Photodetector element using a metal grid transparent electrode and touchless user interface device using the same

Abstract

The purpose of the present invention is to provide a photodetector element which makes it possible to maintain high transparence and increase light detectability, and a touchless user interface device using same.　A photodetector element (10) according to the present disclosure comprises: a metal grid transparent electrode (20) as a first electrode; a transparent electrode (60) as a second electrode facing the metal grid transparent electrode (20); and a sub-pixel (44S) composed of at least one photoelectric conversion layer (44) between the metal grid transparent electrode and the transparent electrode, wherein the metal grid transparent electrode (20) includes a transparent material (22), and a conductive pattern (24P) having metal wirings (24) provided on the transparent material (22), the sub-pixel (44S) includes a sub-sensor area (44SS) in at least a portion thereof, and a region in which the sub-sensor area (44SS) projected from the top surface is provided is at least partially overlapped with a region in which the metal wiring (24) is provided.

Description

[Technical Field]

[0001] The present invention relates to a photodetector element using a metal grid transparent electrode that enables both high visible light transmittance and high external quantum efficiency, particularly in the near-infrared wavelength region, and a touchless user interface device using the same. [Background technology]

[0002] Touch user interfaces that detect touch, such as touch panels, are widely used in smartphones, smart watches, laptops, ATMs, kiosks, e-book readers using electronic paper, etc. Touch user interfaces have a transparent touch panel mounted on a display device such as a monitor.

[0003] In recent years, from the perspectives of further expanding user experience, improving public hygiene awareness, and preventing static electricity, touchless user interfaces have attracted attention as an alternative to touch user interfaces, and vigorous research and development is being conducted on them. One example of a method for realizing a touchless user interface is to use light from a light source such as a laser pointer or reflected light from a pointing means such as a finger as an optical input signal, and to provide a transparent sensor panel or sensor sheet having a photodetector array composed of photodetectors arranged one-dimensionally or two-dimensionally on a display or other display device to detect the position of the optical input signal, thereby performing input operations on a screen, for example.

[0004] Non-Patent Document 1 discloses an organic photodetector array in which an opaque organic photoelectric conversion layer capable of detecting light in the wavelength range of 500 nm to 600 nm is patterned into islands of 10 μm × 10 μm size by photolithography, and an organic photodetector element is mounted for each unit pixel. Patterning each organic photoelectric conversion layer into a minute island shape makes it possible to increase the area ratio of openings with high visible light transmittance, thereby achieving both a high transmittance of 70% in the visible light range and the ability to detect visible light. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] H. Akkerman et al., Integration of large area optical imagers for biometric recognition and touch in displays, J. Soc. Inf. Display., May 2021, P. 1-13 [Non-patent document 2] Peter van de Weijer et al., High-performance thin-film encapsulation for organic light-emitting diodes, Org. Electron., May 2017, Vol. 44, P. 94-98 [Non-patent document 3] PE Malinowski et al., Organic photo-lithography for displays with integrated fingerprint scanner, J. Soc. Inf.Display.,50(1), 1007-1010 (2019). https: / / doi.org / 10.1002 / sdtp.13097 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the effective sensor area of ​​the organic photodetector element disclosed in Non-Patent Document 1 is 100 μm 2 Therefore, the detection current I is also very small. Therefore, it is difficult to use a photodetector array composed of the organic photodetector elements disclosed in Non-Patent Document 1 in a touchless user interface from the standpoint of the signal-to-noise ratio in an actual usage environment. In addition, the organic photodetector element disclosed in Non-Patent Document 1 uses a solid, non-transparent metal film for the cathode, and increasing the effective sensor area to improve the signal-to-noise ratio would impair visible light transmittance.

[0007] Therefore, an object of the present invention is to provide a photodetector element that can improve light detectability while maintaining high transparency, and a touchless user interface device using the same. [Means for solving the problem]

[0008] That is, the present invention is as follows. A photodetector element comprising a metal grid transparent electrode as a first electrode, a transparent electrode as a second electrode facing the metal grid transparent electrode, and a subpixel consisting of at least one photoelectric conversion layer between the metal grid transparent electrode and the transparent electrode, wherein the metal grid transparent electrode comprises a transparent substrate and a conductive pattern having metal wiring provided on the transparent substrate, and the subpixel comprises a subsensor area in at least a portion thereof, and the region where the subsensor area is provided and the region where the metal wiring is provided overlap at least in part when projected from above.

[0009] S TCE-unit is the repeating unit area of ​​the conductive pattern, and S sub―s ensor When is the area of ​​the sub-sensor area, S sub―sensor / S TCE-unit is 1 or more.

[0010] The photodetector element is also characterized in that at least a portion of the sub-sensor area projected from the top surface of the photodetector element overlaps, in at least one direction, with two or more of the metal wirings extending in the same direction.

[0011] The photodetector element has an insulating layer having an opening between the metal grid transparent electrode and the transparent electrode, the subpixel is arranged so as to cover the opening when projected onto the surface from the top surface in the stacking direction, and the subsensor area corresponds to the area where the subpixel and the opening overlap when projected onto the surface from the top surface in the stacking direction.

[0012] In the photodetector element, the shape of the region where the subpixels are provided, projected from above, is at least one selected from the group consisting of a square, a rectangle, an approximately square, and an approximately rectangle.

[0013] The photodetector element includes a subpixel array made up of a plurality of the subpixels arranged at a distance from each other.

[0014] The subpixel array is the photodetector element having a pattern in which the subpixels are arranged two-dimensionally at equal intervals along two orthogonal coordinate axes in parallel planes of the subpixel array.

[0015] S subOPD is the area of ​​the sub-pixel, S subOPD is 25 μm 2 More than 10000μm 2 The photodetector element is as follows:

[0016] The photodetector element has an external quantum efficiency of 15% or more at at least a part of the wavelength in the near-infrared wavelength range of 780 nm to 1200 nm, and a visible light transmittance of 50% or less in the stacking direction of the photodetector element in the region including the sub-sensor area.

[0017] t TCE is the thickness of the metal wiring, and t OPD When the thickness of the sub-sensor area is t TCE is 30 nm or more and 200 nm or less, and (t OPD -t TCE ) is 50 nm or more and 500 nm or less.

[0018] W TCE is the line width of the metal wiring of the metal grid transparent electrode, and G TCE is the gap between adjacent metal wirings extending in the same direction, W TCE is 0.25 μm or more and 5.0 μm or less, and G TCE is 45 μm or less, and (G TCE / W TCE )teeth The photodetector element has a refractive index of 1.0 or more.

[0019] A TCE is the aperture ratio of the conductive pattern, (G TCE A TCE ) is 0.25 μm·% or more and 45 μm·% or less.

[0020] Aperture ratio A of the conductive pattern TCE is 25% or more and less than 100%.

[0021] The photoelectric conversion layer of the photodetector element is an organic photoelectric conversion layer.

[0022] E g optis the optical band gap, the organic photoelectric conversion layer has an optical band gap of E g opt Organic donor materials with E g opt and an organic acceptor material having a Vref of 1.65 eV or less.

[0023] In the photodetector element, the organic acceptor material is at least one selected from the group of non-fullerene acceptor materials consisting of IEICO-4F, IEICO-4Cl, IEICO, DTPC-DFIC, DCI-2, COTIC-4F, PDTTIC-4F, DTPC-IC, 6TIC-4F, COiDFIC, FOIC, F8IC, F10IC, SiOTIC-4F, and P3.

[0024] In the photodetector element, the organic donor material is at least one selected from the group consisting of PTB7-Th (also known as PCE-10), PDTP-DFBT, PDPP3T, PDPP3T-O14, PDPP3T-O16, PDPP3T-O20, PDPP3T-C20, PDPP4T, DPPTfQxT, DPPTQxT, DPPBTQxBT, DPPBTffQxBT, FLP030 (trade name), PBDTT-SeDPP, PBDTT-DPP, PBDTT-FDPP, PDPP2T-TT (PTT-DTDPP), PCDTBT, PCPDTBT, PCPDTFBT, and Si-PCPDTBT.

[0025] The metal wiring is the photodetector element, and includes a metal and an oxide of the metal.

[0026] The conductive pattern is the photodetector element, which comprises a mesh pattern.

[0027] The present invention also provides a photodetector array in which two or more pixels each made of the photodetector element are arranged.

[0028] a wiring section provided on the transparent substrate and having a second conductive pattern electrically connected to the conductive pattern, the wiring section being provided for each pixel; wire is the aperture ratio of the second conductive pattern, -10%≦(A wire -A TCE )≦10%.

[0029] a current collecting portion having a third conductive pattern provided on the transparent substrate and electrically connected to the second conductive pattern, pad is the occupied area ratio of the third conductive pattern per unit area, Γ pad is 50% or more and less than 100%.

[0030] The photodetector array further comprises a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern.

[0031] A dummy is the aperture ratio of the dummy pattern, -10%≦(A dummy -A TCE )≦10%.

[0032] The photodetector array includes an insulating layer provided on the metal grid transparent electrode, a dummy subpixel array including a plurality of dummy subpixels made of the photoelectric conversion layer provided on the insulating layer, and a subpixel array including a plurality of the subpixels, wherein the dummy subpixel array and the subpixel array have the same pattern structure when projected from above.

[0033] The pixel size of the photodetector array is 1 mm 2 More than 25mm 2 The photodetector array is as follows:

[0034] The photodetector array has a pixel density of 2 ppi or more and 15 ppi or less.

[0035] The photodetector array has a pattern in which the pixels are arranged two-dimensionally at equal intervals along two orthogonal coordinate axes in parallel planes of the photodetector array.

[0036] The present invention also provides a touchless user interface device that includes the photodetector array to be placed on the screen of a display or display body, and detects the position at which the optical input signal is irradiated by converting an optical input signal irradiated to the photodetector array into an electrical output signal using the photodetector elements of the photodetector array, thereby enabling input operations to be performed on the screen of the display or display body by the position detection.

[0037] In the touchless user interface device, the optical input signal includes light having at least a part of a wavelength in a near-infrared wavelength region of 780 nm to 1200 nm.

[0038] In the touchless user interface device, the optical input signal is frequency modulated, and the modulation frequency is 0.5 kHz or more and 20 kHz or less.

[0039] The touchless user interface device, wherein the optical input signal is an optical signal emitted from a laser pointer.

[0040] The touchless user interface device, wherein the optical input signal is reflected light from a pointing means.

[0041] In the touchless user interface device, the optical input signal is reflected light from the pointing means that is generated when the pointing means comes into contact with a planar projection light beam formed in space. [Effects of the Invention]

[0042] According to the present invention, it is possible to provide a photodetector element having high transparency and high light detection ability, and a touchless user interface device using the same. [Brief explanation of the drawings]

[0043] [Figure 1] 1A and 1B are a cross-sectional view and a top view of an organic photodetector element according to an embodiment. [Figure 2] FIG. 2 is an enlarged plan view of a metal grid transparent electrode according to an embodiment. [Figure 3] 10 is a diagram illustrating a modified example of a sub-sensor area according to an embodiment. [Figure 4] 1 is a graph of GTCE-external quantum efficiency (EQE, λ: 850 nm, IP: 1.05 mW / cm 2 , V: −2 V) at different line widths. [Figure 5] This is a graph of (GTCE / WTCE)-EQE (λ: 850 nm, IP: 1.05 mW / cm2, V: -2 V) for different line widths. [Figure 6] This is a graph of (GTCE·ATCE)-EQE (λ: 850 nm, IP: 1.05 mW / cm2, V: -2 V) for different line widths. [Figure 7] 1A and 1B are schematic diagrams of an organic photodetector array according to an embodiment and a partially enlarged view of an area AR1. [Figure 8] 3A and 3B are a cross-sectional view and a top view of a dummy pattern portion of an organic photodetector array according to an embodiment. [Figure 9] FIG. 1 is a schematic diagram of a touchless user interface device according to an embodiment. [Figure 10] FIG. 2 is a functional block diagram of a touchless user interface device according to an embodiment. [Figure 11] 1 is a graph comparing the light transmission spectrum of Example A1 with an optical model. [Figure 12] 10 is a graph comparing the light transmission spectrum of Comparative Example A1 with an optical model. [Figure 13] 1 is an optical microscope image of the organic photodetector element of Example B1. [Figure 14] 1 is a graph showing dark current density (Jdark)-voltage (V) characteristics and photocurrent density (Jphoto)-V characteristics of Example B1. [Figure 15] 1 is a graph of wavelength (λ) vs. EQE (V: −2V) for Example B1. [Figure 16] 1 is a graph of light intensity (IP) vs. Jphoto for Example B1. [Figure 17] 1 is a graph comparing the simulation and actual measurement of EQE (V: −2V) of Example B1. [Figure 18] 10 is a histogram of dark current density and photocurrent density of the organic photodetector array of Example D. [Figure 19] 10 is a photograph showing a map operation application on a display using a demonstration model of the touchless user interface device of Example D. [Figure 20] 10 is a photograph of a demonstration model of the touchless user interface device of Example D when operating buttons on a display. [Figure 21] 1A and 1B are schematic plan and cross-sectional views of an organic photodetector array according to one embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0044] An embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail below, but the present invention is not limited to this and various modifications are possible without departing from the spirit of the present invention. The upper and lower limit values ​​of each numerical range in the present embodiment can be arbitrarily combined to form any numerical range. In the drawings, identical elements are given the same symbols and redundant explanations will be omitted. Furthermore, unless otherwise specified, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings. Furthermore, the dimensional ratios in the drawings are not limited to those shown.

[0045] [1. Organic photodetector element] FIG. 1 shows a cross-sectional view (FIG. 1(A)) of an organic photodetector element (hereinafter sometimes referred to as an "organic PD element" or "OPD element") 10 according to this embodiment and a projection view (FIG. 1(B)) of the OPD element 10 projected from above. In FIG. 1(A), incident light traveling from the bottom to the top of the page passes through the metal grid transparent electrode 20 and generates electrons and holes in the organic photoelectric conversion layer 44. As a result, photovoltaic power is generated between the metal grid transparent electrode 20 and the transparent electrode 60, causing a current to flow, and the OPD element 10 is configured to be able to detect incident light.

[0046] As shown in the figure, the OPD element 10 includes a metal grid transparent electrode 20 that functions as a cathode (an example of a "first electrode") and a transparent electrode 60 that faces the metal grid transparent electrode 20 and functions as an anode (an example of a "second electrode"). This configuration prevents a loss of visible light transmittance even when the element area (so-called pixel size) of the OPD element 10 is increased. The OPD element 10 also includes an electron transport layer 42, a hole transport layer 46, an organic photoelectric conversion layer 44, and an insulating layer 80, which are disposed between the metal grid transparent electrode 20 and the transparent electrode 60. The electron transport layer 42 is disposed on the metal grid transparent electrode 20, the organic photoelectric conversion layer 44 and the insulating layer 80 are disposed on the electron transport layer 42, and the hole transport layer 46 is disposed on the organic photoelectric conversion layer 44 and the insulating layer 80. In other words, the insulating layer 80 is provided between the electron transport layer 42 and the hole transport layer 46, and separates the sub-pixels 44S that make up the organic photoelectric conversion layer 44 from each other.

[0047] The metal grid transparent electrode 20 is an electrode that transmits incident light and detects photocurrent generated in the organic photoelectric conversion layer 44 based on the transmitted incident light. The metal grid transparent electrode 20 according to this embodiment has an electrode portion made up of a transparent substrate 22 and a conductive pattern 24P made up of metal wiring 24 provided on the transparent substrate 22. The metal wiring 24 may contain a metal component that provides conductivity and an oxide of the metal component. An example of the configuration of the metal grid transparent electrode 20 is described in detail in the section [1.2 Metal grid transparent electrode 20: Metal grid TCE].

[0048] In this specification, the metal wiring 24 provided on the transparent substrate 22 refers not only to a configuration consisting of metal wiring 24 provided on the transparent substrate 22 in contact with the surface of the transparent substrate 22, but also to a configuration consisting of metal wiring 24 provided on the transparent substrate 22 via another layer provided between the transparent substrate 22 and the metal wiring 24 without contacting the surface of the transparent substrate 22. For example, a transparent conductive inorganic compound layer may be provided between the transparent substrate 22 and the metal wiring 24. Similarly, when one thing is provided or formed on another thing, the two things are not in contact with each other.

[0049] The organic photoelectric conversion layer 44 generates a photocurrent based on incident light. The organic photoelectric conversion layer 44 according to this embodiment can be provided between an electron transport layer 42 and a hole transport layer 46, which are provided on the metal grid transparent electrode 20 so as to cover the metal grid transparent electrode 20.

[0050] Examples of the configurations of the electron transport layer 42, the organic photoelectric conversion layer 44, and the hole transport layer 46 are described in detail in the sections [1.3 Electron transport layer 42 (ETL)], [1.4 Organic photoactive layer 44)], and [1.5 Hole transport layer 46 (HTL)], respectively.

[0051] The transparent electrode 60 is an electrode for detecting a photocurrent generated in the organic photoelectric conversion layer 44 based on incident light. The transparent electrode 60 according to this embodiment is provided on the organic photoelectric conversion layer 44 to the hole transport layer 46. An example of the configuration of the transparent electrode 60 will be described in detail in the section [1.6 Transparent electrode 60 (anode)].

[0052] The organic photoelectric conversion layers 44 of the OPD element 10 (single pixel) according to this embodiment are arranged in an island-like pattern, spaced apart from one another. In this specification, each of these spaced-apart organic photoelectric conversion layers 44 may be referred to as a subpixel 44S. Accordingly, the OPD element 10 (pixel) according to this embodiment includes a plurality of subpixels 44S. The OPD element 10 includes a total of 196 subpixels 44S, arranged two-dimensionally, for example, 14 subpixels vertically and 14 subpixels horizontally (FIG. 7). The projection view of FIG. 1(B) shows four of the subpixels 44S. As shown in FIG. 1(B), each subpixel 44S is spaced apart from its adjacent subpixel 44S by at least its vertical dimension in the plane of the drawing, and is spaced apart from its adjacent subpixel 44S by at least its horizontal dimension in the plane of the drawing. Each subpixel 44S is configured to generate a photocurrent based on incident light. Therefore, one or more sub-pixels 44S in the OPD element 10 generate photocurrent based on incident light, and the OPD element 10 is configured to be able to detect the incidence of light.

[0053] 1A and 1B, a subpixel 44S of the organic photoelectric conversion layer 44 includes a subsensor area 44SS provided on the electron transport layer 42 in contact with or adjacent to the electron transport layer 42, an alignment area 44SA surrounding the subsensor area 44SS in a projection view and provided on the electron transport layer 42 in a side view (cross-sectional view) separated from the electron transport layer 42 via an insulating layer 80, and a connection portion 44SC extending approximately perpendicular to the surface of the transparent substrate 22 to connect the subsensor area 44SS and the alignment area 44SA. As shown in the drawings, the subpixel 44S is formed in, for example, a substantially polygonal shape (e.g., a square or rectangular shape) in a projection view, and in a side view (cross-sectional view), the alignment areas 44SA corresponding to both ends are separated from the electron transport layer 42, and the subsensor area 44SS corresponding to the center connecting the both ends is formed in a substantially U-shape in contact with or adjacent to the electron transport layer 42. In this specification, the area of ​​a single sub-sensor area 44SS in the projection view is S sub―sensor It is sometimes called.

[0054] 2 is an enlarged plan view of the metal grid transparent electrode 20. The metal grid transparent electrode 20 according to this embodiment has a mesh pattern (one example of a "conductive pattern 24P", FIG. 3(A)) formed by a plurality of linearly extending metal wires 24 intersecting at right angles in a mesh pattern. When the conductive pattern 24P made up of a plurality of metal wires 24 has a periodic shape, the area of ​​the repeating unit (unit) in the projection drawing in this specification (the "repeating unit area") is S TCE-unit The mesh pattern of the metal grid transparent electrode 20 according to this embodiment is composed of rectangular shapes that are repeatedly and periodically arranged, and therefore the area of ​​a rectangle or a figure that forms a rectangular shape surrounded by the center line (the dashed line in FIG. 2) of the metal wiring 24 in a plan view is the repeating unit area S TCE -unit is equivalent to

[0055] 1(B), the organic photoelectric conversion layer 44 and the metal wiring 24 of the OPD element 10 according to this embodiment are provided so that, in a top projection, the region where the subsensor area 44SS is provided and the region where the metal wiring 24 is provided at least partially overlap. In other words, in a top projection, at least one metal wiring 24 is provided so as to pass through the subsensor area 44SS of the organic photoelectric conversion layer 44, preferably so as to intersect two different sides of the subsensor area 44SS of the organic photoelectric conversion layer 44 and pass through the subsensor area 44SS.

[0056] By providing such a structure, it is possible to realize a configuration in which electrons generated in the organic photoelectric conversion layer 44 can be easily transported to the nearby metal wiring 24 via the electron transport layer 42. Therefore, it is possible to improve the external quantum efficiency (light detectability) compared to a configuration in which the organic photoelectric conversion layer 44 is provided only in the openings of the conductive pattern 24P in a projection view.

[0057] Additionally, at least one sub-sensor area 44SS (organic photoelectric conversion layer 44) is provided within the OPD element 10 (pixel). This configuration makes it possible to increase the area ratio of the region with relatively high visible light transmittance (region excluding the sub-pixel 44S or sub-sensor area 44SS). This makes it possible to improve the visible light transmittance of the organic photodetector element and organic photodetector array.

[0058] Here, as shown in this embodiment, a plurality of (for example, preferably 10 or more, more preferably 50 or more) subpixels 44S (organic photoelectric conversion layers 44) may be provided spaced apart from one another within the OPD element 10. Such a configuration can improve the detectability of incident light.

[0059] For example, the OPD element 10 may include a first subpixel 44S in which at least one metal wiring 24 passes through the subsensor area 44SS (organic photoelectric conversion layer 44), and a second subpixel 44S that is provided apart from the first subpixel 44S and in which at least one metal wiring 24 passes through the subsensor area 44SS (organic photoelectric conversion layer 44). Here, the metal wiring 24 that passes through the first subpixel 44S and the metal wiring 24 that passes through the second subpixel 44S may be the same.

[0060] As described above, the OPD element of this embodiment includes an organic photoelectric conversion layer 44. However, the photodetector according to the present invention may also include, for example, an inorganic photoelectric conversion layer. That is, the photoelectric conversion layer may be an organic photoelectric conversion layer or an inorganic photoelectric conversion layer made of quantum dots or an inorganic semiconductor, and preferably an organic photoelectric conversion layer. Similarly, the electron transport layer 42 and the hole transport layer 46 may be made of either an organic material or an inorganic material.

[0061] Furthermore, in the projection view of the OPD element 10 (FIG. 1B), S corresponding to the area of ​​the sub-sensor area 44SS sub―sensor and S corresponding to the repeating unit area of ​​the conductive pattern 24P. TCE-unit is S sub―sensor / S TCE-unit ≧1. sub―sensor / S TCE-unit is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. In the example shown in FIG. 1(B), S sub―sensor / S TCE-unit is 5 or more (S sub ―sensor / S TCE-unit ≧5).

[0062] S sub―sensor / S TCE-unitSince S is 1 or more, in at least one direction in the projection view, the sub-sensor area 44SS can be provided on at least one of the metal wirings 24 that extend in the same direction within the conductive pattern 24P and face each other in a direction approximately perpendicular to the extending direction. This relationship holds even if the relative positions of the conductive pattern 24P and the sub-sensor area 44SS are shifted during the lamination process. Therefore, S sub―sensor / S TCE-unit When S is 1 or more, electrons generated in the organic photoelectric conversion layer 44 provided on the opening of the conductive pattern 24P are transported to the nearest metal wiring 24 via the electron transport layer 42 and are easily collected, thereby improving the external quantum efficiency. sub―sensor / S TCE-unit As the number of metal wirings 24 overlapping the sub-sensor area 44SS increases, the charge collection efficiency η cc The external quantum efficiency tends to improve as the S sub―sensor / S TCE-unit There is no particular upper limit to the value of S, and it can be, for example, 100. sub―sensor / S TCE-unit The upper limit of S can be more preferably 85 or less, even more preferably 65 or less, even more preferably 50 or less, and particularly preferably 40 or less. sub―sensor / S TCE-unit As the value of the subpixel 44S decreases, the subpixel 44S can be made smaller, which is preferable because it is possible to reduce the visibility of the organic photodetector element.

[0063] In addition, S sub―sensor / S TCE-unit It is preferable to increase the area of ​​the subsensor 44SS so that, in the projection view, a portion of the subsensor area 44SS overlaps with at least two or more metal wires 24 extending in the same direction. For example, as shown in Fig. 1(B), the subsensor area 44SS may overlap with two metal wires 24 that both extend in the vertical direction of the page, and may overlap with three metal wires 24 that both extend in the horizontal direction of the page.

[0064] With this configuration, even if the sub-sensor area 44SS is manufactured shifted in a direction perpendicular to the extension direction of the metal wiring 24, the sub-sensor area 44SS is arranged to overlap with at least one metal wiring 24, making it possible to collect charges in an optimal manner.

[0065] As described above, the organic photodetector element of this embodiment uses the metal grid transparent electrode 20 as the cathode, the transparent electrode 60 as the anode, and at least the organic photoelectric conversion layer 44 is provided between the cathode and the anode.

[0066] The organic photoelectric conversion layer 44, the anode, the cathode, etc. may be made of conventionally known materials and structures that are generally used in organic photodetector elements.

[0067] For example, the following configurations can be applied to the present invention as the element configuration of the organic photodetector element. (A) Cathode / organic photoelectric conversion layer 44 / anode (B) Cathode / electron transport layer 42 / organic photoelectric conversion layer 44 / anode (C) Cathode / organic photoelectric conversion layer 44 / hole transport layer 46 / anode (D) Cathode / electron transport layer 42 / organic photoelectric conversion layer 44 / hole transport layer 46 / anode

[0068] The symbol " / " in the above (A) to (D) indicates that the layers on either side of the symbol " / " are stacked adjacent to each other. This also applies to the following explanations. The organic photodetector element may have a configuration including two or more organic photoelectric conversion layers 44.

[0069] In addition, the organic photodetector element of this embodiment may be a standard stack (forward type element) in which light is incident from the anode, or an inverse stack (inverse type element) in which light is incident from the cathode. Also, the metal grid transparent electrode 20 or another metal grid transparent electrode may be used as the anode, and the transparent electrode 60 or another transparent electrode may be used as the cathode.

[0070] In the organic photodetector element of this embodiment, the cathode and anode are transparent electrodes, so that an optical input signal may be incident from either the anode side or the cathode side. Preferably, the organic photodetector element is an inverse stack in which light is incident from the cathode side, which is a metal grid transparent electrode.

[0071] The lower limit of the external quantum efficiency of the OPD element 10 at least in part of the near-infrared wavelength region of 780 nm to 1200 nm is preferably 15% or more, more preferably 20% or more, even more preferably 25% or more, and particularly preferably 30% or more. There is no particular limit to the upper limit of the external quantum efficiency, and it can be, for example, preferably 100% or less, more preferably 90% or less, and more preferably 80% or less.

[0072] By setting the lower limit of the external quantum efficiency to 15% or more at least in part of the wavelength range of 780 nm to 1200 nm in the near-infrared wavelength region, the OPD element 10 can exhibit good light detectability in the near-infrared wavelength region.

[0073] Here, there is a trade-off between the external quantum efficiency and the visible light transmittance of the organic photodetector element in the subpixel portion. Therefore, by setting the external quantum efficiency to the above-mentioned upper limit or less, the visible light transmittance of the organic photodetector element in the subpixel portion tends to improve, thereby reducing the visibility of the subpixel portion.

[0074] Because near-infrared light is invisible to the human eye, irradiating it as an optical input signal onto a display such as a monitor does not impair the visibility of the display (the visibility of images, etc. displayed on the display). Furthermore, when using reflected light from a pointing device such as a finger as an optical input signal for a touchless user interface, light from a light source is irradiated onto a person. Even in this case, because near-infrared light is invisible to the human eye, a person can view images, etc. displayed on the display without worrying about the reflected light from the pointing device.

[0075] Furthermore, as disclosed in MJ Mendenhall, AS Nunez, and RK Martin, "Human skin detection in the visible and near infrared," Appl. Opt. 54(35), 10559-10570 (2015), the wavelength region of 780 nm to 1200 nm in the near infrared wavelength region is Human skin has a high reflectance, particularly in the wavelength range of 780 nm to 950 nm, and many commercially available LEDs are available for use as light sources for optical input signals. Therefore, when near-infrared light reflected from a pointing means such as a finger is used as an optical input signal for a touchless user interface, it is preferable that the organic photodetector element be able to detect light with high efficiency at least in part of the wavelength range of 780 nm to 1200 nm near-infrared.

[0076] The visible light transmittance in the stacking direction of the organic photodetector element in the region including the subsensor area 44SS, i.e., in Figure 1(A), the visible light transmittance of the subpixel 44S passing through the metal grid transparent electrode 20, the subsensor area 44SS of the organic photoelectric conversion layer 44, and the transparent electrode 60 as it progresses from the bottom to the top of the paper, is preferably 50% or less, more preferably 40% or less, even more preferably 35% or less, even more preferably 30% or less, even more preferably 25% or less, and particularly preferably 20% or less.

[0077] The lower limit of the visible light transmittance is not particularly limited, and can be, for example, preferably more than 0%, more preferably 5% or more, and even more preferably 10% or more. In order to obtain a high external quantum efficiency in at least a part of the near-infrared wavelength region of 780 nm to 1200 nm, the organic photodetector element of this embodiment selects an organic photoelectric conversion layer 44 having a high extinction coefficient k (absorption coefficient α) in that wavelength region, and / or the film thickness t of the organic photoelectric conversion layer 44 is set to 0. OPD On the other hand, such an organic photoelectric conversion layer 44 has a high light absorptance even in the long wavelength region of visible light (550 nm or more).

[0078] Therefore, by setting the visible light transmittance to 50% or less, it is possible to obtain high external quantum efficiency in the near-infrared wavelength region. Also, by setting the visible light transmittance to the lower limit or more, the visibility of the subpixel 44S tends to be reduced.

[0079] Dark current density J of the organic photodetector element of this embodiment at an applied voltage of −2 V da rk is preferably 10 -4 mA / cm 2 Less than or equal to 10, more preferably -5 mA / cm 2 Below 5 × 10, particularly preferably -6 mA / cm 2 When the dark current density is equal to or less than the upper limit, an organic photodetector element with high detectivity tends to be obtained.

[0080] [1.1 Insulation layer 80: ECL, Edge Cover Layer] The organic photodetector element of this embodiment includes an insulating layer 80 (FIG. 1(A)) provided between the metal grid transparent electrode 20 and the transparent electrode 60. In this embodiment, the insulating layer 80 is laminated on an electron transport layer 42 formed on the metal grid transparent electrode 20 so as to cover the metal grid transparent electrode 20. The insulating layer 80 has a plurality of openings OP (portions of the insulating layer 80 where openings are provided) formed at intervals. The openings OP expose the electron transport layer 42 upward.

[0081] In a projection view projected from the top surface in the stacking direction onto the surface, the subpixels 44S are arranged to cover the openings OP, and the portions of the subpixels 44S that overlap with the openings OP correspond to the sub-sensor areas 44SS, and the portions surrounding the openings OP correspond to the alignment areas 44SA. In the cross-sectional view ( FIG. 1(A) ), the alignment areas 44SA are provided on an insulating layer 80. By providing the insulating layer 80, it is possible to suppress short circuits between the cathodes and anodes in areas other than the subpixels 44S.

[0082] The insulating layer 80 may be made of a conventional material and structure that is generally used in organic photodetector elements and semiconductor elements. The insulating layer 80 is not particularly limited, but may be made of, for example, silicon oxide (SiO X(0<X≦2) ), silicon nitride (SiN X(0<X≦4 / 3) ), silicon oxynitride (SiO X N Y ), aluminum oxide (AlO X(0<X≦3 / 2) Examples of suitable resin layers include inorganic compound layers such as phenolic resin, thermosetting epoxy resin, thermosetting polyimide, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, diallyl phthalate resin, and silicone resin; UV-curable resins such as urethane acrylate, acrylic resin acrylate, epoxy acrylate, silicone acrylate, and UV-curable epoxy resin; and resin layers such as commercially available coating agents. The insulating layer 80 may be made of a single material or may be a laminate of two or more materials.

[0083] The insulating layer 80 having the openings OP can be formed by first dry- or wet-forming a solid film of the material that will become the insulating layer 80 over the entire surface of the device, and then forming the openings OP in the insulating layer 80 using a known patterning method such as photolithography, nanoimprinting, lift-off, or laser ablation. Alternatively, the insulating layer 80 (particularly the aforementioned resin layer) having the openings OP can be formed by pattern printing using a known printing method such as gravure printing, gravure offset printing, letterpress printing, flexographic printing, inkjet printing, or screen printing. If necessary, the formed insulating layer 80 can be cured by ultraviolet light or heat. Alternatively, the insulating layer 80 can be fixed by baking.

[0084] Examples of dry film formation methods for the solid inorganic compound layer used as the insulating layer 80 include vapor phase film formation methods such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition). In order to form a dense inorganic compound layer with few pinholes, the inorganic compound layer is preferably formed by sputtering, PECVD, or ALD (Atomic Layer Deposition). The thickness of the inorganic compound layer is preferably 10 nm or more and 2000 nm or less, more preferably 30 nm or more and 1000 nm or less, and even more preferably 50 nm or more and 500 nm or less. When the thickness of the inorganic compound layer is 10 nm or more, the insulating properties are excellent. When the thickness of the inorganic compound layer is 2000 nm or less, the visible light transmittance is excellent. In addition, the generation of cracks due to bending can be suppressed, and further, the increase in internal stress during film formation can be suppressed, thereby preventing the generation of defects.

[0085] Furthermore, known coating methods such as slot die coating and spin coating, as well as casting methods, can be used as wet film formation methods for the solid resin layer used as the insulating layer 80. The thickness of the resin layer is preferably 100 nm or more and 5000 nm or less, more preferably 500 nm or more and 2500 nm or less, and even more preferably 800 nm or more and 2000 nm or less. A resin layer thickness of 100 nm or more provides excellent insulation properties. A resin layer thickness of 5000 nm or less provides excellent visible light transmittance.

[0086] It is particularly preferable that the insulating layer 80 having the opening OP is formed by forming a solid film of SU-8 (trade name) photocurable epoxy resin on the entire surface of the element, soft baking it, patterning it with exposure, and developing it.

[0087] In this embodiment, the shapes of the subsensor areas 44SS and the subpixels 44S are rectangular or square in a projected view of the OPD element 10 seen from above. However, there are no particular limitations on the shapes of the subsensor areas 44SS and the subpixels 44S, and they may be circular, square, rectangular, polygonal, approximately circular, approximately square, approximately rectangular, approximately polygonal, or the like in the projected view.

[0088] 3A, 3B, 3C, and 3D show square, circular, rectangular, and circular subsensor areas 44SS, respectively. For example, by providing a circular opening in the insulating layer 80, a circular subsensor area 44SS may be formed in a projected view, and a square-shaped subpixel 44S including the circular subsensor area 44SS may be formed. Furthermore, when there are multiple subpixels 44S, each subpixel 44S may have a different shape. The shape of the subpixel 44S is preferably at least one selected from the group consisting of a square, a rectangle, a nearly square, and a nearly rectangular. Note that a nearly square shape refers to a shape having four sides of equal length that form right angles with adjacent sides, including, for example, a shape having four sides of equal length that form right angles with adjacent sides and having arc-shaped corners connecting two adjacent sides. An approximately rectangular shape refers to a shape that has four sides that form right angles with adjacent sides, and includes, for example, a shape that has four sides that form right angles with adjacent sides and has corners that are formed into arcs to connect two adjacent sides.

[0089] [Subpixel 44S] Here, S subOPD Let S be the area of ​​a single subpixel 44S. subOPD is preferably 25 μm 2 More than 10000μm 2 More preferably, it is 100 μm or less. 2 More than 6400μm 2 or less, and more preferably 225 μm 2 Over 4900μm 2 and even more preferably 400 μm or less. 2 More than 3600μm 2and particularly preferably 1600 to 3000 μm. 2 The following is the result.

[0090] S subOPD is 25 μm 2 If it is more than this, the photodetection current will be large, which is preferable. sub OPD is 10,000 μm 2 If it is less than this, it is possible to reduce the visibility of the subpixels 44S with low visible light transmittance to the human eye, which is preferable.

[0091] Furthermore, the area of ​​a single subpixel 44S is preferably at least one-tenth the area of ​​a pixel of the OPD element 10 or less.

[0092] As described above, the OPD element 10 of this embodiment includes a plurality of subpixels 44S formed as islands spaced apart from one another. As shown in Fig. 1(B) , each subpixel 44S is provided on an electron transport layer 42 integrally formed to have the same electrical potential, and is also provided below a hole transport layer 46 integrally formed to have the same electrical potential. Therefore, the plurality of subpixels 44S constituting a pixel are electrically bonded or connected. In other words, one pixel is composed of a plurality of subpixels 44S that are electrically bonded or connected.

[0093] The sub-pixels 44S may be arranged one-dimensionally within the OPD element 10, or may be arranged two-dimensionally as shown in this embodiment. The sub-pixels 44S may also be arranged randomly, or may form any regular arrangement pattern, or may be an arrangement pattern that combines a plurality of these.

[0094] The OPD element 10 of this embodiment has a subpixel array consisting of a pattern in which a plurality of spaced-apart subpixels 44S are arranged, and more preferably has a pattern structure in which a plurality of subpixels 44S are arranged two-dimensionally at equal intervals along two orthogonal coordinate axes in parallel planes of the subpixel array, as shown in FIG. 1(B).

[0095] The significance of constituting a single pixel by electrically joining or connecting a plurality of sub-pixels 44S that are spaced apart from one another will be described below. In general, the current I(λ) detected from an organic photodetector element is expressed by the following equation:

[0096]

number

[0097] where EQE(λ)(%) is the external quantum efficiency of the organic photodetector element, I P (λ)(mW / cm 2 ) is an organic The light intensity irradiated onto the detector element, S (cm 2 ) is the effective sensor area of ​​the organic photodetector element per unit pixel, λ is the wavelength of the irradiating light, q is the elementary charge, h is Planck's constant, and c is the speed of light. In other words, the detected current I is proportional to the effective sensor area S within a unit pixel.

[0098] On the other hand, the effective sensor area of ​​the organic photodetector element disclosed in Non-Patent Document 1 is 100 μm 2 Therefore, the detection current I is also very small.

[0099] In addition, disturbances such as natural light, indoor light, and light emitted from display devices such as displays contain a large amount of visible light, which becomes noise.

[0100] Furthermore, when an optical input signal propagates through space, the optical intensity decreases as the propagation distance d increases. 2 Attenuates with.

[0101] For the above reasons, it is difficult to use the photodetector array made up of organic photodetector elements disclosed in Non-Patent Document 1 in a touchless user interface from the standpoint of the signal-to-noise ratio in an actual usage environment.

[0102] Therefore, the inventors of the present application have noticed that when used in a touchless user interface, high resolution (e.g., 164 ppi (Pixel per inch)) like the photodetector array of Non-Patent Document 1 is not required, and that a pixel pitch of 4 mm to 6 mm (approximately 4 to 7 ppi) in each of two dimensional directions (e.g., orthogonal X-axis and Y-axis directions) is sufficient.

[0103] Furthermore, the inventors of the present application came up with the idea of ​​a configuration in which a photoelectric conversion layer of subpixels smaller than the pixel size is provided within a single pixel by patterning or the like. A photodetector element with such a configuration includes island-shaped subpixels made of organic or inorganic photoelectric conversion layers with a relatively low visible light transmittance within a single pixel, making it possible to increase the area of ​​openings with a relatively high visible light transmittance (i.e., regions where no photoelectric conversion layer is formed). This makes it possible to improve the visible light transmittance of the entire photodetector element.

[0104] The number of subpixels provided within a single pixel may be one or more. For example, by providing subpixels each consisting of a plurality of organic photoelectric conversion layers spaced apart from one another within a single pixel, it is possible to increase the area ratio of openings with relatively high visible light transmittance. This makes it possible to improve the visible light transmittance of the organic photodetector element and organic photodetector array.

[0105] Here, a pixel corresponds to a unit of spatial resolution of a photodetector array. Since one or more photoelectric conversion layers are provided within a single pixel, each photoelectric conversion layer is provided for each subpixel, which is smaller than one pixel. As described above, each photoelectric conversion layer may be formed, for example, by patterning.

[0106] In addition, the inventors of the present application came up with a configuration in which the region where the sub-sensor area within a subpixel is provided, as projected from above, overlaps at least partially with the region where the metal wiring of the metal grid transparent electrode is provided. Here, the sub-sensor area refers to the region of the island-shaped photoelectric conversion layer that functions as a sensor, and more specifically, the region that is adjacent to and faces the electrode.

[0107] This structure allows electrons generated in the photoelectric conversion layer above the openings in the metal grid transparent electrode to be transported to the nearby metal wiring via the electron transport layer and collected, thereby improving the external quantum efficiency (light detectability) of photodetector elements using the metal grid transparent electrode.

[0108] Furthermore, the area of ​​the sub-sensor area within a subpixel may be designed to be equal to or larger than the area of ​​the repeating unit of the conductive pattern of the metal grid transparent electrode, where the area of ​​the sub-sensor area refers to the area of ​​the sub-sensor area when viewed from above (planar view).

[0109] With this configuration, even if the relative positions of the metal grid transparent electrode and the subpixels formed by the photoelectric conversion layer are shifted during manufacturing (the lamination process), at least a portion of the sub-sensor area is arranged to overlap the metal wiring, which, for the reasons described above, makes it possible to more reliably improve the external quantum efficiency (light detectability) of a photodetector element using a metal grid transparent electrode.

[0110] To improve the signal-to-noise ratio, the inventors devised an OPD element 10 in which the pixel size is, for example, 4 mm × 4 mm or less and a plurality of tiny island-shaped organic photoelectric conversion layers 44 are arranged (arrayed) within the pixel as subpixels 44S. This configuration makes it possible to increase the area ratio of subpixels other than the subpixels 44S with low visible light transmittance, thereby increasing the total effective sensor area within the pixel while improving the visible light transmittance of the pixel as a whole. When achieving the same total effective sensor area with the same pixel size, arranging a large number of small-area subpixels 44S is preferable to arranging a small number of large-area subpixels 44S, because this reduces the visibility of the subpixels 44S.

[0111] where Γ subOPD is the area occupancy rate of the subpixel 44S within the repeating pattern unit of the subpixel array (for example, if a subpixel array of area Y is provided for each area X, the area occupancy rate corresponds to "100 × (Y / X) (%)"). subOPD is preferably 3% or more and 25% or less, more preferably 4% or more and 20% or less, even more preferably 5% or more and 15% or less, still more preferably 5.5% or more and 12% or less, and particularly preferably 6% or more and 10% or less. subOPD It is preferable that Γ is 3% or more, since the total effective sensor area of ​​the subpixel array can be increased. subOPD If the ratio is 25% or less, the total area occupied by the subpixels 44S with low visible light transmittance is reduced, which is preferable because the visible light transmittance of the entire organic photodetector element is improved.

[0112] [1.2 Metal grid transparent electrode 20: Metal grid TCE] As shown in FIG. 1(A), the metal grid transparent electrode 20 of this embodiment has a transparent substrate 22 and an electrode portion made up of a conductive pattern 24P made up of metal wiring 24 provided on the transparent substrate 22.

[0113] [1.2.1 Transparent base material] In this embodiment, a transparent substrate 22 is used. Here, "transparent" means that the visible light transmittance is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. Here, the visible light transmittance can be measured in accordance with JIS K 7361-1:1997.

[0114] The transparent substrate 22 may be made of one material or may be made of a laminate of two or more materials. When the transparent substrate 22 is a multilayer structure made of two or more materials, the transparent substrate 22 may be made of a laminate of transparent organic or transparent inorganic substrates, which are examples of the core layer described below, or may be made of a combination of a transparent organic substrate and a transparent inorganic substrate. The transparent substrate 22 may be a single layer or a multilayer structure, and may have a barrier layer, intermediate layer, or the like provided on the core layer. Examples of the transparent substrate 22 include a core layer, a core layer / barrier layer, a core layer / barrier layer / intermediate layer, and a core layer / intermediate layer / barrier layer. It is also possible for a single layer to function as both a barrier layer and an intermediate layer.

[0115] The material for the core layer is not particularly limited, but examples thereof include glass such as quartz glass, other transparent inorganic substrates, polyethylene terephthalate, polyethylene naphthalate, polyimide, and other transparent organic substrates. The thickness of the core layer is preferably 5 μm or more and 2 mm or less, and more preferably 10 μm or more and 1.5 mm or less.

[0116] The intermediate layer is not particularly limited, but examples thereof include silicon compounds (e.g., (poly)siloxanes, silicon oxide, silicon nitride), aluminum compounds (e.g., aluminum oxide), and magnesium compounds (e.g., magnesium fluoride). The thickness of the intermediate layer is preferably 0.01 μm to 100 μm, more preferably 0.01 μm to 10 μm, and even more preferably 0.01 μm to 1 μm. When the thickness of the intermediate layer is within the above range, the adhesion is further improved, and the transparency and durability of the metal grid transparent electrode 20 tend to be further improved.

[0117] The barrier layer has high blocking properties against moisture and oxygen, and contributes to suppressing deterioration of the characteristics of the organic photodetector element due to the intrusion of moisture and oxygen into the organic photodetector element. The gas barrier properties of the barrier layer are as follows: the water vapor permeability (25±0.5°C, relative humidity (90±2)%) measured by a method conforming to JIS K 7129-1992 is 1×10 -7 g / (m 2 24hr)~1×10 -3 g / (m 2 24 hours) Preferably, 1 x 10 -7 g / (m 2 24hr)~1×10 -4 g / (m 2 ·twenty four hr), and more preferably in the range of 1×10 -7 g / (m 2 24hr)~1×1 0 -5 g / (m 2 It is more preferable that the water vapor permeability is in the range of 1×10 24 hr. When the water vapor permeability is in this range, deterioration of characteristics such as a decrease in EQE and an increase in dark current of the organic photodetector element during long-term use can be suppressed. Furthermore, it is preferable that the oxygen permeability measured by a method in accordance with JIS K 7126-1987 is in the range of 1×10 24 hr. -6 mL / m 2 24h atm~1×10 -2 mL / m 2 ·24h·atm is preferred, and 1×10 -6 mL / m 2 24h atm~1×10 -3 mL / m 2 24h atm is more preferable, and 1×10 -6 mL / m 2 24h atm~1×10 -4 mL / m 2 ·24h·atm is even more preferable.

[0118] The barrier layer may have a conventionally known composition, structure, and formation method commonly used in organic photodetector elements. The barrier layer may be a single layer or a laminated structure of two or more layers. In the case of a laminated structure, inorganic compound layers, organic compound layers, or inorganic polymer layers may be laminated together, or inorganic compound layers, organic compound layers, or inorganic polymer layers may be combined and laminated together. Among these, a structure in which inorganic compound layers and organic compound layers are alternately laminated multiple times is preferred to improve the fragility of the barrier layer.

[0119] The inorganic compound layer of the barrier layer is not particularly limited, but may be, for example, silicon oxide (SiO X(0 <X≦2) ), silicon nitride (SiN X(0<X≦4 / 3) ), silicon oxynitride (SiO X N Y ), aluminum oxide (AlO X(0<X≦3 / 2) ), aluminum nitride (AlN), etc. can be used. The thickness of the inorganic compound layer is preferably 30 nm or more and 1000 nm or less, more preferably 50 nm or more and 500 nm or less, and even more preferably 100 nm or more and 200 nm or less. When the thickness of the inorganic compound layer is 30 nm or more, excellent gas barrier properties are achieved. When the thickness of the inorganic compound layer is 1000 nm or less, excellent visible light transmittance is achieved.

[0120] The organic compound layer of the barrier layer is not particularly limited, and examples thereof include thermosetting resins such as phenolic resins, UV-curable resins such as urethane acrylate, acrylic resin acrylate, epoxy acrylate, and silicone acrylate, and commercially available coating agents. The organic compound layer may also have a structure in which particles of a hygroscopic compound are dispersed within the layer. Examples of hygroscopic compounds include metal oxides (e.g., calcium oxide), sulfates, metal halides, and perchlorates. The thickness of the organic compound layer is preferably 0.5 μm to 100 μm, more preferably 5 μm to 50 μm, and even more preferably 10 μm to 30 μm. An organic compound layer having a thickness of 0.5 μm or more provides excellent gas barrier properties. An organic compound layer having a thickness of 100 μm or less provides excellent visible light transmittance.

[0121] The inorganic polymer layer of the barrier layer is not particularly limited, but silicon-containing polymers such as polysilazanes, polysiloxanes, and polysiloxazanes can be used. The thickness of the inorganic polymer layer is preferably 10 nm to 10 μm, more preferably 30 nm to 8 μm, and even more preferably 50 nm to 5 μm. When the thickness of the inorganic polymer layer is 10 nm or more, the gas barrier properties are excellent. When the thickness of the inorganic polymer layer is 10 μm or less, the visible light transmittance is excellent.

[0122] It is particularly preferable to use the same material and structure as the thin film encapsulation layer (TFE) disclosed in Non-Patent Document 2 as the barrier layer.

[0123] [1.2.2 Electrode part]

[0124] The electrode section is composed of a transparent electrode (hereinafter also referred to as a "metal grid transparent electrode" or "metal grid TCE") having a conductive pattern 24P consisting of fine metal wiring 24 on a transparent substrate 22. The metal grid transparent electrode achieves high flexibility and low sheet resistance due to the high ductility and high electrical conductivity of the metal wiring. Additionally, it has the advantage that properties such as visible light transmittance and sheet resistance can be freely changed by adjusting the line width and film thickness of the metal wiring, the gap of the conductive pattern, etc. Furthermore, although the metal wiring itself is opaque, adjusting the line width of the metal wiring to 3 μm or less makes it invisible to the human eye, further improving the transparency (transmittance) of the metal grid transparent electrode itself.

[0125] A "metal grid" electrode includes an electrode in which a plurality of metal wires 24 extending in different directions are provided, thereby providing a plurality of regions surrounded by the metal wires 24, with the intersections of the metal wires 24 serving as vertices. Here, each metal wire 24 may extend linearly or curvedly. The region surrounded by the metal wires 24 is called an aperture, and the portion where the aperture is provided may be called an opening. As described below, the plurality of metal wires 24 may be arranged periodically at a predetermined pitch, or may not be arranged regularly and may be arranged randomly in all or part of the region.

[0126] (Conductive pattern 24P) The conductive pattern 24P may be a regular or irregular pattern. Examples include a mesh pattern formed by a plurality of linearly extending metal wires 24 intersecting in a mesh-like pattern, a honeycomb pattern in which metal wires 24 are provided on the sides of each hexagon so that hexagonal openings are formed without gaps, and a line pattern in which a plurality of substantially parallel metal wires 24 are formed. The conductive pattern 24P may also be an arbitrary combination of a mesh pattern, a honeycomb pattern, and a line pattern. Furthermore, the conductive pattern 24P may be formed so that polygonal openings other than rectangular and hexagonal are formed without gaps. For example, when metal wires 24 defining polygonal openings simultaneously define adjacent polygonal openings, the plurality of polygonal openings are formed without gaps. The conductive pattern 24P may also be configured so that openings of different polygonal shapes are formed. The mesh of the mesh pattern may be square, rectangular, diamond, or the like. The honeycomb pattern may be formed in a regular hexagonal shape with a constant line width, or may be formed, for example, with the line width at the vertices increased so that the vertices of each opening are rounded. The metal wiring 24 forming the line pattern may be straight or curved. Furthermore, even in the metal wiring 24 forming the mesh pattern or honeycomb pattern, some or all of the metal wiring 24 may be curved.

[0127] FIG. 3A shows a mesh pattern having square openings as the conductive pattern 24P, a square sub-sensor area 44SS as the sub-sensor area 44SS, and a square area S corresponding to the area of ​​the sub-sensor area 44SS. sub―sensor and S corresponding to the repeating unit area of ​​the conductive pattern 24P. TCE-unit Toga S sub―sensor / S TCE-unit ≧1. As shown in the figure, S sub―sensor >S TCE-unitTherefore, at least two metal wires 24 extending in a predetermined direction (first direction) in the projection view pass through the subsensor area 44SS, and at least two metal wires 24 extending in a direction perpendicular to the predetermined direction (second direction) pass through the same subsensor area 44SS. Therefore, even if the relative positions of the conductive pattern 24P and the subsensor area 44SS are shifted during the lamination process as shown in Figure 3(E), it is still possible to overlap the subsensor area 44SS and the metal wires 24 in the projection view. Therefore, electrons generated in the organic photoelectric conversion layer 44 are transported to the nearest metal wire 24 via the electron transport layer 42 and are easily collected as charges, thereby improving the external quantum efficiency.

[0128] FIG. 3B shows a mesh pattern having square openings as the conductive pattern 24P, a circular sub-sensor area 44SS as the sub-sensor area 44SS, and a s ub―sensor / S TCE-unit ≧1 (for example, in the figure, S sub―se nsor / S TCE-unit 3(A), even if the relative positions of the conductive pattern 24P and the sub-sensor area 44SS are shifted during the lamination process, the sub-sensor area 44SS and the metal wiring 24 can still be made to overlap in the projection view, thereby improving the external quantum efficiency.

[0129] FIG. 3C shows a mesh pattern having rectangular (oblong) openings as the conductive pattern 24P, a rectangular (oblong) sub-sensor area 44SS as the sub-sensor area 44SS, and S sub―sensor / S TCE-unit 3(D) shows an embodiment having a relationship of ≧1, in which a honeycomb pattern having hexagonal openings is provided as the conductive pattern 24P, and a circular sub-sensor area 44SS is provided as the sub-sensor area 44SS, and S sub―sensor / S TCE-unit≧1. These embodiments also enable the same technical effect to be achieved.

[0130] (Line width) The line width W of the metal wiring 24 TCE is the line width W when the metal wiring 24 is projected onto the surface of the transparent substrate 22 from the side on which the conductive pattern 24P of the transparent substrate 22 is arranged. TCE In the metal wiring 24 having a trapezoidal cross section with a longer base on the interface side with the transparent substrate 22, the width of the surface of the metal wiring 24 in contact with the transparent substrate 22 is the line width W TCE This becomes:

[0131] W TCE is preferably 0.25 μm or more and 5.0 μm or less, more preferably 0.25 μm or more and 4.0 μm or less, even more preferably 0.25 μm or more and 3.0 μm or less, still more preferably 0.25 μm or more and 2.0 μm or less, and particularly preferably 0.25 μm or more and 1.0 μm or less. TCE By making the width W of the metal grid transparent electrode 20 0.25 μm or more, the resistance of the metal grid transparent electrode 20 can be reduced, and the voltage drop due to the detection current can be suppressed, which tends to enable the organic photodetector element to have a larger area. In addition, the increase in electrical resistance due to oxidation or corrosion of the surface of the metal wiring 24 can be sufficiently suppressed. On the other hand, the line width W of the metal wiring 24 TCE Since the gap G of the conductive pattern 24P is 5.0 μm or less, a high aperture ratio is maintained. TCE This allows the area of ​​the repeating unit of the conductive pattern 24P to be reduced, and accordingly the area of ​​the sub-sensor area 44SS can be designed to be smaller. This tends to further improve the visible light transmittance of the entire organic photodetector element, and also tends to simultaneously improve the appearance. Furthermore, the line width W of the metal wiring 24 TCE By adjusting the thickness to 3.0 μm or less, the opaque metal wiring 24 can be made invisible to the human eye. As a result, even when the organic photodetector element is disposed on a display device such as a display, the appearance and design of the display device are not impaired.

[0132] (gap) The gap G of the conductive pattern 24P in this specification TCE (FIG. 2) refers to the shortest (minimum) distance (interval) between adjacent metal wirings 24 that extend in the same direction within the conductive pattern 24P and face each other in a direction approximately perpendicular to the extension direction (however, if the metal wirings 24 extend in a curved shape, the gap G TCE corresponds to the minimum distance between two adjacent metal wirings 24 such that the straight lines approximating the curve are in roughly the same direction at least within a predetermined region).

[0133] In FIG. 4, the horizontal axis represents the gap G of the conductive pattern 24P. TCE The vertical axis represents the external quantum efficiency (EQE) obtained by the simulation, and the simulation results are plotted against different linewidths W TC E As shown in the figure, G TCE The upper limit is preferably 45 μm or less, more preferably 40 μm or less, even more preferably 35 μm or less, even more preferably 30 μm or less, and particularly preferably 25 μm or less.

[0134] In addition, in FIG. 5, the horizontal axis represents the relative value of the gap to the line width (G TCE / W TCE ) and the vertical axis is the external quantum efficiency (EQE) obtained by the simulation. The simulation results are shown for different linewidths W TCE 1 is a graph showing

[0135] As shown in the figure (G TCE / W TCE The lower limit of ) is preferably 1.0 or more, more preferably 1.5 or more, even more preferably 2.0 or more, still more preferably 3.0 or more, even more preferably 5.0 or more, and particularly preferably 7.0 or more.

[0136] (G TCE / W TCE) is 1.0 or more, the aperture ratio is improved, the shadowing effect of the metal wiring 24 is suppressed, and the efficiency of light capture into the organic photoelectric conversion layer 44 is improved, which tends to improve the external quantum efficiency of the organic photodetector element.

[0137] On the other hand, G TCE By making the gap G 45 μm or less, the surface potential distribution in the openings of the conductive pattern 24P tends to be uniform, and therefore the external quantum efficiency of the entire organic photodetector element tends to be improved. The inventors of the present application speculate that the reason why the external quantum efficiency of the entire organic photodetector element is improved by reducing the gap is as follows: Electrons generated by photoexcitation in the organic photoelectric conversion layer 44 provided on the openings of the conductive pattern 24P diffuse in-plane through the electron transport layer 42, which has a high sheet resistance, and are transported to the metal wiring 24. TCE By reducing the distance of electron diffusion from the center of the opening to the metal wiring 24, it is possible to reduce the voltage drop due to the surface resistance of the electron transport layer 42 caused by the in-plane diffusion of electrons. This tends to make the surface potential distribution of the opening of the conductive pattern 24P uniform.

[0138] Charge collection efficiency η, one of the components of external quantum efficiency cc As disclosed in J. Xue et al., A Hybrid Planar-Mixed Molecular Heterojunction Photovoltaic Cell, Advanced Materials, January 2005, Vol. 17, pp. 66-71, the external quantum efficiency tends to improve as the effective voltage (difference in surface potential between the cathode and anode) applied to the organic photoelectric conversion layer 44 increases. Therefore, it is believed that the external quantum efficiency of the entire organic photodetector element can be further improved by making the surface potential distribution of the openings in the conductive pattern 24P uniform for the reasons described above.

[0139] (Opening ratio) Conductive pattern 24P aperture ratio A TCEis preferably 25% or more and less than 100%, more preferably 35% or more and 99% or less, even more preferably 47% or more and 98% or less, even more preferably 68% or more and 97% or less, and particularly preferably 71% or more and 95% or less. TCE When the aperture ratio A is 25% or more, the external quantum efficiency of the organic photodetector element can be improved for the reasons described above. In addition, the visible light transmittance tends to be improved. TCE When the area ratio is less than 100%, the occupancy rate of the metal wiring 24 per unit area increases, which reduces the sheet resistance and tends to enable the area of ​​the organic photodetector element to be increased.

[0140] The "aperture ratio" of the conductive pattern 24P can be calculated using the following formula for the region on the transparent substrate 22 where the conductive pattern 24P is formed.

[0141] Opening ratio=(1−area occupied by conductive pattern 24P (metal wiring 24) / area of ​​transparent base material 22 in the region where conductive pattern 24P is formed)×100

[0142] For example, if the conductive pattern 24P is a mesh pattern in which square openings are formed as shown in Figure 3(A), when the line width is 1 μm and the gap is 19 μm, the area occupied by the conductive pattern 24P per unit area (the area occupied by the metal wiring 24) is approximately 10%, and the area of ​​the openings through which the transparent substrate 22 is exposed is approximately 90%, so the opening rate is approximately 90%.

[0143] In FIG. 6, the horizontal axis represents the gap G of the conductive pattern 24P. TCE and aperture ratio A TCE The vertical axis is the external quantum efficiency (EQE) obtained by the simulation, and the simulation results are plotted against different linewidths W TCE This is a graph showing the (G TCE A TCE ) is the diffusion length (G TCE ) to make the surface potential distribution uniform and the aperture ratio (A TCE) and the increase in the light capture efficiency into the organic photoelectric conversion layer 44 due to the increase in the gap width are used as indicators to improve the external quantum efficiency of the organic photodetector element. For example, if the gap is made smaller at the same line width, the electron diffusion distance is reduced, and the surface potential distribution of the opening is made uniform, resulting in an increase in the charge collection efficiency η cc On the other hand, as the aperture ratio decreases, the light blocking effect of the opaque metal wiring 24 increases, and the amount of light taken in by the organic photoelectric conversion layer 44 decreases. TCE A TCE We focused on the fact that the external quantum efficiency of an organic photodetector element equipped with a metal grid transparent electrode 20 can be improved by adjusting (G TCE A TCE ) is preferably 0.25 μm·% or more and 45 μm·% or less, more preferably 0.45 μm·% or more and 40 μm·% or less, even more preferably 1.0 μm·% or more and 35 μm·% or less, even more preferably 2.0 μm·% or more and 30 μm·% or less, even more preferably 4.0 μm·% or more and 25 μm·% or less, and particularly preferably 6.0 μm·% or more and 22 μm·% or less. (G TCE A TCE ) is 0.25 μm·% or more, the surface potential distribution at the opening can be made uniform while suppressing the decrease in the amount of light taken in due to the light-shielding effect of the metal wiring 24, and the external quantum efficiency of the organic photodetector element can be improved. TCE A TC E ) is 45 μm·% or less, the charge collection efficiency η cc The external quantum efficiency of the organic photodetector element can be improved by increasing the aperture ratio while suppressing the decrease in the TCE A TCE ) is expressed in units of μm·%, and the gap G TCE (μm) Aperture A TCE For example, when the conductive pattern 24P has a gap G of 20 μm, TCE and 90% aperture ratio A TCEIf equipped with (G TCE A TCE ) is expressed as 20 μm × 0.9 = 18 μm·%.

[0144] In this embodiment, the thickness t of the metal wiring 24 TCE is preferably 30 nm or more and 200 nm or less, more preferably 50 nm or more and 170 nm or less, even more preferably 60 nm or more and 150 nm or less, and even more preferably 70 nm or more and 130 nm or less. TCE When the thickness is 30 nm or more, the resistance of the metal grid transparent electrode 20 can be reduced, and the area of ​​the organic photodetector element tends to be increased. In addition, an increase in electrical resistance due to oxidation or corrosion of the surface of the metal wiring 24 tends to be sufficiently suppressed. TCE When the thickness is 200 nm or less, the convex metal wiring 24 can be sufficiently covered and electrical short-circuiting with the counter electrode can be suppressed within an appropriate range for adjusting the film thickness of the organic photoelectric conversion layer 44. In addition, high transparency tends to be exhibited over a wide viewing angle. t TCE can be measured by observing the cross section of the metal grid transparent electrode 20 or the organic photodetector element with an electron microscope (SEM, TEM, STEM), or by observing the plane of the metal grid transparent electrode 20 with a confocal laser microscope or the like. TCE This can also be confirmed by measuring the film thickness profile of the metal grid transparent electrode 20 using a stylus-type thin film step gauge.

[0145] The line width W of the metal wiring 24 TCE , and the gap G of the conductive pattern 24P TCE and aperture ratio A TCE The line width W of the metal wiring 24 can be confirmed by observing the surface or cross section of the metal grid transparent electrode 20 with an electron microscope, a laser microscope, an optical microscope, or the like. TC E and the gap G between the conductive pattern 24P TCE To adjust the value to a desired range, the grooves of a plate used in the manufacturing method of the metal grid transparent electrode 20 described later may be adjusted, or the average particle diameter of metal particles in the ink may be adjusted.

[0146] The metal wiring 24 may contain a metal component M and an oxide of the metal component M. The metal component M is responsible for the conductivity of the metal wiring 24. The mechanism by which the conductivity is exerted by the metal component M is not particularly limited, but is presumed to be similar to the free electron model of metals. The metal component M is not particularly limited, but examples thereof include gold, silver, copper, and aluminum. Of these, copper, which is relatively inexpensive and has high conductivity, is more preferable. By using such a metal component M, the conductivity of the metal grid transparent electrode 20 tends to be further improved. The oxide of the metal component M is not particularly limited, but since it is preferable to select copper as the metal component M for the reasons mentioned above, cuprous oxide, cupric oxide, copper hydroxide, etc. are preferred.

[0147] Furthermore, the metal wiring 24 may contain a non-conductive component in addition to the metal component M that provides conductivity. The non-conductive component is not particularly limited, but examples thereof include oxides of the metal component M and organic compounds. More specifically, these non-conductive components are derived from components contained in the ink described below, and include oxides of the metal component M and organic compounds that remain in the metal wiring 24 after firing.

[0148] The content of the metal component M in the metal wiring 24 is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. There is no particular upper limit to the content of the metal component M, but it is preferably less than 100% by mass. The content of the non-conductive component in the metal wiring 24 is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. There is no particular lower limit to the content of the non-conductive component, but it is more than 0% by mass.

[0149] (sheet resistance) The sheet resistance R of the conductive pattern 24P of the metal grid transparent electrode 20 s_TCE The sheet resistance R is preferably 0.1 Ω / sq. or more and 100 Ω / sq. or less. s_TCEThe upper limit of the sheet resistance R is more preferably 90 Ω / sq. or less, even more preferably 80 Ω / sq. or less, even more preferably 70 Ω / sq. or less, and particularly preferably 60 Ω / sq. or less. s_TCE When the sheet resistance R is 100 Ω / sq. or less, the voltage drop caused by the electrical resistance of the metal grid transparent electrode 20 can be suppressed, and the area of ​​the organic photodetector element tends to be increased. s_TCE is the aperture ratio A of the conductive pattern 24P TCE The thickness t of the metal wiring 24 is reduced. TCE This can be reduced by making adjustments such as increasing the ratio of the metal component M in the metal wiring 24, or selecting a metal component M with high conductivity.

[0150] Sheet resistance R s_TCE is JIS K for the part where the conductive pattern 24P is arranged. 7194:1994. An example of a measuring device for the four-terminal method is "Loresta GP" (product name, manufactured by Mitsubishi Chemical Corporation). s_TCE The measurement can also be performed by a non-contact method using eddy current in accordance with ASTM F 673-02 for the portion where the conductive pattern 24P is arranged.

[0151] (Visible light transmittance) Visible light transmittance (VLT) of the area where the conductive pattern 24P of the metal grid transparent electrode 20 is arranged TCE is preferably 23% or more and 98% or less, more preferably 32% or more and 96% or less, even more preferably 43% or more and 95% or less, still more preferably 55% or more and 94% or less, even more preferably 62% or more and 93% or less, and particularly preferably 69% or more and 92% or less. TCE is the aperture ratio A of the conductive pattern 24P TCE Visible light transmittance (VLT) tends to improve with increasing TCEcan be calculated from the transmission spectrum of the area where the conductive pattern 24P of the metal grid transparent electrode 20 is arranged in accordance with JIS R 3106:2019 or ISO9050:2003. TCE can also be calculated by multiplying the visible light transmittance of the transparent substrate 22 by the aperture ratio of the conductive pattern 24P.

[0152] [1.2.3 Manufacturing method of metal grid transparent electrode 20] A method for manufacturing the metal grid transparent electrode 20 includes a pattern formation process in which a pattern is formed on the transparent substrate 22 using ink containing a metal component M, and a firing process in which the ink is fired to form the conductive pattern 24P.

[0153] [Pattern Forming Process] The pattern formation step is a step of forming a pattern using ink containing metal component M. The pattern formation step is not particularly limited as long as it is a plate-based printing method using a plate having grooves of the desired conductive pattern 24P, but it may include, for example, a step of coating the surface of a transfer medium with ink, a step of bringing the ink-coated surface of the transfer medium into opposition to the convex surface of a relief plate and pressing and contacting them to transfer the ink on the surface of the transfer medium to the convex surface of the relief plate, and a step of bringing the surface of the transfer medium on which the ink remains into opposition to the surface of transparent substrate 22 and pressing and contacting them to transfer the ink remaining on the surface of the transfer medium to the surface of transparent substrate 22.

[0154] The ink used in the pattern formation process contains a metal component M and a solvent, and may also contain a surfactant, a dispersant, a reducing agent, etc. The metal component M may be contained in the ink as metal particles or as a metal complex.

[0155] The average primary particle size of the metal particles is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 30 nm or less. The lower limit of the average primary particle size of the metal particles is not particularly limited, but may be 1 nm or more. By making the average primary particle size of the metal particles 100 nm or less, the line width of the resulting metal wiring 24 can be made thinner. The term "average primary particle size" refers to the particle size of each individual metal particle (so-called primary particle), and is distinct from the average secondary particle size, which is the particle size of an aggregate (so-called secondary particle) formed by a group of multiple metal particles.

[0156] The metal particles are not particularly limited, and examples thereof include metal oxides and metal compounds containing a metal component M such as copper oxide as a constituent atom, and core / shell particles in which the core is a metal component M such as copper and the shell is a metal oxide such as copper oxide that also contains a metal component M as a constituent atom. The form of the metal particles can be determined appropriately from the viewpoints of dispersibility and sinterability.

[0157] The content of metal particles in the ink is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 35% by mass or less, and even more preferably 10% by mass or more and 35% by mass or less, relative to the total mass of the ink composition.

[0158] In the firing step, for example, the metal component M in the ink transferred to the surface of the transparent substrate 22 is sintered to form the conductive pattern 24P. The firing method is not particularly limited as long as it can fuse the metal component M to form a metal component sintered film. The firing may be performed, for example, in a firing furnace, or using plasma, a heating catalyst, ultraviolet light, vacuum ultraviolet light, an electron beam, infrared lamp annealing, flash lamp annealing, a laser, or the like. The resulting metal component sintered film contains a conductive component derived from the metal component M, and may also contain non-conductive components depending on the components used in the ink and the firing temperature.

[0159] [1.3 Electron transport layer 42 (ETL)] The electron transport layer 42 of this embodiment efficiently transports electrons generated by photoexcitation in the organic photoelectric conversion layer 44 to the metal grid transparent electrode 20, which serves as the cathode. The electron transport layer 42 also preferably functions as a hole blocking layer to reduce dark current density. The electron transport layer 42 is formed so as to cover the conductive pattern 24P of the metal grid transparent electrode 20.

[0160] From the viewpoint of electron transportability, the difference between the LUMO of the organic acceptor material and the conduction band or LUMO (Lowest Unoccupied Molecular Orbital) of the electron transport layer 42, or at least one of the defect level or doping level responsible for electron conduction, is preferably within 1.0 eV, more preferably within 0.5 eV, and even more preferably within 0.3 eV. Furthermore, the conduction band or LUMO of the electron transport layer 42, or at least one of the defect level or doping level responsible for electron conduction, is preferably shallower than the energy level determined by the work function of the metal grid transparent electrode 20 (4.65 eV for copper). Furthermore, from the viewpoint of hole blocking property, the valence band or HOMO (Highest Occupied Molecular Orbital) of the electron transport layer 42 is preferably at least 0.3 eV deeper, more preferably at least 0.5 eV deeper, and even more preferably at least 1.0 eV deeper, than the HOMO of the organic donor material.

[0161] The electron transport layer 42 can be made of a conventionally known material and structure that is generally used in organic photodetector elements and organic solar cells. The electron transport layer 42 is not particularly limited, but may be made of IGZO, ZnO, TiO X(1≦X≦2) , SnO X(1≦X≦2) , CeO X(4 / 3≦X≦2) , Nb2O5, Eu2O3, MoO X(2≦X≦3) , AlO X(0<X ≦3 / 2), In2O3, BaSnO4, ZnMgO, ZnS, Bi2S3, etc. The electron transport layer 42 can be understood by those skilled in the art from the following descriptions: Boping Yang et al., "Inorganic top electron transport layer for high performance inverted perovskite solar cells," EcoMat, October 2021, Vol. 3, p. e12127; Liangyou Lin et al., "Inorganic Electron Transport Materials in Perovskite Solar Cells," Advanced Functional Materials, January 2021, Vol. 31, p. 2008300; Kobra Valadi et al., "Metal oxide electron transport materials for perovskite solar cells: a review," 2021, Vol. 19, pp. 2185-2207.

[0162] From the viewpoint of electron transporting properties and hole blocking properties, it is particularly preferable that the electron transporting layer 42 be made of a-IGZO (amorphous IGZO).

[0163] The thickness of the electron transport layer 42 is preferably 5 nm to 100 nm, more preferably 8 nm to 80 nm, even more preferably 10 nm to 60 nm, and particularly preferably 12 nm to 40 nm. A thickness of 5 nm or more is preferred from the viewpoints of electron transport properties and hole blocking properties. A thickness of 100 nm or less is preferred because visible light transmittance is improved.

[0164] The electron transport layer 42 is preferably formed by a vapor phase film formation method such as PVD or CVD, and is particularly preferably formed by a sputtering method or a vacuum deposition method.

[0165] [1.4 Organic photoactive layer 44] The organic photoelectric conversion layer 44 of this embodiment is a (photoelectric conversion) layer that absorbs light containing an optical input signal, separates photoexcited excitons, and generates electron and hole carriers. The organic photoelectric conversion layer 44 preferably includes at least one organic donor material and one organic acceptor material. Furthermore, the organic photoelectric conversion layer 44 of this embodiment has an island-shaped subpixel 44S (or subpixel array) structure for the purpose of improving the visible light transmittance of the entire organic photodetector element.

[0166] The organic photoelectric conversion layer 44 can be made of a conventionally known material, composition, and structure that are generally used in organic photodetector elements and organic solar cells.

[0167] Examples of the structure of the organic photoelectric conversion layer 44 include a planar heterojunction, a bulk heterojunction, and a hybrid type that combines these. A planar heterojunction is a structure having at least one PN junction formed by stacking a layer (P-type layer) made of one or more organic donor materials and a layer (N-type layer) made of one or more organic acceptor materials. A bulk heterojunction is a structure (in layer) in which one or more organic donor materials (or a phase made of one or more organic donor materials) and one or more organic acceptor materials (or a phase made of one or more organic acceptor materials) are mixed and junctioned. The hybrid type can have a structure in which a P-type layer, an i-layer, and an N-type layer are sequentially stacked. Alternatively, the hybrid type can have a structure called an inter-immersion type in which the P-type layer, the i-layer, and the N-type layer are continuously layered without any layer boundaries. From the viewpoint of obtaining high external quantum efficiency, the organic photoelectric conversion layer 44 preferably has a structure having a bulk heterojunction that easily separates excitons.

[0168] For the reasons described above, the organic photoelectric conversion layer 44 of this embodiment preferably photoelectrically converts near-infrared light having at least a part of the wavelength in the near-infrared wavelength region of 780 nm to 1200 nm.

[0169] [Organic acceptor material] The organic acceptor material is a material that has the property of readily accepting electrons, and more specifically, is a material that has electron-accepting properties and exhibits a large electron affinity when used in contact with an organic donor material.

[0170] Optical band gap E of organic acceptor materials g opt For the purpose of photoelectric conversion of the above-mentioned near-infrared light, the optical band gap E in this specification is preferably 1.65 eV or less, more preferably 1.60 eV or less, even more preferably 1.50 eV or less, still more preferably 1.45 eV or less, still more preferably 1.40 eV or less, still more preferably 1.35 eV or less, and particularly preferably 1.30 eV or less. g opt is a value calculated using the longest wavelength at which light absorption begins (light absorption edge) of the material, as is commonly defined in the technical field.

[0171] The organic acceptor material may be a conventionally known material that is generally used in organic photodetector elements and organic solar cells. The organic acceptor material is not particularly limited, but may be C 60 or C 70 , C 84 Fullerenes such as PC 61 BM and PC 71 BM, IC 60 Examples include fullerene derivatives such as BA; non-fullerene acceptors (NFAs), etc. For the purpose of photoelectric conversion of near-infrared light as described above, it is preferable to use a non-fullerene acceptor (NFA) as the organic acceptor material.

[0172] Non-fullerene acceptors (NFAs) include, without particular limitation, IEICO, IEICO-4F, IEICO-4Cl, IEIC, IEIC1, IEIC2, IEIC3, TPE-4DPPDCV, SCPDT-4DPPDCV, SCPDT-PDI4, TVIDTPDI, TVIDTzPDI, DTPC-DFIC, DCI-2, COTIC-4F, PDTTIC-4F, DTPC-IC, 6TIC, 6TIC-4F, F10IC, COi8DFIC, F6IC, F8IC, F10IC, PBI-Por, FOIC, SiOTIC-4F, ATT-2, ATT-1, P2, P3, ITDI, CDTDI, INPIC, INPIC-4F, NFBDT, NFBDT-Me, NFBDT-F, IHIC, BTP, BTP-4F, BTP-4Cl, ITIC, ITIC-F, ITIC-M (m-ITIC), ITIC-DM, ITIC-Th, ITIC-Th1, O-IDTBR, EH-IDTBR, IDT-2BR, IDT-2BR1, IDT-2PDI, IDT-N, IDT-T-N, IDT2Se, IDT2Se-4F, IDT-4CN, IDT-BOC6, IDTT(TCV)2, IDTT(TCV)³, IDTT(TCV)4, IDTT-2BM, IDTIDT-IC, IDTIDSe-IC, BDTIT-M, BDTThIT-M, FDICTF, IDSe―T-IC, IC-C6IDT-IC, IT-M, IT-DM, IT-4F, IT―4Cl, BT-IC, BT-CIC, P(NDI2OD―T2), P(NDI2HD―T2), P(NDI2TOD―T2), PNDIS―HD, P(IDT―NDI), PNDI―T10, NDI-CNTVT, ITCC-M, ITC6-IC, ITCPTC, Ph-DTDP-IC, Ph-DTDP-TIC, Ph-DTDP-TTIC, NFTI, MPU1(2), DC-IDT2T, INIC2, INIC3, DTCC-IC, N2200, DFBDT, CZTT-IC, NDIC, DTCFO-IC, MO-IDIC, IC―2IDT―IC, m―IDTV―PhIC, PTB4F, BDSeIC, TC―FIC, M1, IDTT―2BM, DOC2C6―IC, A4T-16, SN6IC-4F, Y1, Y1-4F, Y1, Y2, Y5, Y6, Y1-4F, Y6Se, Y6-Se-4Cl, Y14, AQx, BTCIC-4Cl, BTPV-4F, IUIC,Examples include ITVfIC and IEICS-4F.

[0173] In addition, the non-fullerene acceptor (NFA) is, for example, Dong Meng et al., Near-infrared Materials: The Turning Point of Organic Photovoltaics, Advanced Materials, 2021, Accepted Author Manuscript 2107330, Hao-Wen Cheng et al., Toward High-Performance Semitransparent Organic Photovoltaics with Narrow-Bandgap Donors and Non-Fullerene Acceptors, Advance Energy Materials, 2021, P. 2102908, Yiwen Wang et al., Recent Progress and Challenges toward Highly Stable Nonfullerene Acceptor-Based Organic Solar Cells, Advance Energy Materials, 2021, Vol. 11, P. 2003002, Andrew Wadsworth et al., Critical review of the molecular design progress in non-fullerene electron acceptors towards commercially viable organic solar cells Alternative p-doped hole transport material for low operating voltage and high efficiency organic light-emitting diodes, Chemical Society Reviews, 2019, Vol. 48, P. 1596-1625, Cenqi Yan et al., Non-fullerene acceptors for organic solar cells, Nature Reviews Materials, 2018, Vol. 3, P. 18003, Leiping Duan et al., Progress in non-fullerene acceptor based organic solar cells, Solar Energy Materials and Solar Cells, May 2019, Vol. 193, P. 22-65, Guangye Zhang et al., Non-fullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells, Chemical Reviews, 2018, Vol. 118, P. 3447-3507, Pei Cheng et al., Next-generation organic photovoltaics based on non-fullerene acceptors, Nature Photonics, 2018, Vol. 12, P. 131-142, Lichun Chang et al., Ternary organic solar cells based on non-fullerene acceptors: A review, Organic Electronics, March 2021, Vol. 90, P. 106063, Materials described in Huiting Fu et al., Advances in Non-Fullerene Acceptor Based Ternary Organic Solar Cells, Solar RRL, December 2017, Vol. 2, P. 1700158, etc. can be used and understood by those skilled in the art.

[0174] From the viewpoint of obtaining high external quantum efficiency in the near-infrared region described above, the organic acceptor material is preferably at least one selected from the non-fullerene acceptor group consisting of IEICO, IEICO-4F, IEICO-4Cl, DTPC-DFIC, DCI-2, COTIC-4F, PDTTIC-4F, DTPC-IC, 6TIC, 6TIC-4F, F10IC, COi8DFIC, F6IC, F8IC, F10IC, PBI-Por, FOIC, SiOTIC-4F, ATT-2, P3, ITDI, and BTP-4Cl. From the same viewpoint, it is particularly preferable that the organic acceptor material is at least one selected from the non-fullerene acceptor group consisting of IEICO-4F, IEICO-4Cl, IEICO, DTPC-DFIC, DCI-2, COTIC-4F, PDTTIC-4F, DTPC-IC, 6TIC-4F, COiDFIC, FOIC, F8IC, F10IC, SiOTIC-4F, and P3.

[0175] [Organic donor material] The organic donor material is a material that has the property of readily donating electrons, and more specifically, is a material that has electron donating properties and has a small ionization potential when used in contact with an organic acceptor material.

[0176] Optical band gap E of organic donor materials g opt For the purpose of photoelectric conversion of the above-mentioned near-infrared light, is preferably 1.65 eV or less, more preferably 1.63 eV or less, even more preferably 1.62 eV or less, still more preferably 1.61 eV or less, and particularly preferably 1.60 eV or less.

[0177] The organic donor material may be a conventionally known material commonly used in organic photodetector elements and organic solar cells. The organic donor material is not particularly limited, but examples thereof include PTB7-Th (also known as PCE-10), PDTP-DFBT, PDPP3T, PDPP3T-O14, PDPP3T-O16, PDPP3T-O20, PDPP3T-C20, PDPP4T, DPPTfQxT, DPPTQxT, DPPBTQxBT, DPPBTffQxBT, FLP030 (trade name), PBDTT-SeDPP, PBDTT-DPP, PBDTT-FDPP, PDPP2T-TT (PTT-DTDPP), PCDTBT, PCPDTBT, PCPDTFBT, Si-PCPDTBT, PCPDT-BSe, PBDTTT-E, PBDTTT-C, PBDTTT-CF, P Examples include SBT-BT, C3-DPPTT-T, C3-DPPTT-Se, C3-DPPTT-Te, PDPP-DTS, DPPTBI, DPPTDTSffBzDTST, ZnP2-DPP, P3, P(ffDITDQx-BT), PFDPPSe-C18, CS-DP, BDP-OMe, P2-Bronstein, PFDQ, PTBEHT, PDPPTDTPT, PDPPSDTPS, PDTTDPP, PDTP-DTDPP(Bu), P2-Aso, PTTDTP, APFO-Green1, P1-Ying, P1-Iraqi, F2, CDTDOP, CEHTP, TTV2, TBDPTV, PPor1, and P3TPQ.

[0178] In addition, organic donor materials can be used, for example, as described in Dong Meng et al., Near-infrared Materials: The Turning Point of Organic Photovoltaics, Advanced Materials, 2021, Accepted Author Manuscript 2107330, Hao-Wen Cheng et al., Toward High-Performance Semitransparent Organic Photovoltaics with Narrow-Bandgap Donors and Non-Fullerene Acceptors, Advance Energy Materials, 2021, P. 2102908, Yiwen Wang et al., Recent Progress and Challenges toward Highly Stable Nonfullerene Acceptor-Based Organic Solar Cells, Advance Energy Materials, 2021, Vol. 11, P. 2003002, Andrew Wadsworth et al., Critical review of the molecular design progress in non-fullerene electron acceptors towards commercially viable organic solar cells Alternative p-doped hole transport material for low operating voltage and high efficiency organic light-emitting diodes, Chemical Society Reviews, 2019, Vol. 48, P. 1596-1625, Cenqi Yan et al., Non-fullerene acceptors for organic solar cells, Nature Reviews Materials, 2018, Vol. 3, P. 18003, Leiping Duan et al., Progress in non-fullerene acceptor based organic solar cells, Solar Energy Materials and Solar Cells, May 2019, Vol. 193, P. 22-65, Guangye Zhang et al., Non-fullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells, Chemical Reviews, 2018, Vol. 118, P. 3447-3507, Pei Cheng et al., Next-generation organic photovoltaics based on non-fullerene acceptors, Nature Photonics, 2018, Vol. 12, P. 131-142, Lichun Chang et al., Ternary organic solar cells based on non-fullerene acceptors: A review, Organic Electronics, March 2021, Vol. 90, P. 106063, Materials described in Huiting Fu et al., Advances in Non-Fullerene Acceptor Based Ternary Organic Solar Cells, Solar RRL, December 2017, Vol. 2, P. 1700158, etc. can be used and understood by those skilled in the art.

[0179] From the viewpoint of obtaining high external quantum efficiency and low dark current density in the near-infrared region described above, the organic donor material is preferably at least one selected from the group consisting of PTB7-Th (also known as PCE-10), PDTP-DFBT, PDPP3T, PDPP3T-O14, PDPP3T-O16, PDPP3T-O20, PDPP3T-C20, PDPP4T, DPPTfQxT, DPPTQxT, DPPBTQxBT, DPPBTffQxBT, FLP030 (trade name), PBDTT-SeDPP, PBDTT-DPP, PBDTT-FDPP, PDPP2T-TT (PTT-DTDPP), PCDTBT, PCPDTBT, PCPDTFBT, and Si-PCPDTBT.

[0180] The thickness of the organic photoelectric conversion layer 44 in the sub-sensor area 44SS provided on the metal wiring 24 is set to t OPD When (t OPD -t TCE ), that is, the difference in thickness between the organic photoelectric conversion layer 44 and the metal wiring 24 in the sub-sensor area 44SS is preferably 50 nm or more and 500 nm or less, more preferably 100 nm or more and 450 nm or less, even more preferably 140 nm or more and 380 nm or less, even more preferably 160 nm or more and 330 nm or less, and particularly preferably 180 nm or more and 280 nm or less. (t OPD -t TCE ) is 50 nm or more, the organic photoelectric conversion layer 44 of the sub-sensor area 44SS can sufficiently cover the convex metal wiring 24, and further, a sufficient distance from the opposing anode can be secured, thereby suppressing electrical short circuits. OPD Since it increases exponentially with t OPD The external quantum efficiency tends to improve with increasing t OPD -t TCE ) is 500 nm or less, the charge collection efficiency η ccAs disclosed in J. Xue et al., A Hybrid Planar-Mixed Molecular Heterojunction Photovoltaic Cell, Advanced Materials, January 2005, Vol. 17, pp. 66-71, the charge collection efficiency η cc In the region where the organic photoelectric conversion layer 44 is sufficiently thick, OPD Also, (t OPD -t TCE ) is 500 nm or less, the visible light transmittance of the organic photodetector in the subpixel 44S portion is improved, which tends to reduce the visibility of the subpixel 44S.

[0181] t OPD is (t OPD -t TCE ) is not particularly limited as long as it can be adjusted to the above range, but is preferably 80 nm or more and 700 nm or less, more preferably 150 nm or more and 500 nm or less, even more preferably 200 nm or more and 400 nm or less, and particularly preferably 250 nm or more and 350 nm or less. OPD is preferably in the above range for the reasons described above.

[0182] t OPD can be determined from the process conditions of dry film formation, wet film formation, or patterning printing using a calibration curve of the process conditions and film thickness of the organic photoelectric conversion layer 44. It can also be confirmed by observing the cross section of the organic photodetector element with an electron microscope (SEM, TEM, STEM). Furthermore, EDX (energy dispersive X-ray analysis) is used to map the EDX intensity of the K shell of the carbon atom C in the observation field of the electron microscope image of the cross section of the organic photodetector element, and the region with the highest EDX intensity of the carbon atom C between the metal wiring 24 and the counter electrode (e.g., anode) can be used to measure the film thickness of the organic photoelectric conversion layer 44.

[0183] The organic photoelectric conversion layer 44 can be formed by a conventional method commonly used for organic photodetector elements and organic solar cells. For example, an organic photoelectric conversion layer 44 having a bulk heterojunction structure can be formed by dry film formation, such as co-evaporation of one or more organic donor materials and one or more organic acceptor materials. Alternatively, an organic photoelectric conversion layer 44 having a bulk heterojunction structure can be formed by wet film formation using a known coating method such as slot die coating or spin coating or a casting method, where the ink for forming the organic photoelectric conversion layer is prepared by dissolving predetermined amounts of one or more organic donor materials and one or more organic acceptor materials in an appropriate solvent, followed by drying and annealing as necessary. The drying and annealing conditions of the ink for forming the organic photoelectric conversion layer can be adjusted to control the nano-level phase separation structure of a phase composed of one or more organic donor materials and a phase composed of one or more organic acceptor materials, thereby adjusting the morphology of the bulk heterojunction.

[0184] The solvent for the ink for forming the organic photoelectric conversion layer can be a conventionally known solvent that is commonly used in organic photodetector elements and organic solar cells. Examples of the solvent include aromatic solvents such as toluene, xylene, mesitylene, and cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; ether-based solvents such as aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA), and aromatic ethers such as 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; aliphatic ester-based solvents such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; and ester-based solvents such as aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, and n-butyl benzoate.

[0185] Additives such as chloronaphthalene and 1,8-diodooctane can be added to the ink for forming the organic photoelectric conversion layer as needed to adjust the morphology of the bulk heterojunction.

[0186] To form the subpixels 44S, first, a solid film of the organic photoelectric conversion layer 44 is dry- or wet-formed over the entire surface of the device using the method described above. Then, the subpixels 44S can be formed on the solid film of the organic photoelectric conversion layer 44 using a known patterning method such as photolithography, nanoimprinting, lift-off, or laser ablation. A particularly preferred patterning method is the method disclosed in Non-Patent Document 3. Alternatively, the subpixels 44S may be formed by pattern-printing an ink for forming the organic photoelectric conversion layer using a known printing method such as gravure printing, gravure offset printing, letterpress printing, flexographic printing, inkjet printing, or screen printing, followed by drying and, if necessary, annealing.

[0187] [1.5 Hole transport layer 46 (HTL)] The hole transport layer 46 of this embodiment efficiently transports holes generated by photoexcitation in the organic photoelectric conversion layer 44 to the anode. In addition, the hole transport layer 46 preferably also functions as an electron blocking layer for the purpose of reducing dark current density.

[0188] From the viewpoint of hole transportability, the difference between the valence band or HOMO of the hole transport layer 46, or at least one of the defect level and doping level responsible for hole conduction, and the HOMO of the organic donor material is preferably within 0.5 eV, more preferably within 0.3 eV. From the viewpoint of electron blocking property, the conduction band or LUMO of the hole transport layer 46 is preferably at an energy level shallower by 0.3 eV or more, more preferably at least 0.5 eV, and even more preferably at least 1.0 eV, than the LUMO of the organic acceptor material.

[0189] The hole transport layer 46 can be made of a conventionally known material and structure that is generally used in organic photodetector elements and organic solar cells. The hole transport layer 46 is not particularly limited, but may be made of MoO X(2≦X≦3) , Cu- x O (1≦X≦2) , CuS, CuI, CuPc , CuSCN, CIS, CuCrO2, CuGaO2, NiO x(1≦X≦2) , CoO x(1≦X≦1.5) , PbS, CrO x(1≦X≦5) , MoS2, VO x(1≦X≦ 2.5) The hole transport layer 46 may be formed by, for example, the method described in Arumugam, GM et al., Inorganic hole transport layers in inverted perovskite solar cells: A review, Nano Select., Vol. 2, pp. 1081-1116, June 2021. From the viewpoint of hole transporting properties and electron blocking properties, the hole transport layer 46 is made of MoO X(2≦X≦3) It is particularly preferred that:

[0190] The thickness of the hole transport layer 46 is preferably 5 nm to 300 nm, more preferably 10 nm to 200 nm, even more preferably 30 nm to 100 nm, and particularly preferably 50 nm to 80 nm. A thickness of 5 nm or more is preferred from the viewpoints of hole transportability and electron blocking property. A thickness of 300 nm or less is preferred because visible light transmittance is improved.

[0191] The hole transport layer 46 is preferably formed by a vapor phase deposition method such as PVD or CVD, and is particularly preferably formed by a sputtering method or a vacuum deposition method.

[0192] [1.6 Transparent electrode 60 (Anode)] The transparent electrode 60 of this embodiment is used as the anode of the organic photodetector element, and contributes to improving the transparency of the organic photodetector element, while simultaneously collecting the holes generated in the organic photoelectric conversion layer 44 as charges.

[0193] The transparent electrode 60 of this embodiment can be made of conventional materials and structures commonly used in organic photodetector elements and organic solar cells, without any particular limitations. Examples include the metal grid transparent electrode 20 (or metal grid only), transparent conductive inorganic compounds, conductive polymers such as PEDOT:PSS, metal nanowires such as silver nanowires, and carbon materials such as graphene. These materials may be used alone or in combination. From the viewpoints of high visible light transmittance and low sheet resistance, the transparent electrode 60 of this embodiment is preferably the metal grid transparent electrode 20 (or metal grid only) or a transparent conductive inorganic compound, and more preferably a transparent conductive inorganic compound. Furthermore, from the viewpoint of improving the flexibility of the organic photodetector element, the transparent electrode 60 of this embodiment is preferably the metal grid transparent electrode 20 (or metal grid only) or a conductive polymer.

[0194] The material used for the transparent conductive inorganic compound is not particularly limited as long as it is an inorganic compound that has high transmittance in the visible light region and exhibits conductivity. For example, In2O3-based compounds such as ITO, SnO2-based compounds such as ATO and FTO, ZnO-based compounds such as AZO and GZO, (ZnO-In2O3)-based compounds such as Zn2In2O5 and Zn3In2O2, In4Sn3O 12 Examples include (In2O3-SnO2) systems such as Zn2SnO4 and ZnSnO3, and (ZnO-SnO2) systems such as Zn2SnO4 and ZnSnO3. Other known materials used for transparent conductive oxides can also be used. Among these, it is preferable to use ITO (indium tin oxide), which is the most widely used and has excellent transparency and conductivity.

[0195] The film thickness of the transparent conductive inorganic compound is preferably 10 nm or more and 1000 nm or less, more preferably 10 nm or more and 500 nm or less, even more preferably 10 nm or more and 300 nm or less, and particularly preferably 10 nm or more and 200 nm or less. When the film thickness of the transparent conductive inorganic compound is 10 nm or more, the sheet resistance of the transparent conductive inorganic compound can be reduced, and the organic photodetector element tends to be larger in area. On the other hand, when the film thickness of the transparent conductive inorganic compound is 1000 nm or less, a decrease in the visible light transmittance of the transparent conductive inorganic compound tends to be suppressed.

[0196] The upper limit of the sheet resistance of the transparent conductive inorganic compound is preferably 500 Ω / sq. or less, more preferably 200 Ω / sq. or less, even more preferably 100 Ω / sq. or less, and particularly preferably 50 Ω / sq. or less. When the sheet resistance of the transparent conductive inorganic compound is 500 Ω / sq. or less, the organic photodetector element tends to be larger in area. There is no particular restriction on the lower limit of the sheet resistance of the transparent conductive inorganic compound layer, and an example of this is 0.1 Ω / sq.

[0197] The lower limit of the visible light transmittance of the transparent conductive inorganic compound is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more. When the visible light transmittance of the transparent conductive inorganic compound layer is 60% or more, the transparency of the organic photodetector element tends to be improved. The upper limit of the visible light transmittance of the transparent conductive inorganic compound is not particularly limited, and can be, for example, 100% or less.

[0198] The transparent conductive inorganic compound is preferably formed into a film by a vapor phase film formation method such as PVD or CVD, and is particularly preferably formed into a film by a sputtering method or a vacuum deposition method.

[0199] [1.7 Sealing layer] Like the barrier layer described above, the encapsulating layer has high barrier properties against moisture and oxygen. The provision of the encapsulating layer contributes to preventing degradation of the organic photodetector element's performance due to the intrusion of moisture and oxygen into the organic photodetector element. The encapsulating layer can be formed on the anode and further formed to cover the organic photodetector element or organic photodetector array except for a portion of the current collector 110 exposed for connection to an external terminal. The encapsulating layer can be formed using a conventionally known composition, structure, and formation method commonly used in organic photodetector elements and organic solar cells, and preferably has the same composition and structure as the barrier layer described above. It is particularly preferable to use the thin-film encapsulating layer (TFE) disclosed in Non-Patent Document 2 as the encapsulating layer. Alternatively, a barrier laminate film can be used in which the barrier layer described above or the thin-film encapsulating layer disclosed in Non-Patent Document 2, and an adhesive layer with gas barrier properties are sequentially laminated on the material used as the core layer of the transparent substrate 22. When the barrier laminate film is used as a sealing layer, it is laminated so that the adhesive layer adheres to the anode, and sealing can be performed using a known lamination method using heat, pressure, light, or the like.

[0200] [2. Organic Photodetector Array] Fig. 7(A) is a schematic diagram of an organic photodetector array (hereinafter sometimes referred to as an "OPD array"), and Fig. 7(B) is a partial enlarged view of area AR1 in Fig. 7(A). The OPD array includes a plurality of OPD elements 10, a current collecting section 110, a wiring section 120 for electrically connecting the current collecting section 110 to each OPD element 10, and a dummy pattern section 130.

[0201] The OPD array of this embodiment includes a plurality of OPD elements 10 arranged two-dimensionally and spaced apart along two orthogonal coordinate axes (the up-down direction and the left-right direction on the paper) in a parallel plane. The plurality of OPD elements 10 are arranged regularly and at equal intervals in each direction. However, this is not limited thereto, and the OPD array may include a plurality of OPD elements 10 arranged one-dimensionally, or a plurality of OPD elements 10 arranged randomly. Furthermore, as described above, each OPD element 10 may include a subpixel array made up of a plurality of subpixels 44S arranged two-dimensionally and spaced apart along two orthogonal coordinate axes (the up-down direction and the left-right direction on the paper) in a parallel plane.

[0202] The organic photodetector element is an element that receives a voltage (usually a reverse bias) from an external circuit and extracts electron and hole carriers generated by photoexcitation in the organic photoelectric conversion layer 44 to the external circuit as a photodetection current. Each organic photodetector element constitutes a single pixel of the organic photodetector array. The organic photodetector element may have the configuration of the OPD element 10 or any of the other organic photodetector elements described above.

[0203] The organic photodetector array of this embodiment can include a current collecting section 110 that is connected to a terminal from an external circuit and that transmits a voltage signal applied from the external circuit to the organic photodetector element and transmits a photodetection current to the external circuit. The organic photodetector array of this embodiment can also include a wiring section 120 that electrically connects the organic photodetector element and the current collecting section 110.

[0204] [Wiring section 120] The organic photodetector array of this embodiment can include a wiring section 120 having a second conductive pattern that is provided on the transparent substrate 22 and electrically connected to the conductive pattern 24P (metal wiring 24). The wiring section 120 can be provided independently for each pixel. That is, the wiring of the wiring section 120 that connects to the metal wiring 24 of the first OPD element 10 provided in the OPD array and the wiring of the wiring section 120 that connects to the metal wiring 24 of the second OPD element 10 are configured to be electrically insulated. This allows each OPD element 10 to function as an independent pixel.

[0205] Here, in order to achieve uniform visible light transmittance across the entire organic photodetector array, A wire is the aperture ratio of the second conductive pattern, -10%≦(A wire -A TCE )≦10%. More preferably, −8%≦(A wire -A TC E )≦8%, more preferably −6%≦(A wire -A TCE )≦6%, particularly preferably −4%≦(A wire -A TCE )≦4%.

[0206] This configuration makes it possible to suppress variations in visible light transmittance between the region where the conductive pattern 24P is provided and the region where the second conductive pattern is provided, and therefore, when the organic photodetector array is disposed on the screen of a display or other display device, it becomes possible to suppress variations in the appearance of images displayed on the screen of the display device.

[0207] (line width, gap) The line width W of the metal wiring 24 constituting the second conductive pattern wireis preferably 0.25 μm or more and 5.0 μm or less, more preferably 0.25 μm or more and 4.0 μm or less, even more preferably 0.25 μm or more and 3.0 μm or less, still more preferably 0.25 μm or more and 2.0 μm or less, and particularly preferably 0.25 μm or more and 1.0 μm or less. In addition, for the purpose of making the visible light transmittance and the visibility of the metal wiring 24 uniform throughout the organic photodetector array, W wire is W TCE It is preferable that the line width is the same as W wire When the width W of the metal wiring 24 is 0.25 μm or more, the wiring resistance can be reduced, and the area of ​​the organic photodetector array tends to be increased. In addition, an increase in electrical resistance due to oxidation or corrosion of the surface of the metal wiring 24 can be sufficiently suppressed. On the other hand, when the width W of the metal wiring 24 is 0.25 μm or more, the wiring resistance can be reduced, and the area of ​​the organic photodetector array tends to be increased. wire By making the line width W of the metal wiring 24 5.0 μm or less, the visibility of the opaque metal wiring 24 can be reduced. wire By adjusting the gap G of the second conductive pattern to 3.0 μm or less, the opaque metal wiring 24 can be made invisible to the human eye. This means that even when the organic photodetector array is disposed on a display such as a display, the appearance and design of the display are not impaired. wire is the aperture ratio A wire The second conductive pattern and W are arranged so that the wire In order to make the visible light transmittance and the visibility of the metal wiring 24 uniform over the entire organic photodetector array, wir e is G TCE It is preferable that the gap value is the same as that of the

[0208] [Current collecting section 110] The organic photodetector array of this embodiment can include a current collecting section 110 having a third conductive pattern provided on the transparent substrate 22 and electrically connected to the second conductive pattern. The current collecting section 110 is a section for collecting the photodetection current detected by the OPD element 10 constituting each pixel and supplying it to an external circuit. The current collecting section 110 can be, for example, a contact pad (bonding pad) for connecting to an external FPC (Flexible Printed Circuits). The device may be equipped with a

[0209] Gamma pad is the occupied area ratio of the third conductive pattern per unit area, Γ pad is preferably 50% or more and less than 100%. pad The lower limit of the area ratio Γ of the third conductive pattern is more preferably 60% or more, and even more preferably 70% or more. pad When the value is within the above range, the electrical connection with the external terminal is improved, the resistance of the current collecting portion 110 can be reduced, and the voltage drop of the applied voltage tends to be suppressed.

[0210] The "occupancy area ratio" of the conductive pattern 24P can be calculated using the following formula for the region on the transparent substrate 22 where the conductive pattern 24P is formed.

[0211] Occupancy rate = (area occupied by conductive pattern 24P / area of ​​transparent substrate 22 in the region where conductive pattern 24P is formed) × 100

[0212] For example, when the third conductive pattern is a square mesh pattern as shown in FIG. 3A, if the line width is 5 μm and the gap is 10 μm, the area occupied by the third conductive pattern per unit area (the area occupied by the metal wiring 24) is about 56%, so the occupied area ratio Γ pad is approximately 56%.

[0213] (line width, gap) The line width W of the metal wiring 24 constituting the third conductive pattern padis preferably 0.25 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and even more preferably 1 μm or more and 6 μm or less. pad When the gap G of the third conductive pattern is within the above range, the connectivity with the external terminal is improved, the sheet resistance of the current collecting portion 110 can be reduced, and the voltage drop of the applied voltage tends to be suppressed. pad is the occupied area ratio Γ p ad The third conductive pattern and W are arranged so that the pad It can be set appropriately depending on the situation.

[0214] [Dummy pattern portion 130] The organic photodetector array of this embodiment can include a dummy pattern section 130 configured to be electrically insulated from the conductive pattern 24P and the second and third conductive patterns 24P. The dummy pattern section 130 may be provided between two adjacent OPD elements 10. For example, when the multiple OPD elements 10 included in the organic photodetector array are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes (however, as shown in FIG. 7 , this includes an embodiment in which the OPD elements 10 are arranged at equal intervals along one coordinate axis and at equal intervals along the other coordinate axis, but with different intervals for each coordinate axis), the dummy pattern sections 130 may be arranged at equal intervals along the two orthogonal coordinate axes between the two adjacent OPD elements 10.

[0215] Figure 7 shows a dummy pattern portion 130 that is arranged between two adjacent OPD elements 10 on the first coordinate axis (horizontal direction on the paper), and a dummy pattern portion 130 that is arranged between two adjacent OPD elements 10 on the second coordinate axis (vertical direction on the paper).

[0216] The dummy pattern 130 may have the same configuration as the metal grid transparent electrode 20 of the OPD element 10. By using the same configuration, it becomes possible to share the manufacturing process for the metal grid transparent electrode 20 of the OPD element 10 and the dummy pattern 130.

[0217] By providing the dummy pattern portion 130 in the region where the OPD element 10 is not provided, it is possible to suppress the difference in visible light transmittance between the two regions. dummy When the aperture ratio of the dummy pattern is -10%≦(A dummy -A TCE )≦10%. More preferably, −8%≦(A dummy -A TCE )≦8%, more preferably −6%≦(A dummy -A TCE )≦6%, particularly preferably −4%≦(A du mmy -A TCE )≦4%.

[0218] (line width, gap) The line width W of the metal wiring 24 that constitutes the dummy pattern portion 130 dummy is preferably 0.25 μm or more and 5.0 μm or less, more preferably 0.25 μm or more and 4.0 μm or less, even more preferably 0.25 μm or more and 3.0 μm or less, still more preferably 0.25 μm or more and 2.0 μm or less, and particularly preferably 0.25 μm or more and 1.0 μm or less. In addition, for the purpose of making the visible light transmittance and the visibility of the metal wiring 24 uniform throughout the organic photodetector array, W dummy is W TCE It is preferable that the line width is the same as W d ummy By making the line width W of the metal wiring 24 0.25 μm or more, an increase in electrical resistance due to oxidation or corrosion of the surface of the metal wiring 24 can be sufficiently suppressed. dummy By making the line width W of the metal wiring 24 5.0 μm or less, the visibility of the opaque metal wiring 24 can be reduced. dummy By adjusting the gap G of the dummy pattern portion 130 to 3.0 μm or less, the opaque metal wiring 24 can be made invisible to the human eye. As a result, even when the organic photodetector array is disposed on a display device such as a display, the appearance and design of the display device are not impaired. dummy is the aperture ratio Adummy The pattern of the dummy pattern portion 130 and W are adjusted so that the value falls within the above range. dummy In order to make the visible light transmittance and the visibility of the metal wiring 24 uniform over the entire organic photodetector array, dummy is G TCE It is preferable that the gap value is the same as that of the

[0219] [Dummy subpixel] Fig. 8 shows a cross-sectional view and a projection view of a dummy subpixel 44SD provided in an area AR3 on the dummy pattern portion 130 in Fig. 7. The cross-sectional view and the projection view of the subpixel 44S provided in an area AR2 in the OPD element 10 in Fig. 7 correspond to Fig. 1.

[0220] As shown in FIG. 8 , the organic photodetector array 100 of this embodiment may include an insulating layer 80 provided on the dummy pattern portion 130, and an organic photoelectric conversion layer (dummy subpixels 44SD) provided on the insulating layer 80 and insulated from the dummy pattern portion 130. The insulating layer 80 on the dummy pattern portion 130 may have substantially the same thickness and composition as the insulating layer 80 of the OPD element 10. By providing the insulating layer 80 with substantially the same thickness and composition, it is possible to use a common manufacturing process for both insulating layers 80, i.e., to simultaneously form the insulating layer 80 of the OPD element 10 and the insulating layer 80 on the dummy pattern portion 130. The insulating layer 80 on the metal grid transparent electrode 20 of the OPD element 10 may further have openings OP by patterning.

[0221] Unlike the organic photoelectric conversion layer 44 of the OPD element 10, the organic photoelectric conversion layer (dummy subpixels 44SD) on the dummy pattern portion 130 is provided at a position spaced approximately the same distance from the electron transport layer 42 via the insulating layer 80 in the cross-sectional view ( FIG. 8(A) ). Therefore, the organic photoelectric conversion layer (dummy subpixels 44SD) on the dummy pattern portion 130 is insulated from the dummy pattern portion 130. Therefore, no current is detected in the dummy pattern portion 130. Note that by making the thickness of the organic photoelectric conversion layer (dummy subpixels 44SD) on the dummy pattern portion 130 approximately the same as the thickness of the alignment area 44SA of the OPD element 10, it is possible to standardize the manufacturing processes for both organic photoelectric conversion layers. In other words, it is possible to simultaneously form the organic photoelectric conversion layer 44 of the OPD element 10 and the organic photoelectric conversion layer (dummy subpixels 44SD) on the dummy pattern portion 130. The dummy subpixels 44SD are not limited to being provided on the insulating layer 80 provided on the dummy pattern portion 130 or the electron transport layer 42, but may also be provided, for example, on the insulating layer 80 provided on the transparent substrate 22, the metal grid transparent electrode 20 outside the OPD element 10 region, or the wiring portion 120.

[0222] The organic photodetector array 100 (OPD array 100) of this embodiment additionally includes dummy subpixels 44SD provided in the region between the OPD elements 10. This reduces the difference in visible light transmittance between the region where the OPD elements 10 are provided and the region between the OPD elements 10 (the region where the dummy pattern portions 130 are provided; see FIG. 7 ). Additionally, providing the dummy subpixels 44SD also reduces the occurrence of interference fringes compared to a case where the dummy subpixels 44SD are not provided. Therefore, when the OPD array 100 is provided on the screen of a display or display device, as described below with reference to FIG. 9 and other figures, it is possible to reduce interference fringes due to light emitted from the display or display device, thereby improving the visibility of the display or display device. Therefore, an organic photodetector array including the organic photodetector elements disclosed in this embodiment can be suitably applied to touchless user interfaces.

[0223] The reason why providing the dummy subpixel 44SD makes interference fringes less observable when applied to a touchless user interface is thought to be as follows.

[0224] When the organic photodetector array 100 according to this embodiment is applied to an existing display, the light-emitting pixels of the display are approximately 200 to 300 μm square, and the distance between the light-emitting pixels and the organic photodetector array 100 (the distance perpendicular to the screen) is approximately several mm. Therefore, the visibility of interference fringes caused by the OPD element 10 of the organic photodetector array 100 or caused by the subpixels 44S within the OPD element 10 is expressed by the following equation: As a result, the interference fringes that occur are small, making them difficult to visually recognize.

[0225] [Number 2] V = (Imax-Imin) / (Imax+Imin) =|sin(πad / λL) / (πad / λL)|

[0226] where V is the visibility (intensity) of the interference fringes. max is the light intensity of the bright part of the interference fringes. min is the light intensity of the dark areas of the interference fringes; a is the light source width; λ is the emission wavelength; d is the pitch of the OPD elements 10 (e.g., the center-to-center distance between adjacent photodetector elements 10) or the pitch of the subpixels 44S within the OPD elements 10 (e.g., the center-to-center distance between adjacent subpixels 44S); and L is the distance from the light-emitting pixel of the display to the organic photodetector array 100.

[0227] The pitch of the interference fringes is expressed by the following formula: Therefore, the pitch of the interference fringes caused by the OPD element 10 of the organic photodetector array 100 or caused by the subpixels 44S within the OPD element 10 is small, on the order of several hundred μm, and is difficult to visually recognize. [Number 3] X=mDλ / d

[0228] where X is the pitch of the interference fringes, m is the interference order (an integer), and D is the distance from the organic photodetector array 100 to the observer.

[0229] As described above, the visibility of both the interference fringes caused by the OPD elements 10 of the organic photodetector array 100 and the interference fringes caused by the subpixels 44S within the OPD elements 10 is low. However, in a configuration in which the OPD elements 10 are spaced apart from each other (FIG. 7) and the subpixels 44S within each OPD element 10 are spaced apart from each other (FIG. 1), it has been found that the respective interference fringes may overlap, resulting in interference fringes of visible intensity and pitch. Therefore, the organic photodetector array 100 of this embodiment includes dummy subpixels 44SD provided in regions between the OPD elements 10. Providing the dummy subpixels 44SD makes it possible to suppress the occurrence of interference fringes that occur when the OPD elements 10 are spaced apart from one another, and therefore makes it possible to suppress the occurrence of interference fringes of visible intensity and pitch that occur when interference fringes caused by the OPD elements 10 of the organic photodetector array 100 and interference fringes caused by the subpixels 44S within the OPD elements 10 are superimposed.

[0230] [Dummy subpixel array] Here, the arrangement structure of the plurality of organic photoelectric conversion layers (each organic photoelectric conversion layer is sometimes referred to as a "dummy subpixel 44SD," and the arrangement structure consisting of the plurality of dummy subpixels 44SD is sometimes referred to as a "dummy subpixel array") that are arranged separately from one another in the projection view and the arrangement structure of the plurality of organic photoelectric conversion layers 44 that are arranged separately within the OPD element 10 in the projection view may be the same pattern structure. For example, both may be two-dimensional arrangement structures in the projection view. Furthermore, the pitch of the dummy subpixel array in the first direction and / or the second direction may be the same as the pitch of the subpixel array in the first direction and / or the second direction.

[0231] [Materials and Processes for the Wiring Portion 120, the Current Collecting Portion 110, and the Dummy Pattern Portion 130] The wiring portion 120 and the current collecting portion 110 are not particularly limited as long as they can be electrically connected to the conductive pattern 24P, and conventionally known materials and configurations that are generally used in organic photodetector elements can be applied. Materials that can be used for the wiring portion 120, the current collecting portion 110, and the dummy pattern portion 130 include metals such as gold, silver, copper, aluminum, and molybdenum, metal laminates such as molybdenum / aluminum / molybdenum, and metal alloys thereof.

[0232] The second conductive pattern, the third conductive pattern, and the dummy pattern portion 130 may be made of the same materials, have the same structure, and have the same design adjustment range as the conductive pattern 24P of the metal grid transparent electrode 20. For the purpose of simplifying the manufacturing process, it is preferable to simultaneously form the second conductive pattern, the third conductive pattern, and the dummy pattern portion 130 with the conductive pattern 24P using the above-described manufacturing method for the metal grid transparent electrode 20. To prevent a decrease in external quantum efficiency due to a voltage drop in the current collecting portion 110, the above-described metal, metal laminate, or metal alloy may be laminated on the third conductive pattern by vacuum deposition, sputtering, or the like.

[0233] 〔pixel〕 The pixel size of the organic photodetector array of this embodiment is preferably 1 mm 2 More than 25mm 2 It is preferably 2 mm or less. 2 More than 21mm 2 It is preferably 4 mm or less. 2 Over 16mm 2 and even more preferably 6 mm or less. 2 Over 13mm 2 It is particularly preferably 7 mm or less. 2 More than 11mm 2 The pixel size is 1mm. 2 This tends to increase the total effective sensor area in the pixel and increase the photodetection current. 2 This is preferable because it allows the pixel density, which will be described later, to be sufficiently large, and a touchless user interface device using the organic photodetector array of this embodiment can achieve an operational feel equivalent to that of a touch user interface device using a conventional touch panel.

[0234] The pixel density of the organic photodetector array of this embodiment is preferably 2 ppi or more and 15 ppi or less, more preferably 3 ppi or more and 10 ppi or less, even more preferably 3.5 ppi or more and 9 ppi or less, even more preferably 3.8 ppi or more and 8 ppi or less, and particularly preferably 4 ppi or more and 7 ppi or less. A pixel density of 2 ppi or more can achieve a sufficiently smooth operational feel in a touchless user interface device using the organic photodetector array of this embodiment. A pixel density of 15 ppi or less is preferable because it allows for a larger pixel size, which tends to increase the photodetection current for the reasons described above. Note that, in this specification, ppi stands for pixel per inch.

[0235] The pixel density can be calculated by a known calculation method depending on the arrangement pattern of the organic photodetector array. For example, in the case of the two-dimensional arrangement pattern shown in Figure 7, it may be simply calculated using the following formula:

[0236]

number

[0237] where P Pixel-x (mm) and P Pixel-y (mm) are the pixel pitches in the X-axis direction (horizontal direction on the paper) and the Y-axis direction (vertical direction on the paper). For example, in the organic photodetector array of Figure 7, Pixel-x =P Pixel-y = 6.24 (mm), the pixel density is approximately 4 ppi.

[0238] [3. Touchless User Interface]

[0239] FIG. 9 is a schematic diagram of a touchless user interface device (hereinafter, sometimes referred to as a "UI device") according to this embodiment. FIG. 10 is a functional block diagram of a UI device 200. The UI device 200 includes an OPD array 100 provided on a display or a display body, and a position detection unit 210 connected to the OPD array 100 and detecting a position at which an optical input signal is input based on an electrical output signal output from the OPD array 100. For example, the OPD array 100 may be attached to the screen of a display D or a display body (for the sake of explanation, the two are shown separated in FIG. 9). When incident light IL (optical input signal) is irradiated, each pixel in the OPD array 100 converts the optical input signal into an electrical output signal and outputs it. Therefore, the position detection unit 210 of the UI device 200 is configured to detect the position at which the optical input signal is input (the position irradiated by incident light IL) by receiving an electrical output signal from a specific pixel.

[0240] Here, the display D corresponds to a part that displays an image in a display device such as an LCD device, an OLED device, an electronic paper device, an electrochromic display device, etc. The display body corresponds to a part where an image is projected or displayed by a projector or the like, such as a wall surface or a screen, in addition to the display D.

[0241] The OPD array 100 is provided on such a display D or display body. This allows the user to view the image displayed on the display body through the OPD array. The user can also direct incident light IL at a specific position in the image displayed on the display body (for example, (1) a position in the image where a menu icon is displayed, or (2) a position on a map displayed as an image), causing the OPD array 100 to detect the incident light IL and output it as an electrical output signal.

[0242] The position detection unit 210 of the UI device 200 can detect that incident light IL has been irradiated at a specific position on the image. For example, the position detection unit 210 of the UI device 200 may be composed of a storage medium that non-volatilely stores a computer program for receiving an electrical output signal output from the OPD array 100 and a processor (a GPU, a CPU, or other computing device) for executing the computer program. Furthermore, the processor of the position detection unit 210 may be realized, for example, by a processor (a GPU, a CPU, or other computing device) that constitutes a video generation unit P that generates a video signal provided in the display device. In this case, the processor may be configured to receive the electrical output signal output from the OPD array 100 and, based on the electrical output signal, generate a video signal to be displayed on the display D (for example, (1) based on incident light incident on a display position of a menu icon, generate a video signal for displaying a detailed menu of the menu icon on the display, or (2) based on incident light incident on a position on a map displayed as an image, generate a video signal of an enlarged map centered on that position).

[0243] As described above, an OPD array 100 is provided on the display D or display body, and the OPD element 10 at the position where the optical input signal, which is incident light IL, is irradiated converts the optical input signal into an electrical output signal, thereby detecting the position where the optical input signal is irradiated, thereby making it possible to perform input operations on the screen of the display D or display body.

[0244] [Optical input signal] Here, the optical input signal preferably contains light having at least a part of a wavelength in the near-infrared wavelength region of 780 nm to 1200 nm. As described above, near-infrared light is invisible to the human eye, and therefore, even if it is irradiated as an optical input signal onto a display such as a display, it does not impair the visibility of the display (the visibility of images, etc. displayed on the display).

[0245] The light intensity of the optical input signal on the irradiation surface of the OPD element 10 (for example, the lower surface of the transparent substrate 22 onto which the incident light IL is incident) is not particularly limited, but may be, for example, 10-4 mW / cm 2 More than 10mW / cm 2 The light intensity is preferably 10 -3 mW / cm 2 More than 1mW / cm 2 More preferably, 10 -2 mW / cm 2 More than 0.5mW / cm 2 The light intensity is 10 -4 mW / cm 2 This makes it easy to detect light using the organic photodetector element of this embodiment. 2 By keeping the temperature below 100°C, the impact on the human body tends to be further reduced.

[0246] Here, the optical input signal may be a signal having a predetermined frequency such as a pulse signal, a signal having a phase fluctuation, or a signal having an amplitude fluctuation, etc. For example, by configuring an optical signal having a constant output to be modulated to input a pulse signal, it becomes easy to extract the detection signal of the optical input signal to be detected from the entire optical detection signal including disturbances such as natural light, indoor light, and light emitted from a display such as a display.

[0247] Known modulation methods can be used for signal modulation, including, but not limited to, frequency modulation, phase modulation, and amplitude modulation. Frequency modulation is preferred, with the modulation frequency preferably being 0.5 kHz to 20 kHz, more preferably 0.6 kHz to 10 kHz, even more preferably 0.7 kHz to 5 kHz, and particularly preferably 0.8 kHz to 3 kHz. A modulation frequency of 0.5 kHz or higher facilitates extraction of the detection signal of the optical input signal (e.g., a continuous pulse signal consisting of a 1 kHz rectangular wave) from the overall photodetection signal, which includes signals detecting disturbances such as natural light, indoor light, and light emitted from a display device. On the other hand, a modulation frequency of 20 kHz or lower tends to be lower than the cutoff frequency determined by the capacitance of the organic photodetector element of this embodiment and the resistance of the wiring portion 120, making it easier to extract the detection signal of the optical input signal. Known signal processing methods can be used to extract the detection signal of the modulated optical input signal from the overall photodetection signal. For example, when a frequency-modulated optical input signal is used, a low-pass filter, a high-pass filter, a band-pass filter, a band elimination filter (band-stop filter), a lock-in amplifier, or the like can be used, or a combination of these can be used.

[0248] The UI device 200 may further include a light source LS, such as a laser pointer shown in FIG. 9B, as a pointing means PD for outputting an optical input signal. Here, the pointing means PD may be equipped with a modulation unit for generating a frequency-modulated, phase-modulated, or amplitude-modulated signal, as described above. The OPD array can detect the position where the pointing means PD is irradiated with the optical input signal, thereby enabling screen input operations.

[0249] Alternatively, the UI device may be configured to reflect light output from a light source LS onto a hand or finger serving as pointing means PD and detect the reflected light as an optical input signal. Here, the light source LS may be configured to form a planar projection light beam (surface light source LS2) in space. FIG. 9(A) shows an embodiment in which a surface light source LS2 parallel to the display is formed in space based on light output from a point light source LS. A user can extend a hand or finger serving as pointing means PD to a predetermined position on the surface light source LS2. The light from the extended position is incident on the OPD array 100 as reflected light, allowing the UI device 200 to detect the position where the optical input signal is irradiated.

[0250] The UI device may further include a detection position identification means for identifying the detection position based on the detection signal (electrical output signal) of the optical input signal acquired from the OPD array. Such a detection position identification means may be a conventionally known detection position identification means mounted on a touch panel or the like. For example, the detection position identification means may be composed of a computer program that calculates the signal centroid position in the X-axis direction (horizontal direction on the page) and the Y-axis direction (vertical direction on the page) shown in FIG. 7 and executes arithmetic processing to identify the signal centroid position as the detection position, and a processor that executes the computer program. The computer program may also include instructions for executing some or all of the various arithmetic processing described in this embodiment. Furthermore, the computer program may be stored in a semiconductor device or other recording medium that can non-transitory record information. In addition to the method of identifying the detection position based on the signal centroid, a method of fitting the detection signal in the X-axis direction and the detection signal in the Y-axis direction shown in FIG. 7 with a Gaussian function, a Lorentz function, or the like to calculate the peak position and then identifying the detection position may be used. [Example]

[0251] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0252] <<Example A>> The optical characteristics and optical model of an organic photodetector element using a metal grid transparent electrode will be specifically described below.

[0253] Example A1 <<Manufacturing of metal grid transparent electrodes>> [Preparation of transparent substrate] Alkali-free glass (manufactured by Corning, product name: EAGLE XG, thickness 1.1 mm) was used as the transparent substrate.

[0254] [ink] Cuprous oxide nanoparticles with a particle diameter of 21 nm, a dispersant (manufactured by BYK, product name: Disperbyk-145), a surfactant (manufactured by Seimi Chemical, product name: S-611), and ethanol were mixed and dispersed to prepare an ink containing 20% ​​by mass of cuprous oxide nanoparticles.

[0255] [Production of metal grid transparent electrode 20] First, ink was applied to the surface of a transfer medium. Then, the ink-coated surface of the transfer medium was placed opposite a plate with conductive grooves, and the plate was pressed against the plate to transfer some of the ink to the raised areas of the plate. The remaining ink-coated surface of the transfer medium was then placed opposite a transparent substrate, and the plate was pressed against the transparent substrate to transfer the desired conductive pattern of ink onto the transparent substrate. Next, the conductive ink-coated film (dispersion coating film) on the transparent substrate was irradiated with 1.2 kW plasma for 496 seconds in a reducing atmosphere to reduce the cuprous oxide in the dispersion coating film to copper. This resulted in a sintered copper film, resulting in a metal grid transparent electrode with a mesh-patterned conductive pattern.

[0256] <Evaluation of metal grid transparent electrodes> [Measurement of line width, gap, and film thickness, and calculation of repeating unit area and aperture ratio] The metal grid transparent electrode thus obtained was photographed using a confocal laser microscope to confirm the line width W of the metal wiring of the conductive pattern. TCEand film thickness t TCE , and the gap G of the conductive pattern TCE Using these values, the repeating unit area S of the conductive pattern was calculated. TCE-unit and aperture ratio A TCE The results are shown in Table 1.

[0257] [Calculation of visible light transmittance] Visible light transmittance (VLT) of metal grid transparent electrode TCE is the transparent substrate with a visible light transmittance of 92% and a conductive pattern with an aperture ratio of A TCE The results are shown in Table 1.

[0258] [Table 1]

[0259] [Sheet resistance measurement] The sheet resistance of the conductive pattern of the metal grid transparent electrode is determined by the conductivity of the metal wiring, the film thickness t TCE and aperture ratio A TCE The conductivity of the metal wiring was calculated using the following method. First, the sheet resistance of the test area consisting of the conductive pattern formed simultaneously with the metal grid transparent electrode was measured using Loresta GP (product name, manufactured by Mitsubishi Chemical Corporation). Next, the conductivity of the metal wiring was calculated from the obtained sheet resistance using the film thickness and aperture ratio measured from a planar photograph of the conductive pattern in the test area taken with a confocal laser microscope. The calculated sheet resistance of the metal grid transparent electrode is shown in Table 1.

[0260] <<Manufacturing of organic photodetector elements>> [Formation of electron transport layer] A 16-nm thick a-IGZO film was deposited as an electron transport layer on the metal grid transparent electrode by sputtering, and then patterned by photolithography and wet etching to remove unnecessary portions of the a-IGZO.

[0261] [Insulating layer formation] Next, SU-8 was applied as an insulating layer by spin coating, soft-baked, patterned exposed, and developed to form an insulating layer (thickness 1.8 μm) with an opening OP corresponding to the sub-sensor area described below.

[0262] [Formation of a solid organic photoelectric conversion layer] Per 1 mL of chlorobenzene solvent, PTB7-Th (also known as PCE-10, E g opt = 1.60 eV, HOMO = -5.20 eV, LUMO = -3.59 eV) and 8 mg of IEICO-4F (E g opt = 1.24 eV, HOMO = -5.44 eV, LUMO = -4.19 eV) was dissolved in 12 mg of tetrahydrofuran. Next, 40 μL of chloronaphthalene was added per 1 mL of the solvent chlorobenzene to prepare an ink for forming an organic photoelectric conversion layer. The obtained ink for forming an organic photoelectric conversion layer was formed into a wet film by spin coating, dried at room temperature, and annealed at 60 °C for 20 minutes to obtain a dry film thickness of t OPD A solid film of an organic photoelectric conversion layer having a bulk heterojunction structure with a thickness of 300 nm was formed.

[0263] [Subpixel and subpixel array formation] Next, the resulting solid film of the organic photoelectric conversion layer was patterned into a subpixel array having a pattern structure in which approximately square subpixels were arranged two-dimensionally at equal intervals along the orthogonal coordinate axes of the X and Y axes, using a known photolithography patterning technique for organic semiconductor materials, such as that described in Non-Patent Document 3. The design of the formed subpixel array is as follows.

[0264] <Design of organic photodetector element> (X-axis, Y-axis) Subpixel: 60μm×60μm, S subOPD :3600μm 2 Sub-sensor area: 50μm x 50μm, S sub―sensor :2500μm2 Pattern pitch P subOPD :240μm×240μm · Sub-pixel area occupancy rate Γ within a pattern unit subOPD :6.25%

[0265] [Formation of hole transport layer and anode] MoO as a hole transport layer x A 60 nm thick ITO film was then deposited on the hole transport layer by vacuum deposition.

[0266] [Formation of sealing layer] Finally, a PET film (125 μm, Melinex® ST504) was used as a sealing layer. TM A barrier laminate film (total thickness 160 μm) was used, in which a known thin film sealing layer and an adhesive layer having gas barrier properties, such as those described in Non-Patent Document 2, were sequentially laminated on the anode. The barrier laminate film was laminated so that the adhesive layer was in contact with the anode, and the organic photodetector element was sealed by laminating them under pressure.

[0267] <Evaluation of the optical properties of organic photodetector elements> The visible light transmittance of the organic photodetector element was calculated using the following method. The optical transmittance spectrum of the organic photodetector element was measured using an ultraviolet-visible-near-infrared spectrometer (UV-vis-NIR spectroscopy, Agilent Cary 5000). The visible light transmittance was calculated from the acquired optical transmittance spectrum in accordance with JIS R 3106:2019 or ISO 9050:2003. The results are shown in Table 1.

[0268] [Comparative Example A1] The [formation of subpixels and subpixel arrays] of Example A1 was omitted, and a solid organic photoelectric conversion layer was used. A metal grid transparent electrode and an organic photodetector element using the same were fabricated and evaluated using the same procedures as in Example A1. The results are shown in Table 1.

[0269] From Example A1 and Comparative Example A1, it can be seen that by forming the organic photoelectric conversion layer into an island-shaped subpixel or a subpixel array structure in which two or more such subpixels are arranged, even when a near-infrared detection organic photoelectric conversion layer with low visible light transmittance is used, visible light is transmitted with high efficiency from areas where no subpixels are formed, thereby improving the visible light transmittance of the entire organic photodetector element. Specifically, the visible light transmittance in the stacking direction of the organic photodetector element in the subpixel portion of Example A1 is about 17%, the same as in Comparative Example A1. In Example A1, the area occupancy rate Γ of the subpixel portion subOPD By adjusting the transmittance to 6.25%, the visible light transmittance was improved to 64%.

[0270] Optical model of the light transmission spectrum of an organic photodetector element

[0271] The optical transmission spectrum T(λ) of an organic photodetector element that uses a metal grid transparent electrode as the cathode and has subpixels (or subpixel arrays) in the organic photoelectric conversion layer is modeled by the following equation:

[0272]

number

[0273] where T OPD (λ) is the light transmission spectrum of the multilayer structure of the transparent substrate / electron transport layer / organic photoelectric conversion layer / hole transport layer / anode / sealing layer made of the above-mentioned materials and configuration, and is a model of the light transmission spectrum in the stacking direction of the organic photodetector element in the subpixel portion excluding the conductive pattern. Similarly, T OPEN(λ) is the light transmission spectrum of the multilayer structure of the transparent substrate / electron transport layer / insulating layer / hole transport layer / anode / sealing layer made of the above-mentioned materials and configuration, and is a model of the light transmission spectrum in the stacking direction of the organic photodetector element in the part where no subpixels are formed, excluding the conductive pattern. Cu (λ) is the optical transmittance spectrum of the metal wiring itself. OPD (λ) and T OPEN (λ) was calculated using Setfos, an optoelectronics electrical and optical property simulator software manufactured by FLUXiM AG. The optical simulation was performed using an optical calculation method based on the transfer matrix formalism. The input parameters for the simulation were the wavelength dependence of the optical constants (refractive index: n, extinction coefficient: k) of the constituent materials of each layer measured by spectroscopic ellipsometry and the film thickness described above. .T Cu (λ) was modeled as a laminated structure that simulated the distribution of copper and cuprous oxide in the metal wiring and the distribution of voids, and optical simulation was performed on this model using the same method. The visible light transmittance was calculated from the calculated light transmission spectrum in accordance with JIS R 3106:2019 or ISO9050:2003. The visible light transmittance was calculated as T OPD (λ) is 22%, T OPEN (λ) at 80%, T Cu (λ) was 10%.

[0274] Figure 11 shows a comparison of the light transmission spectrum of the organic photodetector element of Example A1 with the light transmission spectrum calculated using the optical model described above. Figure 11 shows that the optical model can reproduce the light transmission spectrum of the organic photodetector element of the present invention, represented by Example A1. The visible light transmittance calculated from the light transmission spectrum based on the optical model was 64%, which is close to the measured value (64%) of Example A1. Furthermore, for Comparative Example A1, Γ subOPDA similar model can be created by setting the transmittance of the optical fiber to 100%. Figure 12 shows a comparison of the light transmission spectrum of Comparative Example A1 and the modeled light transmission spectrum. Figure 12 shows that the optical model can also reproduce the actually measured light transmission spectrum of Comparative Example A1. Similarly, the visible light transmittance (18%) calculated from this optical model was also close to the actually measured value (17%) of Comparative Example A1.

[0275] <<Example B>> The electrical characteristics of an organic photodetector element using a metal grid transparent electrode will be specifically described below.

[0276] Example B1

[0277] Line width W in the conductive pattern of the metal grid transparent electrode TCE and Gap G TCE The process was modified as shown in Table 2 by changing the groove pattern of the plate used in the pattern formation process. The firing process for the metal grid transparent electrode was also changed to irradiating 1.2 kW plasma for 540 seconds. In addition, slot die coating was used instead of spin coating in the [Formation of a solid film of the organic photoelectric conversion layer] process, and the drying and annealing process was performed all at once at 60°C for 5 minutes. Furthermore, the design was changed as follows in [Formation of subpixels and subpixel arrays] of Example A1. A metal grid transparent electrode and an organic photodetector element using it were fabricated using the same procedures as in Example A1.

[0278] <Design of organic photodetector element> (X-axis, Y-axis) Subpixel: 70μm×70μm, S subOPD :4900μm 2 Sub-sensor area: 50μm x 50μm, S sub―sensor :2500μm 2 Pattern pitch P subOPD :240μm×240μm Number of subpixels N subOPD :9 pieces x 9 pieces, 81 pieces · Sub-pixel area occupancy rate Γ within a pattern unit subOPD :8.5% Total effective sensor area S total-sensor :0.2025mm 2 Pixel size: 1.99mm x 1.99mm, approx. 4.0mm 2

[0279] The metal grid transparent electrode was evaluated in the same manner as in Example A1, and the results are shown in Table 2.

[0280] An optical microscope image of the organic photodetector element of Example B1 is shown in FIG. 13 (note that components having the same functions as those in other embodiments are given the same reference numerals and detailed description thereof will be omitted).

[0281] <Characteristics evaluation of organic photodetector elements> [Evaluation of current density-voltage characteristics (JV characteristics)] The current density-voltage characteristics were evaluated in a nitrogen atmosphere glove box at room temperature. First, the external terminals from a semiconductor parameter analyzer (Agilent 4155C) were connected to the current collectors electrically connected to the cathode and anode of the organic photodetector element. The voltage was swept from -3 V to +2 V at a scan rate of 5 mV / s, and the current of the organic photodetector element was measured. The final measured current was calculated as the total effective sensor area S total-sens or The current density was calculated by dividing the dark current density (J dark The photocurrent density (J)-voltage (V) characteristics were measured by the above procedure in a dark room. photo )-V characteristics are measured in a dark room against the light intensity (I P ) is about 0.30mW / cm 2 The above operation was performed while irradiating an optical input signal with a wavelength (λ) of 850 nm. dark -V characteristics and J photo The dark current density at an applied voltage of -2 V is shown in Table 2.

[0282] [External quantum efficiency (EQE) characterization] External quantum efficiency was measured using a custom-made setup consisting of a tungsten halogen lamp, a monochromator (Oriel, Cornerstone 130), The organic photodetector element was placed in a nitrogen-environmented box sealed with a quartz window. With a voltage of -2 V applied to the organic photodetector element, the wavelength of the optical input signal was swept from 300 nm to 1100 nm in 10 nm increments. The optical input signal was irradiated onto the organic photodetector element through a circular aperture with a diameter of 1 mm, and the detected photocurrent was measured. The external quantum efficiency of the organic photodetector element at each wavelength was calculated by dividing the measured detected photocurrent by the total effective sensor area of ​​the subpixel array within the illuminated area to calculate the photocurrent density. This was then converted to external quantum efficiency based on a calibration curve for a Si photodiode measured under the same conditions. Figure 15 shows the wavelength (λ) dependence of the external quantum efficiency (EQE) at an applied voltage of -2 V.

[0283] [Light Intensity (I P ) Response evaluation Using the same equipment as that used for measuring the current density-voltage characteristics, the organic photodiode was The light intensity (I P ) to 2 x 10 -4 mW / cm 2 ~7.5×10 -1 mW / cm 2 By sweeping the photocurrent density (J p hoto ) light intensity (I P The wavelength of the optical input signal was 850 nm, and the voltage applied to the organic photodetector element was -2 V. Figure 16 shows the light intensity (I P)—Photocurrent density (J photo ) graph is shown.

[0284] [Calculation of visible light transmittance] Based on the optical model described above, the visible light transmittance of the organic photodetector element was calculated using the parameters listed in Table 2. The results are shown in Table 2.

[0285] [Table 2]

[0286] Examples B2 to B4

[0287] Line width W in the conductive pattern of the metal grid transparent electrode TCE and Gap G TCE The groove pattern of the plate used in the pattern formation process was changed as shown in Table 2. Otherwise, a metal grid transparent electrode and an organic photodetector element using the same were produced and evaluated in the same manner as in Example B1.

[0288] 13, in a top view, the region where the subsensor area 44SS is provided and the region where at least one metal wire 24 is provided at least partially overlap. In other words, the subsensor area 44SS is formed on at least a portion of at least one (e.g., two or three or more) metal wire 24. The at least one (e.g., two or three or more) metal wire 24 extends so as to intersect with two different sides of the subsensor area 44SS. Furthermore, the at least one (e.g., two or three or more) metal wire 24 extends so as to intersect with two different sides of the first subsensor area 44SS and also extends so as to intersect with two different sides of the second subsensor area 44SS.

[0289] In addition, in Figure 13, the same relationship as that of the first metal wiring 24 holds for at least one (e.g., two or more) second metal wirings 24 that extend in a direction different from that of the first metal wiring 24 (e.g., a perpendicular direction).

[0290] Therefore, in a projection view projected from above, the area in which the sub-sensor area 44SS is provided and the area in which at least one first metal wiring 24 is provided overlap at least in part, and the area in which the same sub-sensor area 44SS is provided and the area in which at least one second metal wiring 24 extending in a different direction from the first metal wiring 24 are provided overlap at least in part.

[0291] 13, it can be seen that in at least one direction, a sub-sensor area 44SS is provided on at least one or more metal wirings 24 that extend in the same direction within the conductive pattern 24P and face each other in a direction approximately perpendicular to the extending direction. sub―sensor / S TCE- unit By setting the value of 2 to 25, which is 1 or more, the sub-sensor area 44SS is provided so as to overlap with the metal wiring 24 even if the relative positions of the conductive pattern 24P and the sub-pixel 44S are shifted during the lamination process. This makes it possible to obtain a high external quantum efficiency of 15% or more at least in a part of the wavelength range of the near-infrared wavelength of 780 nm to 1200 nm (see Table 2 and FIG. 15). Furthermore, as shown in Table 2, these organic photodetector elements have a 10 -5 mA / cm 2 It can be seen that the following extremely low dark current density is exhibited. Furthermore, the organic photodetector elements of Examples B1 to B4 exhibit a high visible light transmittance of 60% or more.

[0292] From the above, it can be seen that the organic photodetector element of the present invention exhibits high photodetectivity due to high external quantum efficiency and extremely low dark current density, and can also simultaneously exhibit high visible light transmittance (see Table 2 and FIG. 14).

[0293] Furthermore, as shown in FIG. 16, the organic photodetector element of Example B1 was 10 -4 mW / cm 2 to 1 mW / cm 2 It can be seen that the photodetection current has a linear response over a wide range of light intensities.

[0294] <<Example C>> Hereinafter, a preferred range of design for a metal grid transparent electrode for improving the external quantum efficiency (EQE) of an organic photodetector element using the metal grid transparent electrode will be specifically described.

[0295] <External quantum efficiency (EQE) simulation> 〔simulation〕 The electrical and optical properties simulator software for optoelectronics, Setfos, manufactured by FLUXiM AG, and the large-area organic semiconductor simulator software, LAOSS, manufactured by FLUXiM AG, were used to simulate the metallization. We performed a simulation of an organic photodetector element using a talgrid transparent electrode.

[0296] Setfos is a system for simulating multilayer organic phosphatase structures based on the Transfer Matrix Formalism. The optical characteristics (particularly the optical absorption characteristics) of the detector element are used to calculate the carrier distribution of electrons and holes generated by photoexcitation, and the electron and hole carriers are calculated based on a mathematical model of drift-diffusion. This software simulates the electrical characteristics of organic photodetector elements, such as photocurrent density, by simulating the charge transport process of holes.

[0297] Setfos was used to model the multilayer structure of the organic photodetector element, which was placed on the metal wiring and the conductive pattern opening, respectively, and J photoThe -V characteristics were simulated. The multilayer structure on the metal wiring was transparent substrate / metal wiring / electron transport layer / organic photoelectric conversion layer / hole transport layer / anode / sealing layer, and the multilayer structure on the aperture was transparent substrate / quasi-perfectly transparent electrode / electron transport layer / organic photoelectric conversion layer / hole transport layer / anode / sealing layer.

[0298] Here, the pseudo-perfectly transparent electrode is a pseudo-electrode that does not absorb light, which is incorporated into the Setfos calculation program. The input parameters for the optical property simulation are the optical constants (refractive index: n The wavelength dependence of the extinction coefficient (k) and the film thickness were used. The input parameters for the electrical characteristics simulation, such as the mobility and energy levels of electrons and holes in each layer, were set by referring to literature values.

[0299] Next, the surface potential distribution of the electron transport layer / metal grid transparent electrode was measured using LAOSS. The distribution was calculated using two-dimensional finite element modeling (2D FEM). Specifically, the surface potential of each element and the J calculated by Setfos were photo The local current density was calculated based on the -V characteristics, and the differential equation that represents the relationship between the voltage drop according to Ohm's law as the local current density diffuses in the planar direction of the electron transport layer / metal grid transparent electrode was calculated until it converged for the entire system, and the surface potential distribution and current density distribution were calculated. s (λ) was calculated, and the external quantum efficiency (EQE) was calculated using the following formula.

[0300]

number

[0301] where λ is the wavelength of light, I P (λ) is the light intensity, 1.05 mW / cm 2 In addition, q is the elementary charge, h is Planck's constant, and c is the speed of light.

[0302] The input parameters for the 2D FEM were as follows to simulate Example B1: Conductive pattern settings: Mesh pattern, W TCE 1 μm, G TCE 19 μm Sheet resistance of the metal wiring part of the metal grid transparent electrode: 2.6Ω / sq. Sheet resistance of electron transport layer: 35×10 9 Ω / sq. Applied voltage: -2V

[0303] [Comparison of simulation and actual measurements] A comparison of the simulated external quantum efficiency (EQE) and the actual measurement (Example B1) is shown in Figure 17. It was confirmed that the external quantum efficiency measured could be reproduced by the simulation.

[0304] [Design optimization of metal grid transparent electrodes through simulation] Using this simulation, the metal wiring line width W TCE 0.5μm to 10μm, conductive pattern gap G TCE , (G TCE / W TCE ) is 1.0 or more and (W TC E +G TCE The external quantum efficiency (EQE) was simulated when the wavelength was changed within a range of 80 μm or less. The external quantum efficiency (EQE) gap G for each linewidth is shown in Figure 4. TCE Similarly, Fig. 5 shows the simulated external quantum efficiency (EQE) (G TCE / W TCE Similarly, Fig. 6 shows the simulated external quantum efficiency (EQE) (G TCE A TCE ) indicates dependency.

[0305] From Figures 4 and 5, the metal wiring width W of the metal grid transparent electrode TCE At the same time, the gap between the conductive patterns is adjusted to GTCE Then, (G TCE / W TCE ) is 1.0 or more and G TCE It can be seen that the external quantum efficiency (EQE) of an organic photodetector element using a metal grid transparent electrode can be improved by adjusting the aperture ratio of the conductive pattern to A TCE Then, (G TCE A TCE ) to between 0.25 μm·% and 45 μm·% It can be seen that the external quantum efficiency (EQE) of an organic photodetector element using a metal grid transparent electrode can be further improved. This is because the diffusion length (G TCE ) to make the surface potential distribution uniform and improve the charge collection efficiency η cc At the same time, the W of the metal wiring is improved. TCE By reducing the aperture ratio (A TCE This indicates that the external quantum efficiency (EQE) of organic photodetector elements can be improved by increasing the SiO2 content, suppressing the light-blocking effect of metal wiring, and improving the light capture efficiency of the organic photoelectric conversion layer.

[0306] <<Example D>> Hereinafter, an organic photodetector array having organic photodetector elements using a metal grid transparent electrode and a touchless user interface device using the same will be specifically described.

[0307] Example D Based on the results of Examples B and C, a metal grid transparent electrode design similar to that of Example B1 was implemented on an organic photodetector array. The organic photodetector array had a structure with a two-dimensional pattern in which pixels made of the organic photodetector elements described below were arranged at equal intervals along the orthogonal coordinate axes, with 16 in the X-axis direction and 16 in the Y-axis direction, for a total of 256 pixels.

[0308] <Design of organic photodetector element (pixel)> (X-axis, Y-axis) Subpixel: 70μm×70μm, S subOPD :4900μm 2 Sub-sensor area: 50μm x 50μm, S sub―sensor :2500μm 2 Pattern pitch P subOPD :240μm×240μm Number of subpixels N subOPD :14 pieces x 14 pieces, 196 pieces · Sub-pixel area occupancy rate Γ within a pattern unit subOPD :8.5% Total effective sensor area S total-sensor :0.49mm 2 Pixel size: 3.19mm x 3.19mm, approx. 10.2mm 2

[0309] <Design of organic photodetector array> (X-axis, Y-axis) Sensor area: 96.77mm x 96.77mm Pixel pitch: 6.24mm x 6.24mm Number of pixels: 16 x 16, 256 Pixel density: 4.2ppi

[0310] <<Manufacturing of metal grid transparent electrodes, wiring parts, current collecting parts, and dummy pattern parts>> The metal grid transparent electrode 20, the wiring portion 120, the current collecting portion 110, and the dummy pattern portion 130 were formed collectively by the following printing and firing process. The metal grid transparent electrode 20 provided for each pixel had a line width W TC E and Gap G TCECorresponding groove patterns were provided on the plate so that the wiring portion 120 and the dummy pattern portion 130 had corresponding groove patterns so that the aperture ratios would be described later. Similarly, a corresponding groove pattern was provided on the plate so that the current collecting portion 110 had the occupation area ratios described later. Using the plate, conductive pattern-shaped ink coating films (dispersion coating films) corresponding to the metal grid transparent electrode 20, wiring portion 120, current collecting portion 110, and dummy pattern portion 130 were printed simultaneously on the transparent substrate by the same pattern formation procedure as in Example B1. Next, the conductive pattern 24P of the metal grid transparent electrode 20, the second conductive pattern of the wiring portion 120, the third conductive pattern of the current collecting portion 110, and the dummy pattern portion 130 were produced by the same firing process procedure as in Example B1, except that 1.2 kW plasma was irradiated for 590 seconds in a reducing atmosphere. Note that the conductive pattern 24P, the second and third conductive patterns, and the dummy pattern portion were all mesh patterns.

[0311] Each wiring portion and each current collecting portion is electrically independent for each pixel, and the second conductive pattern of each wiring portion is electrically connected to the conductive pattern 24P of each pixel and the third conductive pattern of each current collecting portion.

[0312] <Evaluation of metal grid transparent electrodes, wiring, current collecting, and dummy pattern areas> The metal grid transparent electrode 20, the wiring section 120, the current collecting section 110, and the dummy pattern section 130 were measured for the gaps of the conductive pattern 24P, the second and third conductive patterns, and the dummy pattern section, as well as the line width and film thickness of the metal wiring, using representative planar photographs taken with a confocal laser microscope. Using these values, the repeating unit area S of the conductive pattern 24P was calculated. TCE-unit and aperture ratio A TCE The results are shown in Table 3.

[0313] [Table 3]

[0314] In addition, for the second conductive pattern and the dummy pattern portion, these numerical values ​​are used to calculate the aperture ratio A wire and aperture ratio A dummy The results are shown below.

[0315] <Wiring section (second conductive pattern)> Line width: 1 μm Gap: 15μm ·Aperture ratio A wire :88%

[0316] <Dummy pattern area> Line width: 1 μm Gap: 15μm~19μm ·Aperture ratio A wire :88%~90%

[0317] As shown in Table 3, the aperture ratio A of the conductive pattern of Example D TCE The rate was 87%. wire and A dummy are all A TCE This allowed the non-pixel areas to have the same visible light transmittance as the pixels, achieving uniform visibility.

[0318] In addition, for the third conductive pattern, these values ​​are used to calculate the occupied area ratio Γ pad The results are shown below.

[0319] <Current collecting part (third conductive pattern)> Line width: 5 μm Gap: 10μm ·Occupied area ratio Γ pad :55.6% Fabrication of organic photodetector arrays

[0320] An electron transport layer and an insulating layer were sequentially formed on the obtained metal grid transparent electrode using the same procedure as in Example B1. The openings OP of the insulating layer on the metal grid transparent electrode were patterned and formed to correspond to the subsensor areas of the above-described <Design of Organic Photodetector Element (Pixel)> for each pixel. Next, using the same procedure as in Example B1, a solid film of an organic photoelectric conversion layer was formed over the entire organic photodetector array by slot die coating using the ink for forming the organic photoelectric conversion layer. The organic photoelectric conversion layer was then patterned using the same procedure as in Example B1, except that the <Design of Organic Photodetector Element (Pixel)> described above was achieved in the [Formation of Subpixels and Subpixel Arrays] section of Example B1. During the patterning of the organic photoelectric conversion layer, dummy subpixel arrays with the same design as the subpixel arrays were formed on the insulating layer in areas other than the pixels (i.e., areas without openings OP in the insulating layer) over the entire organic photodetector array. The dummy subpixel array was separated by an insulating layer from the metal grid transparent electrode 20, the wiring portion 120, and the dummy pattern portion 130, and therefore had a structure in which it did not function as an organic photodetector element. Except for this, an organic photodetector array was fabricated in the same manner as in Example B1, in which pixels made up of organic photodetector elements were two-dimensionally arranged at equal intervals along the orthogonal coordinate axes, 16 in the X-axis direction and 16 in the Y-axis direction, for a total of 256 pixels, so as to achieve the <Design of Organic Photodetector Array>.

[0321] <Evaluation of organic photodetector array> A flexible printed circuit board was pressure-bonded to the current collecting portion 110 of the organic photodetector array and connected to an external control circuit. The organic photodetector array and external control circuit were then housed in a housing so that only the array sensor area of ​​the organic photodetector array was exposed. The external control circuit was also connected to a control laptop via USB, and the organic photodetector array was evaluated.

[0322] In a dark room, the dark current density (J dark In addition, in the same dark room, the array sensor area of ​​the organic photodetector array was exposed to a light beam with a wavelength of 850 nm and a light intensity of 46 μW / cm 2 The photocurrent density (J) of each pixel at an applied voltage of -2V was measured. photo ) were measured. Figure 18 shows histograms of the dark current density and photocurrent density of the organic photodetector array. The mode values ​​of the dark current density and photocurrent density were calculated from these histograms. The results are shown in Table 3.

[0323] The external quantum efficiency (EQE) was calculated from the mode of the obtained photocurrent density. The results are shown in Table 3.

[0324] Table 3 shows that the organic photodetector array also had electrical characteristics equivalent to those of the organic photodetector element of Example B1. This demonstrates that the organic photodetector array of the present invention can be made large-area and mass-produced industrially.

[0325] "Configuration and Evaluation of Touchless User Interface Device" [Configuration of Touchless User Interface Device] The organic photodetector array housed in the housing was placed on the display of the control notebook computer mentioned above.

[0326] In addition, a laser pointer capable of emitting three rectangular wave continuous pulse optical signals with a wavelength of 850 nm and frequencies of 1202 Hz, 962 Hz, and 801 Hz was used as the optical input signal. The laser pointer is equipped with two buttons, transmission button A and transmission button B, and the frequency can be changed by operating these buttons. Specifically, the mechanism is as follows.

[0327] If no send button is pressed: 1202Hz square wave continuous pulse light signal When send button A is pressed: 962Hz square wave continuous pulse light signal When Send Button B is pressed: 801Hz square wave continuous pulse light signal

[0328] The light intensity at the laser pointer's emitting surface is approximately 18 mW / cm at any frequency. 2 It was.

[0329] [Signal processing of photodetection signals] The photodetection signal of the organic photodetector array was passed through a digital bandpass filter corresponding to each of the three frequencies mentioned above, thereby extracting only the detection signal of the optical input signal from the entire photodetection signal, which included signals detecting disturbances such as natural light, indoor light, and light emitted from display devices such as displays. At the same time, only the photodetection signal with the largest frequency was selected from the three frequencies mentioned above, and signal processing was performed to extract it as a signal to be used in the detection position identification means described below.

[0330] Furthermore, the obtained detection signals were fitted with Gaussian functions in the X-axis and Y-axis directions, and the signal centroid positions in the X-axis and Y-axis directions were calculated from the peak positions. A detection position identification means was used to identify the detection position using these signal centroid positions.

[0331] [Screen operation using a touchless user interface device] Using the identified detected position, software was implemented that allows mouse movement on the map of a map operation application (Google Earth, manufactured by Google) and scrolling up, down, left, and right, as well as zooming in and out, using the methods described below.

[0332] Mouse movement on the map was controlled using the detected position of an optical detection signal that responded to a 1202 Hz rectangular wave continuous pulse optical signal.

[0333] The map scrolling operation was controlled by detecting the optical detection signal in response to a 962 Hz rectangular wave continuous pulse optical input signal transmitted by pressing the transmitter button A, and using the displacement of the detected position to control the scrolling operation.

[0334] The zoom-in / zoom-out operation of the map was controlled by detecting the photodetection signal in response to a continuous pulse light input signal of 801 Hz square wave emitted by pressing transmitter button B, and detecting the decrease (increase) in the spot diameter of the photodetection position when the distance between the laser pointer and the organic photodetector array was shortened (lengthened).

[0335] Fig. 19(a) is a photograph showing the state where a map in a map operation application is scrolled left and right using the touchless user interface device of the present invention. Fig. 19(b) is a photograph showing the state where a map in a map operation application is zoomed in using the touchless user interface device of the present invention.

[0336] In another configuration, we constructed a touchless user interface device in which a surface light source with a wavelength of 850 nm and a frequency of 1202 Hz, a rectangular wave continuous pulse signal, was formed using multiple near-infrared LED light sources arranged around the periphery of the array sensor area, and the reflected light generated by touching the surface light source with a finger as a pointing means was used as an optical input signal. The surface light source was adjusted so that it was projected onto a parallel plane separated from the organic photodetector array.

[0337] The optical input signal was detected by the organic photodetector array, and the detection position was identified using the same operation as in the above [Signal processing of optical detection signal]. Software control was implemented that allows selection of buttons displayed on the display using this detection position.

[0338] FIG. 20 is a photograph showing the operation of buttons on a screen simulating an ATM on a display by touching a near-infrared surface light source formed in space using the touchless user interface device of the present invention.

[0339] 19 and 20 show that an organic photodetector array, which is an array of two or more organic photodetector elements using a metal grid transparent electrode according to the present invention that simultaneously possesses both high visible light transmittance and high external quantum efficiency, can detect optical input signals without impairing the visibility of a display or other display device, and can be suitably used as a touchless user interface device.

[0340] [Second embodiment] Different embodiments of the present invention will be described below, but components that are understood by those skilled in the art to have the same or similar functions as those in other embodiments will be appropriately given the same or similar names or symbols, and descriptions thereof will be omitted or simplified, and the description will focus on the differences.

[0341] FIG. 21 is a schematic diagram of the OPD array 300 viewed from above to explain the arrangement of the pixels 300P and dummy pixels 300DP of the OPD array 300 according to this embodiment.

[0342] The OPD array 300 includes a transparent substrate 322 and a plurality of pixels 300P spaced apart from one another on the transparent substrate 322.

[0343] Each pixel 300P is configured to be able to detect incident light and includes an OPD element. The OPD element includes a first transparent electrode 320 formed on a transparent substrate 322, a plurality of organic semiconductor layers 344 spaced apart from one another on the first transparent electrode 320, and a second transparent electrode 360 ​​formed on the plurality of organic semiconductor layers 344. With this configuration, incident light generates electrons and holes in the organic semiconductor layer 344, generating a photovoltaic force between the first transparent electrode 320 and the second transparent electrode 360, causing a current to flow. Therefore, the OPD element of each pixel 300P is configured to be able to detect incident light. The OPD element of each pixel 300P of the OPD array 300 may have a configuration that is the same as or similar to that of the OPD element 10, or a different configuration, as long as it is capable of detecting incident light.

[0344] The first transparent electrode 320 may have a known configuration, for example, the first transparent electrode 320 may be a metal grid transparent electrode 20, or a transparent electrode having a different configuration.

[0345] The organic semiconductor layers (sometimes referred to as "organic semiconductor films") 344 are provided spaced apart from one another on the same first transparent electrode 320. In this embodiment, nine organic semiconductor layers 344 (3 x 3) are provided spaced apart from one another on the same first transparent electrode 320. By providing a plurality of organic semiconductor layers spaced apart from one another in this manner, even if the organic semiconductor layers have low transparency, light can be transmitted between adjacent organic semiconductor layers. Therefore, even if the OPD array 300 is provided on the screen of a display or display body, it is possible to suppress a decrease in visibility of the display or display body.

[0346] The organic semiconductor layer 344 may have a known configuration. For example, the organic semiconductor layer 344 may have the same configuration as the organic photoelectric conversion layer 44, or may be formed in the form of a flat film as shown in Fig. 21. The organic semiconductor layer 344 may be formed from a material that can be used for the organic photoelectric conversion layer 44 shown in other embodiments, or may be formed from another material.

[0347] The second transparent electrode 360 ​​is provided on a plurality of organic semiconductor layers 344 that are provided spaced apart from one another on the same first transparent electrode 320. The second transparent electrode 360 ​​may have the same configuration as the transparent electrode 60, or may be formed in the shape of a flat film as shown in FIG.

[0348] 21, the pixels 300P are arranged in a checkerboard pattern. That is, the pixels 300P are arranged spaced apart from one another in a first direction (the left-right direction on the paper in the figure), and are arranged spaced apart from one another in a second direction (the up-down direction on the paper in the figure), and a pixel 300P is also arranged at a position that is intermediate between adjacent pixels 300P in the first direction and corresponds to the intermediate position between adjacent pixels 300P in the second direction.

[0349] By adopting a configuration in which the pixels 300P are spaced apart in this manner, it is possible to increase the detection resolution compared to a case in which pixels are densely packed by providing pixels at intermediate positions between adjacent pixels 300P in the first and second directions. In other words, when the pixels are densely packed, the possibility that multiple pixels will detect incident light for the same optical input signal increases, which may actually decrease the detection resolution. On the other hand, when the pixels 300P are spaced apart, the possibility that multiple pixels will detect incident light for the same optical input signal decreases, making it possible to suppress a decrease in detection resolution.

[0350] The distance between adjacent pixels 300P may be, for example, equal to or greater than the length of a single pixel 300P. For example, the distance between adjacent pixels 300P in a first direction may be equal to or greater than the length of the pixels 300P in the first direction. Alternatively, the distance between adjacent pixels 300P in the first direction may be equal to or less than twice the length of the pixels 300P in the first direction. Similarly, the distance between adjacent pixels 300P in a second direction perpendicular to the first direction may be equal to or greater than the length of the pixels 300P in the second direction. Alternatively, the distance between adjacent pixels 300P in the second direction may be equal to or less than twice the length of the pixels 300P in the second direction.

[0351] Furthermore, the pixels 300P in this embodiment are arranged in a checkerboard pattern. Since the pixels 300P are arranged evenly in this manner, it is possible to reduce the possibility that none of the pixels will detect incident light.

[0352] Furthermore, dummy pixels 300DP are provided between adjacent pixels 300P on the transparent substrate 322. Here, the dummy pixels 300DP refer to regions provided with organic semiconductor layers 344D that are insulated and therefore do not have the function of detecting incident light.

[0353] Each dummy pixel 300DP has a plurality of organic semiconductor layers 344D spaced apart and insulated from one another on the transparent substrate 322. In this embodiment, nine organic semiconductor layers 344D (3 × 3) are spaced apart from one another on the transparent substrate 322. As shown in the figure, the organic semiconductor layer 344D of each dummy pixel 300DP is not electrically connected to at least one of the first transparent electrode 320 and the second transparent electrode 360, and therefore no current flows through it, and therefore it is configured not to detect incident light. An insulating film (not shown) may be formed on the organic semiconductor layer 344D, and a second transparent electrode 360 ​​may be formed on the organic semiconductor layer 344D.

[0354] However, the dummy pixel 300DP is not limited to the configuration shown in this embodiment. For example, the dummy pixel 300DP may have the same structure as the pixel 300P, but may be insulated by not providing wiring connecting the current collecting portion 110 to the dummy pixel 300DP. This configuration allows at least a portion of the manufacturing process for the pixel 300P and the dummy pixel 300DP to be shared. Even in the configuration shown in FIG. 21 , by providing the organic semiconductor layer 344 and the organic semiconductor layer 344D at the same height from the surface of the transparent substrate 322 and using the same material, it is possible to share at least a portion of the film formation process for the organic semiconductor layer 344 and the organic semiconductor layer 344D.

[0355] The number, size, and shape of the organic semiconductor layers 344D included in the pixel 300P and the dummy pixel 300DP may be different. For example, the organic semiconductor layers 344 included in the pixel 300P may be four, with two in the first direction and two in the second direction, forming a 2×2 arrangement, while the organic semiconductor layers 344D included in the dummy pixel 300DP may be two, with two in the first direction and one in the second direction, forming a 2×1 arrangement.

[0356] As shown in Figure 21, the multiple dummy pixels 300DP are arranged in a checkerboard pattern. That is, the pixels 300P and the dummy pixels 300DP are alternately arranged in a first direction (the horizontal direction of the paper in the figure) and alternately arranged in a second direction (the vertical direction of the paper in the figure). However, the sizes of the pixels 300P and the dummy pixels 300DP may be different. For example, the width of the pixel 300P in the first direction may be more than twice the width of the dummy pixel 300D in the first direction.

[0357] According to the OPD array 300 configured as described above, dummy pixels 300DP are provided between adjacent pixels 300P, which makes it possible to suppress the occurrence of interference fringes that occur when the OPD elements of the pixels 300P are spaced apart from each other. This makes it possible to suppress the occurrence of visible interference fringes that occur when interference fringes caused by the OPD elements and interference fringes caused by the organic semiconductor layer 344, which is formed at a distance, are superimposed on each other.

[0358] Therefore, when an OPD array 300 is provided on the screen of a display or display body as described using Figure 9, etc., it is possible to suppress interference fringes due to light emitted from the display or display body, thereby improving the visibility of the display or display body. [Industrial Applicability]

[0359] The organic photodetector element using the metal grid transparent electrode of this embodiment, which enables both high visible light transmittance and high external quantum efficiency, can detect optical input signals without impairing the visibility of a display device such as a display, and is suitable for use in touchless user interface devices, making it industrially applicable.

[0360] As described above, the organic photodetector element using the metal grid transparent electrode according to this embodiment has at least one subpixel 44S formed of an organic photoelectric conversion layer 44. This subpixel 44S at least partially includes a subsensor area 44SS. In a top projection of the organic photodetector element, the area where the subsensor area 44SS is provided and the area where the metal wiring 24 is provided are arranged so as to at least partially overlap. This configuration facilitates transport of electrons generated in the organic photoelectric conversion layer 44 to the nearby metal wiring 24 via the electron transport layer 42, thereby improving external quantum efficiency. Furthermore, this configuration allows for an increase in the area ratio of the area with relatively high visible light transmittance (area excluding the subpixel 44S) even when a near-infrared detection material with low visible light transmittance is used for the organic photoelectric conversion layer 44. This allows for an improvement in the visible light transmittance of the organic photodetector element and the organic photodetector array as a whole. Furthermore, by designing the area of ​​the subsensor area 44SS to be equal to or larger than the area of ​​the repeating unit of the conductive pattern 24P of the metal grid transparent electrode 20, even if the relative positions of the two are shifted during manufacturing (lamination process), it is possible for the region where the subsensor area 44SS is provided to at least partially overlap with the region where the metal wiring 24 is provided. This enables the organic photodetector element of the present invention to exhibit high light detectability due to high external quantum efficiency and extremely low dark current density, while also enabling it to exhibit high visible light transmittance.

[0361] The metal wiring 24 of the metal grid transparent electrode 20 may also be manufactured by a printing method. Forming the metal wiring 24 by a printing method makes it possible to easily provide metal wiring 24 having a thickness of 30 nm or more. In addition, it is possible to easily change the gap between the metal wirings, the line width, etc. The inventors of the present application have found that if the gap between the metal wirings is made too small, the light is blocked by the metal wiring 24, reducing the light capture efficiency into the organic photoelectric conversion layer 44. Conversely, if the gap is made too large, the diffusion distance of electrons in the openings to the metal wiring 24 in the in-plane direction within the electron transport layer 42 increases, thereby actually reducing the charge collection efficiency η c c By noting that the external quantum efficiency decreases, the range of the product of the gap and the aperture ratio for increasing the external quantum efficiency was derived as described above.

[0362] Furthermore, the inventors of the present application have discovered an organic photodetector array in which two or more organic photodetector elements are arranged, which enables both high visible light transmittance and high external quantum efficiency of the present invention, as well as an optical input signal and signal processing method suitable for this, and have constructed a new type of touchless user interface device.

[0363] Furthermore, the present invention can be modified in various ways without departing from the spirit of the present invention. For example, some components of one embodiment can be added to other embodiments within the scope of ordinary creativity of a person skilled in the art. Also, some components of one embodiment can be replaced with corresponding components of other embodiments.

[0364] The following additional notes are provided regarding the above-described embodiments.

[0365] (Appendix 1) A photodetector element comprising a metal grid transparent electrode as a first electrode, a transparent electrode as a second electrode facing the metal grid transparent electrode, and a subpixel formed of at least one organic semiconductor layer between the metal grid transparent electrode and the transparent electrode, the metal grid transparent electrode comprises a transparent substrate and a conductive pattern having metal wiring provided on the transparent substrate; the subpixel comprises at least a portion of a sub-sensor area; an area where the sub-sensor area is provided and an area where the metal wiring is provided, when projected from above, at least partially overlap each other; Photodetector element.

[0366] (Appendix 2) S TCE-unit is the repeating unit area of ​​the conductive pattern, and S sub―s ensor When is the area of ​​the sub-sensor area, S sub―sensor / S T CE-unit is greater than or equal to 1, 2. The photodetector element of claim 1.

[0367] (Appendix 3) At least a part of the sub-sensor area projected from the upper surface of the photodetector element overlaps, in at least one direction, with two or more of the metal wirings extending in the same direction. 3. The photodetector element according to claim 1 or 2.

[0368] (Appendix 4) providing an insulating layer having an opening between the metal grid transparent electrode and the transparent electrode; the subpixel is arranged so as to cover the opening when projected onto a surface from an upper surface in a stacking direction, the sub-sensor area corresponds to an area where the sub-pixel and the opening overlap when projected onto the surface from the upper surface in the stacking direction; 4. A photodetector element according to any one of claims 1 to 3.

[0369] (Appendix 5) the shape of the region in which the subpixels are provided, projected from above, is at least one selected from the group consisting of a square, a rectangle, a substantially square, and a substantially rectangle; 5. A photodetector element according to any one of claims 1 to 4.

[0370] (Appendix 6) a subpixel array including a plurality of the subpixels spaced apart from one another; 6. A photodetector element according to any one of claims 1 to 5.

[0371] (Appendix 7) the subpixel array has a pattern in which the subpixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the subpixel array; 7. The photodetector element of claim 6.

[0372] (Appendix 8) S subOPD is the area of ​​the subpixel, S subOPD is 25 μm 2 More than 10000μm 2 Below is the 8. A photodetector element according to any one of claims 1 to 7.

[0373] (Appendix 9) The photodetector element is The external quantum efficiency at at least a part of the wavelength in the near-infrared wavelength region of 780 nm to 1200 nm is 15% or more, The visible light transmittance in the stacking direction of the photodetector element in the region including the sub-sensor area is 50% or less. A photodetector element according to any one of claims 1 to 8.

[0374] (Appendix 10) t TCE is the thickness of the metal wiring, and t OPD is the film thickness of the sub-sensor area, tTCE is 30 nm or more and 200 nm or less, (t OPD -t TCE ) is 50 nm or more and 500 nm or less, 10. A photodetector element according to any one of claims 1 to 9.

[0375] (Appendix 11) W TCE is the line width of the metal wiring of the metal grid transparent electrode, G TCE is the gap between adjacent metal wirings extending in the same direction, W TCE is 0.25 μm or more and 5.0 μm or less, G TCE is 45 μm or less, and (G TCE / W TCE ) is greater than or equal to 1.0, 11. A photodetector element according to any one of claims 1 to 10.

[0376] (Appendix 12) A TCE is the aperture ratio of the conductive pattern, (G TCE A TCE ) is between 0.25 μm·% and 45 μm·%. 12. The photodetector element of claim 11.

[0377] (Appendix 13) Aperture ratio A of the conductive pattern TCE is greater than or equal to 25% and less than 100%; 13. The photodetector element of claim 12.

[0378] (Appendix 14) The organic semiconductor layer is an organic semiconductor layer configured to be capable of photoelectric conversion. 14. A photodetector element according to any one of claims 1 to 13.

[0379] (Appendix 15) Eg opt When is the optical band gap, The organic semiconductor layer is g opt Organic donor materials with E g opt and an organic acceptor material having a dc-substrate of 1.65 eV or less. 15. The photodetector element of claim 14.

[0380] (Appendix 16) the organic acceptor material is at least one selected from the group of non-fullerene acceptor materials consisting of IEICO-4F, IEICO-4Cl, IEICO, DTPC-DFIC, DCI-2, COTIC-4F, PDTTIC-4F, DTPC-IC, 6TIC-4F, COiDFIC, FOIC, F8IC, F10IC, SiOTIC-4F, and P3; 16. The photodetector element of claim 15.

[0381] (Appendix 17) the organic donor material is at least one selected from the group consisting of PTB7-Th (also known as PCE-10), PDTP-DFBT, PDPP3T, PDPP3T-O14, PDPP3T-O16, PDPP3T-O20, PDPP3T-C20, PDPP4T, DPPTfQxT, DPPTQxT, DPPBTQxBT, DPPBTffQxBT, FLP030, PBDTT-SeDPP, PBDTT-DPP, PBDTT-FDPP, PDPP2T-TT (PTT-DTDPP), PCDTBT, PCPDTBT, PCPDTFBT, and Si-PCPDTBT; 17. The photodetector element according to claim 15 or 16.

[0382] (Appendix 18) the metal wiring includes a metal and an oxide of the metal; 18. A photodetector element according to any one of claims 1 to 17.

[0383] (Appendix 19) The conductive pattern comprises a mesh pattern. 19. A photodetector element according to any one of claims 1 to 18.

[0384] (Appendix 20) A photodetector array in which two or more pixels each consisting of the photodetector element according to any one of claims 1 to 19 are arranged.

[0385] (Appendix 21) a wiring section provided on the transparent substrate and having a second conductive pattern electrically connected to the conductive pattern, the wiring section being provided for each pixel; A TCE is the aperture ratio of the conductive pattern, A wire is the aperture ratio of the second conductive pattern, -10%≦(A wire -A TCE )≦10%; 21. The photodetector array of claim 20.

[0386] (Appendix 22) a current collecting portion provided on the transparent substrate and having a third conductive pattern electrically connected to the second conductive pattern; Gamma pad is the occupied area ratio of the third conductive pattern per unit area, Gamma pad is greater than or equal to 50% and less than 100%; 22. The photodetector array of claim 21.

[0387] (Appendix 23) a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern; 23. The photodetector array of any one of claims 20 to 22.

[0388] (Appendix 24) A TCE is the aperture ratio of the conductive pattern, Adummy is the aperture ratio of the dummy pattern, -10%≦(A dummy -A TCE )≦10%; 24. The photodetector array of claim 23.

[0389] (Appendix 25) an insulating layer provided on the metal grid transparent electrode; and a dummy subpixel array including a plurality of dummy subpixels each made of an organic semiconductor layer provided on the insulating layer; a subpixel array including a plurality of the subpixels; the dummy subpixel array and the subpixel array projected from above have the same pattern structure; 25. The photodetector array of any one of claims 20 to 24.

[0390] (Appendix 26) The pixel size of the photodetector array is 1 mm 2 More than 25mm 2 Below is the 26. The photodetector array of any one of claims 20 to 25.

[0391] (Appendix 27) The pixel density of the photodetector array is 2 ppi or more and 15 ppi or less. 27. The photodetector array of any one of claims 20 to 26.

[0392] (Appendix 28) the photodetector array has a pattern in which the pixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the photodetector array; 28. The photodetector array of any one of claims 20 to 27.

[0393] (Appendix 29) 29. A photodetector array according to any one of claims 20 to 28 for arrangement on a screen of a display or display body, using the photodetector elements of the photodetector array to convert an optical input signal irradiated onto the photodetector array into an electrical output signal, thereby detecting a position where the optical input signal is irradiated; The position detection is configured to enable input operation to the screen of the display or the display body, Touchless user interface device.

[0394] (Appendix 30) 30. The touchless user interface device of claim 29, wherein the optical input signal includes light having at least a portion of a wavelength in a near-infrared wavelength region of 780 nm to 1200 nm.

[0395] (Appendix 31) The optical input signal is frequency modulated, and the modulation frequency is 0.5 kHz or more and 20 kHz or less. 31. The touchless user interface device of claim 29 or 30.

[0396] (Appendix 32) the optical input signal is an optical signal emitted from a laser pointer; 32. A touchless user interface device according to any one of claims 29 to 31.

[0397] (Appendix 33) the optical input signal is reflected light from an indicating means; 32. A touchless user interface device according to any one of claims 29 to 31.

[0398] (Appendix 34) the optical input signal is a reflected light from the pointing means that is generated when the pointing means comes into contact with a planar projection light beam formed in space; 34. The touchless user interface device of claim 33.

[0399] (Appendix 35) A transparent substrate; a plurality of pixels spaced apart from one another on the transparent substrate, each pixel having a photodetector element; a plurality of dummy pixels provided on the transparent substrate at a distance from each other and insulated from each other between two of the pixels; Each of the photodetector elements has a first transparent electrode formed on the transparent substrate, a plurality of organic semiconductor layers spaced apart from one another on the first transparent electrode, and a second transparent electrode formed on the plurality of organic semiconductor layers; Each of the dummy pixels has a plurality of organic semiconductor layers spaced apart from one another on the transparent substrate. Photodetector array.

[0400] (Appendix 36) The plurality of pixels and the plurality of dummy pixels are are arranged alternately in the first direction, and They are arranged alternately in a second direction perpendicular to the first direction. 36. The photodetector array of claim 35.

[0401] (Appendix 37) The plurality of organic semiconductor layers of the pixel and the plurality of organic semiconductor layers of the dummy pixel are made of the same material and are provided at the same height with respect to the surface of the transparent substrate. 37. The photodetector array of claim 35 or 36.

[0402] (Appendix 38) the first transparent electrode comprises a metal grid transparent electrode having a conductive pattern having metal wiring provided on the transparent substrate; 38. The photodetector array of any one of claims 35 to 37. [Explanation of symbols]

[0403] 10 Organic photodetector element (OPD element) 20 Metal grid transparent electrode 22 Transparent base material 24 Metal wiring 24P conductive pattern 42 Electron transport layer 44 Organic photoelectric conversion layer 44S subpixel 44SS Sub-sensor area 44SA Alignment Area 44SC connection part 46 Hole transport layer 60 Transparent electrode 80 insulating layer 100 Organic Photodetector Array (OPD Array) 110 Current collector 120 Wiring section 130 Dummy pattern section 200 Touchless User Interface Device (UI Device) OP opening D Display IL Incident light (optical input signal) PD instruction means LS light source (point light source) LS2 Planar projection luminous flux (surface light source)

Claims

1. A photodetector element comprising: a metal grid transparent electrode as a first electrode; a transparent electrode as a second electrode facing the metal grid transparent electrode; and a plurality of subpixels each composed of a plurality of organic semiconductor layers spaced apart between the metal grid transparent electrode and the transparent electrode, the metal grid transparent electrode comprises a transparent substrate and a conductive pattern having metal wiring provided on the transparent substrate; the subpixel comprises at least a portion of a sub-sensor area; a region where the sub-sensor area is provided and a region where the metal wiring is provided, projected from above, at least partially overlap each other; S TCE-unit is the repeating unit area of ​​the conductive pattern, and S sub-sensor is the area of ​​the sub-sensor area, S sub-sensor / S TCE-unit is greater than or equal to 1, Photodetector element.

2. At least a part of the sub-sensor area projected from the upper surface of the photodetector element overlaps, in at least one direction, with two or more of the metal wirings extending in the same direction. The photodetector element according to claim 1 .

3. providing an insulating layer having an opening between the metal grid transparent electrode and the transparent electrode; the subpixel is arranged so as to cover the opening when projected onto a surface from an upper surface in a stacking direction, the sub-sensor area corresponds to an area where the sub-pixel and the opening overlap when projected onto the surface from the upper surface in the stacking direction; The photodetector element according to claim 1 .

4. the shape of the region in which the subpixels are provided, projected from above, is at least one selected from the group consisting of a square, a rectangle, a substantially square, and a substantially rectangle; The photodetector element according to claim 1 .

5. a subpixel array consisting of the plurality of subpixels, the subpixel array having a pattern in which the subpixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the subpixel array; The photodetector element according to claim 1 .

6. S subOPD is the area of ​​the subpixel, S subOPD is 25 μm 2 10000 μm or more 2 Below is the The photodetector element according to claim 1 .

7. The photodetector element is The external quantum efficiency at at least a part of the wavelength in the near-infrared wavelength region of 780 nm to 1200 nm is 15% or more, a visible light transmittance in the stacking direction of the photodetector element in a region including the sub-sensor area is 50% or less; The photodetector element according to claim 1 .

8. t TCE is the thickness of the metal wiring, and t OPD is the film thickness of the sub-sensor area, t TCE is 30 nm or more and 200 nm or less, (t OPD -t TCE ) is 50 nm or more and 500 nm or less, The photodetector element according to claim 1 .

9. W TCE is the line width of the metal wiring of the metal grid transparent electrode, G TCE is the gap between adjacent metal wirings extending in the same direction, W TCE is 0.25 μm or more and 5.0 μm or less, G TCE is 45 μm or less, and (G TCE / W TCE ) is 1.0 or greater, The photodetector element according to claim 1 .

10. A TCE is the aperture ratio of the conductive pattern, (G TCE ・A TCE ) is 0.25 μm·% or more and 45 μm·% or less, The photodetector element according to claim 9 .

11. Aperture ratio A of the conductive pattern TCE is 25% or more and less than 100%; The photodetector element according to claim 10.

12. The organic semiconductor layer is an organic semiconductor layer configured to be capable of photoelectric conversion. The photodetector element according to claim 1 .

13. E gopt When is the optical band gap, The organic semiconductor layer is gopt an organic donor material having an E gopt and an organic acceptor material having a valence of 1.65 eV or less. The photodetector element according to claim 12.

14. the organic acceptor material is at least one selected from the group of non-fullerene acceptor materials consisting of IEICO-4F, IEICO-4Cl, IEICO, DTPC-DFIC, DCI-2, COTIC-4F, PDTTIC-4F, DTPC-IC, 6TIC-4F, COi8DFIC, FOIC, F8IC, F10IC, SiOTIC-4F, and P3; The photodetector element according to claim 13.

15. the organic donor material is at least one selected from the group consisting of PTB7-Th (also known as PCE-10), PDTP-DFBT, PDPP3T, PDPP3T-O14, PDPP3T-O16, PDPP3T-O20, PDPP3T-C20, PDPP4T, DPPTfQxT, DPPTQxT, DPPBTQxBT, DPPBTffQxBT, FLP030, PBDTT-SeDPP, PBDTT-DPP, PBDTT-FDPP, PDPP2T-TT (PTT-DTDPP), PCDTBT, PCPDTBT, PCPDTFBT, and Si-PCPDTBT; The photodetector element according to claim 13 or 14.

16. the metal wiring includes a metal and an oxide of the metal; The photodetector element according to claim 1 .

17. The conductive pattern comprises a mesh pattern. The photodetector element according to claim 1 .

18. A photodetector array in which two or more pixels each comprising the photodetector element according to claim 1 are arranged.

19. a photodetector element including a metal grid transparent electrode as a first electrode, a transparent electrode as a second electrode facing the metal grid transparent electrode, and a plurality of subpixels each including a plurality of organic semiconductor layers spaced apart between the metal grid transparent electrode and the transparent electrode; the metal grid transparent electrode comprises a transparent substrate and a conductive pattern having metal wiring provided on the transparent substrate; the subpixel comprises at least a portion of a sub-sensor area; a photodetector array in which two or more pixels each made of the photodetector element are arranged, wherein an area in which the sub-sensor area is provided and an area in which the metal wiring is provided overlap at least partially when projected from above, a wiring section provided on the transparent substrate and having a second conductive pattern electrically connected to the conductive pattern, the wiring section being provided for each pixel; A TCE is the aperture ratio of the conductive pattern, A wire is the aperture ratio of the second conductive pattern, -10%≦(A wire -A TCE )≦10%; Photodetector array.

20. a current collecting portion provided on the transparent substrate and having a third conductive pattern electrically connected to the second conductive pattern; Gamma pad is the occupied area ratio of the third conductive pattern per unit area, Gamma pad is 50% or more and less than 100%; 20. The photodetector array of claim 19.

21. a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern; 20. The photodetector array of claim 18.

22. a photodetector element including a metal grid transparent electrode as a first electrode, a transparent electrode as a second electrode facing the metal grid transparent electrode, and a plurality of subpixels each including a plurality of organic semiconductor layers spaced apart between the metal grid transparent electrode and the transparent electrode; the metal grid transparent electrode comprises a transparent substrate and a conductive pattern having metal wiring provided on the transparent substrate; the subpixel comprises at least a portion of a sub-sensor area; an area where the sub-sensor area is provided and an area where the metal wiring is provided, when projected from above, at least partially overlap each other; and two or more pixels each made of the photodetector element are arranged. A photodetector array comprising a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern, A TCE is the aperture ratio of the conductive pattern, A dummy is the aperture ratio of the dummy pattern, -10%≦(A dummy -A TCE )≦10%; Photodetector array.

23. an insulating layer provided on the metal grid transparent electrode; and a dummy subpixel array including a plurality of dummy subpixels each made of an organic semiconductor layer provided on the insulating layer; a subpixel array including a plurality of the subpixels; the dummy subpixel array and the subpixel array, when projected from above, both have a two-dimensional array structure, and a pitch of the dummy subpixel array in a first direction and / or a second direction is the same as a pitch of the subpixel array in the first direction and / or a second direction.

20. The photodetector array of claim 18.

24. The pixel size of the photodetector array is 1 mm 2 25mm or more 2 Below is the 20. The photodetector array of claim 18.

25. The pixel density of the photodetector array is 2 ppi or more and 15 ppi or less.

20. The photodetector array of claim 18.

26. the photodetector array has a pattern in which the pixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the photodetector array; 20. The photodetector array of claim 18.

27. A photodetector array according to claim 18 for placement on a screen of a display or a display body, using the photodetector elements of the photodetector array to convert an optical input signal irradiated onto the photodetector array into an electrical output signal, thereby detecting a position where the optical input signal is irradiated; The position detection is configured to enable input operation to the screen of the display or the display body, Touchless user interface device.

28. 28. The touchless user interface device of claim 27, wherein the optical input signal includes light having a wavelength in at least a portion of a near-infrared wavelength range from 780 nm to 1200 nm.

29. the optical input signal is frequency modulated, and the modulation frequency is 0.5 kHz or more and 20 kHz or less; 28. The touchless user interface device of claim 27.

30. the optical input signal is an optical signal emitted from a laser pointer; 28. The touchless user interface device of claim 27.

31. the optical input signal is reflected light from an indicating means; 28. The touchless user interface device of claim 27.

32. the optical input signal is a reflected light from the pointing means that is generated when the pointing means comes into contact with a planar projection light beam formed in space; 32. The touchless user interface device of claim 31.

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