoelectrically converts red light, are stacked in the semiconductor substrate. [13] Solid-state imaging device according to claim 8, wherein a plurality of the organic photoelectric conversion sections are stacked in each pixel, the plurality of organic photoelectric conversion sections performing the photoelectric conversion in respective wavelength ranges that differ from each other.