Photodetector element using transparent electrode with metal grid and non-touch user interface device using same

Abstract

The purpose of the present invention is to provide a photodetector element capable of improving photodetectability while maintaining high transparency, and a non-touch user interface device using the photodetector element. This photodetector element (10) is provided with: a metal grid transparent electrode (20), which is a first electrode; a transparent electrode (60), which is a second electrode and faces the metal grid transparent electrode (20); and a sub-pixel (44S) that includes at least one photoelectric conversion layer (44) and is positioned between the metal grid transparent electrode and the transparent electrode, in which the metal grid transparent electrode (20) is provided with a transparent substrate (22) and a conductive pattern (24P) having a metal wiring (24) provided on the transparent substrate (22). The sub-pixel (44S) is provided with a sub-sensor region (44SS) in at least a portion thereof, and a region in which the sub-sensor region (44SS) is provided and a region in which the metal wiring (24) is provided overlap in at least a portion thereof when projected from the upper surface.

Description

Technical Field

[0001] The present invention relates to a photodetector element using a metal grid transparent electrode capable of simultaneously achieving high visible light transmittance and high external quantum efficiency, particularly in a near-infrared wavelength region, and a touchless user interface device using the photodetector element. Background Art

[0002] Touch-type user interfaces such as touch panels that detect being touched are widely used in, for example, smartphones, smart watches, notebook computers, ATMs, kias, and electronic book terminals using electronic paper. A touch-type user interface includes a transparent touch panel provided on a display such as a display.

[0003] In recent years, non-touch user interfaces have attracted attention instead of touch user interfaces from the perspectives of further expanding user experience, improving public hygiene awareness, and dealing with static electricity, and research and development is being vigorously promoted. As an example for realizing a non-touch user interface, for example, it is proposed that light from a light source such as a laser pointer or reflected light from an indicating member such as a finger is used as an optical input signal, and a transparent sensor panel or sensor sheet having a photodetector array composed of one-dimensional or two-dimensionally arranged photodetectors is arranged on a display such as a display, and the position of the optical input signal is detected, thereby performing input operations such as screen input.

[0004] Non-patent document 1 discloses an organic photodetector array in which each unit pixel is equipped with an organic photodetector element, wherein the organic photodetector element is formed by patterning a non-transparent organic photoelectric conversion layer capable of detecting light in a wavelength region of 500 nm to 600 nm into an island shape having a size of 10 μm×10 μm using photolithography technology. By patterning each organic photoelectric conversion layer into a tiny island shape, the area ratio of the opening portion having a high visible light transmittance can be increased, thereby achieving a transmittance of up to 70% in the visible light region and detection of visible light at the same time.

[0005] Prior art literature

[0006] Non-patent literature

[0007] Non-patent literature 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

[0008] 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

[0009] Non-patent literature 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

[0010] Problem that the invention aims to solve

[0011] However, the effective sensor area of ​​the organic photodetector element disclosed in Non-Patent Document 1 is 100 μm 2 The detection current I is small. Therefore, from the perspective of the SN ratio in an actual use environment, it is difficult to use the photodetector array composed of organic photodetector elements disclosed in non-patent document 1 for a non-touch user interface. In addition, the organic photodetector element disclosed in non-patent document 1 uses a non-transparent metal solid film in the cathode. If the effective sensor area is increased to improve the SN ratio, the visual recognition light transmittance will be impaired.

[0012] Therefore, an object of the present invention is to provide a photodetector element capable of improving light detectability while maintaining high transparency, and a touchless user interface device using the photodetector element.

[0013] Solutions for solving problems

[0014] That is, the present invention is as follows.

[0015] A photodetector element comprises: a metal grid transparent electrode, which is a first electrode; a transparent electrode, which is a second electrode, the second electrode being opposite to the metal grid transparent electrode; and a sub-pixel, which comprises at least one photoelectric conversion layer and is located between the metal grid transparent electrode and the transparent electrode, wherein the metal grid transparent electrode comprises a transparent substrate and a conductive pattern, the conductive pattern comprises a metal wiring arranged on the transparent substrate, the sub-pixel comprises a sub-sensor area in at least a portion, and the area where the sub-sensor area is provided overlaps with the area where the metal wiring is provided in at least a portion when projected from the upper surface.

[0016] According to the photodetector element, wherein, in the S TCE-unit Assume that the repeating unit area of ​​the conductive pattern and S sub-sensor When S is set as the area of ​​the sub-sensor region, sub-sensor / S TCE-unit is 1 or more.

[0017] In addition, according to the photodetector element, it is characterized in that at least a portion of the sub-sensor area of ​​the photodetector element when projected from the upper surface overlaps with two or more of the metal wirings extending in the same direction in at least any one direction.

[0018] According to the photodetector element, an insulating layer having an opening is provided between the metal grid transparent electrode and the transparent electrode, the sub-pixel is configured to cover the opening when projected onto the surface from the upper surface in the stacking direction, and the sub-sensor area is equivalent to the area where the sub-pixel and the opening overlap when projected onto the surface from the upper surface in the stacking direction.

[0019] According to the photodetector element, the shape of the region where the sub-pixel is provided when projected from the upper surface is at least one shape selected from the group consisting of a square, a rectangle, a substantially square, and a substantially rectangular shape.

[0020] According to the photodetector element, the photodetector element includes a sub-pixel array including a plurality of the sub-pixels disposed at intervals.

[0021] According to the photodetector element, the sub-pixel array has a pattern in which the sub-pixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the sub-pixel array.

[0022] According to the photodetector element, wherein, in the S subOPD When S is set to the area of ​​the sub-pixel, subOPD 25μm 2 Above and 10000μm2 the following.

[0023] According to the photodetector element, the external quantum efficiency of the photodetector element at a wavelength of at least a part of the near-infrared wavelength region of 780nm to 1200nm is greater than 15%, and the visible light transmittance of the photodetector element in the stacking direction in the area including the sub-sensor area is less than 50%.

[0024] According to the photodetector element, wherein, at t TCE Assume the thickness of the metal wiring and t OPD When the film thickness of the sub-sensor region is set to TCE is greater than 30nm and less than 200nm, (t OPD -t TCE ) is greater than 50nm and less than 500nm.

[0025] According to the photodetector element, wherein W TCE Set the line width of the metal wiring of the metal grid transparent electrode and set G TCE When W is set as the gap between the adjacent metal wirings extending in the same direction, TCE is 0.25 μm or more and 5.0 μm or less, G TCE is less than 45 μm, and (G TCE / W TCE ) is greater than 1.0.

[0026] According to the photodetector element, wherein A TCE When the aperture ratio of the conductive pattern is set to (G TCE ·A TCE ) is greater than or equal to 0.25 μm·% and less than or equal to 45 μm·%.

[0027] According to the photodetector element, wherein the aperture ratio A of the conductive pattern TCE It is 25% or more and less than 100%.

[0028] According to the photodetector element, wherein the photoelectric conversion layer is an organic photoelectric conversion layer.

[0029] According to the photodetector element, wherein, in the E g opt When the optical band gap is set, the organic photoelectric conversion layer has a bulk heterojunction structure, and the bulk heterojunction structure has at least E g opt Organic donor materials with a voltage below 1.65 eV and E g opt It is an organic acceptor material with a V below 1.65 eV.

[0030] According to the photodetector element, the organic acceptor material is at least one material 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.

[0031] According to the photodetector element, the organic donor material is at least one material selected from the group consisting of PTB7-Th (alias: 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.

[0032] According to the photodetector element, wherein the metal wiring contains a metal and an oxide of the metal.

[0033] According to the photodetector element, the conductive pattern includes a mesh pattern.

[0034] In addition, the present invention is a photodetector array in which two or more pixels including the photodetector elements are arranged.

[0035] According to the photodetector array, the photodetector array includes a wiring portion having a second conductive pattern provided on the transparent substrate and electrically connected to the conductive pattern, wherein the wiring portion is provided for each pixel, and when A wire When the aperture ratio of the second conductive pattern is -10%≤(A wire -A TCE )≤10%.

[0036] According to the photodetector array, it has a collector having a third conductive pattern provided on the transparent substrate and electrically connected to the second conductive pattern, pad When the area ratio of the third conductive pattern per unit area is Γ pad It is 50% or more and less than 100%.

[0037] According to the photodetector array, it includes a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern.

[0038] According to the photodetector array, wherein A dummy When the aperture ratio of the dummy pattern is -10%≤(A dummy -A TCE )≤10%.

[0039] According to the photodetector array, it comprises: a dummy sub-pixel array, which comprises a plurality of dummy sub-pixels, and the dummy sub-pixels include an insulating layer arranged on the metal grid transparent electrode; and the photoelectric conversion layer arranged on the insulating layer; and a sub-pixel array, which comprises a plurality of the sub-pixels, and the dummy sub-pixel array and the sub-pixel array have the same pattern structure when projected from the upper surface.

[0040] According to the photodetector array, wherein the pixel size of the photodetector array is 1 mm 2 Above and 25mm 2 the following.

[0041] According to the photodetector array, wherein a pixel density of the photodetector array is greater than or equal to 2 ppi and less than or equal to 15 ppi.

[0042] According to the photodetector array, 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.

[0043] In addition, a non-touch user interface device is provided, which has the photodetector array for being configured on the screen of a display or a display body. The non-touch user interface device uses the photodetector elements of the photodetector array to convert the light input signal irradiated to the photodetector array into an electrical output signal, thereby detecting the position irradiated with the light input signal. The non-touch user interface device is configured to be able to perform input operations on the screen of the display or the display body through the position detection.

[0044] According to the non-touch user interface device, the optical input signal includes light having a wavelength of at least a part of a near-infrared wavelength region of 780 nm to 1200 nm.

[0045] According to the non-touch user interface device, the optical input signal is frequency modulated, and the modulation frequency is greater than or equal to 0.5 kHz and less than or equal to 20 kHz.

[0046] According to the non-touch user interface device, wherein the optical input signal is an optical signal emitted from a laser pointer.

[0047] According to the non-touch user interface device, wherein the optical input signal is reflected light from an indication component.

[0048] According to the non-touch user interface device, the optical input signal is reflected light from the pointing member generated by bringing the pointing member into contact with a planar projection beam formed in space.

[0049] Effects of the Invention

[0050] According to the present invention, it is possible to provide a photodetector element having high transparency and high light detectability and a touchless user interface device using the photodetector element. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 1 is a cross-sectional view and a projection view projected from above of an organic photodetector element according to one embodiment.

[0052] Figure 2 is an enlarged top view of a metal grid transparent electrode according to one embodiment.

[0053] Figure 3 This is a modified example of the sub-sensor area of ​​one embodiment.

[0054] Figure 4 is the G under line width difference TCE -External quantum efficiency (EQE, λ: 850nm, IP: 1.05mW / cm 2 , V:-2V) graph.

[0055] Figure 5 is the line width difference (G TCE / W TCE )-EQE (λ: 850nm, IP: 1.05mW / cm 2 , V:-2V) graph.

[0056] Figure 6 is the line width difference (G TCE ·A TCE )-EQE (λ: 850nm, IP: 1.05mW / cm 2 , V:-2V) graph.

[0057] Figure 7 is a schematic diagram of an organic photodetector array according to an embodiment and a partial enlarged view of a region AR1.

[0058] Figure 81 is a cross-sectional view and a projection view from above of a dummy pattern portion of an organic photodetector array according to one embodiment.

[0059] Fig. 9 is a schematic diagram of a touchless user interface device according to one embodiment.

[0060] Fig.10 is a functional block diagram of a touchless user interface device according to one embodiment.

[0061] Fig.11 This is a graph comparing the light transmission spectrum of Example A1 and the optical model.

[0062] Fig.12 This is a graph comparing the light transmission spectrum and the optical model of Comparative Example A1.

[0063] Fig.13 This is an optical microscope image of the organic photodetector element of Example B1.

[0064] Fig.14 is the dark current density (J) of Example B1 dark )-voltage (V) characteristics and photocurrent density (J photo )-V characteristics diagram.

[0065] Fig.15 This is a graph of wavelength (λ)-EQE (V: -2 V) of Example B1.

[0066] Fig.16 is the light intensity (IP) of Example B1-J photo of charts.

[0067] Fig.17 This is a graph comparing the simulation and actual measurement of EQE (V: -2 V) of Example B1.

[0068] Fig.18 is a histogram of dark current density and photocurrent density of the organic photodetector array of Example D.

[0069] Fig.19 This is a photograph of a verification machine using the non-touch user interface device of Example D operating a map operation application on a display.

[0070] Fig. 20 This is a photograph of a verification machine using the non-touch user interface device of Example D performing button operations on a display.

[0071] Fig.21 Schematic top view and cross-sectional view of an organic photodetector array according to one embodiment. DETAILED DESCRIPTION

[0072] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") is described in detail, but the present invention is not limited thereto and can be variously modified within the scope of the main purpose thereof. The upper limit value and the lower limit value within each numerical range of the present embodiment can be arbitrarily combined to form an arbitrary numerical range. In addition, in the accompanying drawings, the same reference numeral is marked on the same element, and repeated description is omitted. In addition, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the accompanying drawings unless otherwise specified. Furthermore, the dimensional ratios of the accompanying drawings are not limited to the ratios shown in the drawings.

[0073] [1. Organic photodetector element]

[0074] Figure 1 A cross-sectional view ( Figure 1 (A)) and a projection diagram of the OPD element 10 projected from the upper surface ( Figure 1 (B)). Figure 1 In (A), incident light traveling from the bottom of the paper to the top of the paper passes through the metal grid transparent electrode 20, generating electrons and positive holes in the organic photoelectric conversion layer 44. As a result, a photoelectromotive force is generated between the metal grid transparent electrode 20 and the transparent electrode 60, and a current flows, so that the OPD element 10 is configured to detect incident light.

[0075] 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 is arranged opposite to the metal grid transparent electrode 20 and functions as an anode (an example of a "second electrode"). By setting such a structure, even if the element area (so-called pixel size) of the OPD element 10 is increased, the visible light transmittance is not impaired. In addition, the OPD element 10 includes an electron transport layer 42, a hole transport layer 46, an organic photoelectric conversion layer 44, and an insulating layer 80 that are arranged between the metal grid transparent electrode 20 and the transparent electrode 60. The electron transport layer 42 is arranged on the metal grid transparent electrode 20, the organic photoelectric conversion layer 44 and the insulating layer 80 are arranged on the electron transport layer 42, and the hole transport layer 46 is arranged on the organic photoelectric conversion layer 44 and on the insulating layer 80. In other words, the insulating layer 80 is arranged between the electron transport layer 42 and the hole transport layer 46 to separate the sub-pixels 44S constituting the organic photoelectric conversion layer 44 from each other.

[0076] The metal grid transparent electrode 20 is an electrode for transmitting incident light and detecting a photocurrent generated in the organic photoelectric conversion layer 44 based on the transmitted incident light. The metal grid transparent electrode 20 of this embodiment has a transparent substrate 22 and an electrode portion formed by a conductive pattern 24P, and the conductive pattern 24P is composed of a metal wiring 24 provided on the transparent substrate 22. The metal wiring 24 may also include a metal component that bears conductivity and an oxide of the metal component. An example of the structure of the metal grid transparent electrode 20 is described in detail in the item [1.2 Metal grid transparent electrode 20: Metal grid TCE].

[0077] In addition, the metal wiring 24 provided on the transparent substrate 22 in this specification includes not only a structure consisting of the metal wiring 24 provided on the transparent substrate 22 in contact with the surface of the transparent substrate 22, but also a structure consisting of the metal wiring 24 provided on the transparent substrate 22 without contacting the surface of the transparent substrate 22 via other layers provided between the transparent substrate 22 and the metal wiring 24. For example, a transparent conductive inorganic compound layer may be provided between the transparent substrate 22 and the metal wiring 24. Similarly, when another object is provided or formed on a certain object, the case where the certain object and the other object are not in contact is included.

[0078] The organic photoelectric conversion layer 44 generates photocurrent based on incident light. The organic photoelectric conversion layer 44 of this embodiment can be provided between the electron transport layer 42 and the hole transport layer 46 provided on the metal grid transparent electrode 20 so as to cover the metal grid transparent electrode 20 .

[0079] In the items [1.3 Electron transport layer 42 (ETL)], [1.4 Organic photoactive layer 44 (Organic photoactive layer)] and [1.5 Hole transport layer 46 (HTL)], examples of the structures of the electron transport layer 42, the organic photoactive layer 44 and the hole transport layer 46 are described in detail, respectively.

[0080] 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 of this embodiment is provided on the organic photoelectric conversion layer 44 or the hole transport layer 46. An example of the structure of the transparent electrode 60 is described in detail in the item [1.6 Transparent Electrode 60 (Anode)].

[0081] The organic photoelectric conversion layers 44 of the OPD element 10 (single pixel) of this embodiment are arranged in an island shape with intervals between each other. In this specification, the plurality of organic photoelectric conversion layers 44 arranged with intervals between each other are sometimes referred to as sub-pixels 44S. Therefore, the OPD element 10 (pixel) of this embodiment has a plurality of sub-pixels 44S. The OPD element 10 has, for example, 14 sub-pixels 44S arranged two-dimensionally in the longitudinal direction and 14 sub-pixels 44S in the lateral direction, totaling 196 sub-pixels 44S ( Figure 7 ). Figure 1 The projection diagram of (B) shows four sub-pixels 44S therein. As shown in the figure, each sub-pixel 44S is arranged to be spaced apart from a sub-pixel 44S adjacent in the vertical direction of the paper by a distance greater than the size of each sub-pixel 44S in the vertical direction of the paper when viewed from above, and to be spaced apart from a sub-pixel 44S adjacent in the horizontal direction of the paper by a distance greater than the size of each sub-pixel 44S in the horizontal direction of the paper. The sub-pixels 44S are each configured to generate a photocurrent based on incident light. Therefore, the OPD element 10 is configured to detect incident light by causing one or more sub-pixels 44S in the OPD element 10 to generate a photocurrent based on incident light.

[0082] like Figure 1 (A) and Figure 1 As shown in (B), the sub-pixel 44S as the organic photoelectric conversion layer 44 has: a sub-sensor region 44SS, which is disposed on the electron transport layer 42 in contact with or close to the electron transport layer 42; an alignment region 44SA, which surrounds the sub-sensor region 44SS in the projection view, and is disposed on the electron transport layer 42 with a gap between the insulating layer 80 when viewed from the side (in the cross-sectional view); and a connecting portion 44SC, which extends substantially perpendicularly to the surface of the transparent substrate 22 to connect the sub-sensor region 44SS and the alignment region 44SA. As shown in the figure, the sub-pixel 44S is formed in a substantially polygonal shape (e.g., a square or a rectangle) in the projection view, and when viewed from the side (in the cross-sectional view), the alignment regions 44SA corresponding to the two end portions are spaced apart from the electron transport layer 42, and the sub-sensor region 44SS corresponding to the central portion connecting the two end portions is formed in a substantially U-shape in contact with or close to the electron transport layer 42. In this specification, the area of ​​a single sub-sensor region 44SS in the projection diagram is sometimes referred to as S sub-sensor .

[0083] Figure 2 2 is an enlarged plan view of the metal grid transparent electrode 20. The metal grid transparent electrode 20 of this embodiment includes a mesh pattern (an example of the "conductive pattern 24P", Figure 3(A)), the grid pattern is formed by a plurality of metal wirings 24 extending in straight lines and crossing at right angles to form a grid pattern. When the conductive pattern 24P composed of a plurality of metal wirings 24 is composed of a periodic shape, in this specification, the area of ​​the repetitive unit (unit) in the projection diagram ("repetitive unit area") is sometimes referred to as S TCE-unit The mesh pattern of the metal grid transparent electrode 20 of this embodiment is composed of rectangles arranged repeatedly and periodically. Therefore, the center line ( Figure 2 The area of ​​the rectangle enclosed by the dotted line in the figure or the area of ​​the rectangular shape is equivalent to the repeating unit area S TCE-unit .

[0084] like Figure 1 As shown in (B), the organic photoelectric conversion layer 44 and the metal wiring 24 of the OPD element 10 of this embodiment are arranged so that, in the projection diagram when projected from the upper surface, the area where the sub-sensor area 44SS is provided overlaps at least a part with the area where the metal wiring 24 is provided. In other words, it is arranged so that, in the projection diagram when projected from the upper surface, at least one metal wiring 24 passes through the sub-sensor area 44SS of the organic photoelectric conversion layer 44, preferably passes through the sub-sensor area 44SS of the organic photoelectric conversion layer 44 while crossing two different sides of the sub-sensor area 44SS of the organic photoelectric conversion layer 44.

[0085] With such a structure, electrons generated in the organic photoelectric conversion layer 44 can be transported to the nearby metal wiring 24 via the electron transport layer 42. Therefore, compared with a structure in which the organic photoelectric conversion layer 44 is provided only in the opening of the conductive pattern 24P in the projection diagram, the external quantum efficiency (light detection) can be improved.

[0086] In addition, at least one sub-sensor region 44SS (organic photoelectric conversion layer 44) is provided in the OPD element 10 (pixel). With such a structure, the area ratio of the region with high visible light transmittance (region other than the sub-pixel 44S or the sub-sensor region 44SS) can be relatively increased. Therefore, the visible light transmittance of the organic photodetector element and the organic photodetector array can be improved.

[0087] Here, as shown in this embodiment, a plurality of (for example, preferably 10 or more, more preferably 50 or more) sub-pixels 44S (organic photoelectric conversion layers 44) may be provided at intervals within the OPD element 10. With such a structure, the detectability of incident light can be improved.

[0088] For example, the OPD element 10 may include: a first sub-pixel 44S, in which at least one metal wiring 24 passes through the sub-sensor region 44SS (organic photoelectric conversion layer 44); and a second sub-pixel 44S, which is spaced apart from the first sub-pixel 44S and in which at least one metal wiring 24 passes through the sub-sensor region 44SS (organic photoelectric conversion layer 44). Here, the metal wiring 24 passing through the first sub-pixel 44S and the metal wiring 24 passing through the second sub-pixel 44S may be the same.

[0089] As described above, the OPD element of this embodiment has an organic photoelectric conversion layer 44. However, the photodetector of the present invention may have an inorganic photoelectric conversion layer, for example. That is, for the photoelectric conversion layer, an organic photoelectric conversion layer, an inorganic photoelectric conversion layer formed by quantum dots or inorganic semiconductors can be used, and an organic photoelectric conversion layer can be preferably used. Similarly, the electron transport layer 42 and the hole transport layer 46 may be composed of organic substances or inorganic substances.

[0090] Furthermore, in the projection diagram of the OPD element 10 ( Figure 1 In (B), S corresponding to the area of ​​the sub-sensor region 44SS sub-sensor and S corresponding to the repeating unit area of ​​the conductive pattern 24P TCE-unit Preferably S sub-sensor / S TCE-unit ≥1.S sub-sensor / S TCE-unit It is preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. Figure 1 In the embodiment shown in (B), S sub-sensor / S TCE-unit 5 or more (S sub-sensor / S TCE-unit ≥5).

[0091] By making S sub-sensor / S TCE-unit 1 or more, so that in the projection diagram, the sub-sensor area 44SS can be provided on at least one of the metal wirings 24 extending in the same direction in the conductive pattern 24P and facing the direction substantially perpendicular to the extending direction in at least any one direction. This relationship also holds true when the relative positions of the conductive pattern 24P and the sub-sensor area 44SS are offset during the lamination process. Therefore, by making S sub-sensor / S TCE-unit When S is greater than 1, 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, making it easier to collect charges, thereby improving the external quantum efficiency. sub-sensor / S TCE-unitAs the number of metal wirings 24 overlapping the sub-sensor region 44SS increases, the number of metal wirings 24 tends to increase, and the external quantum efficiency tends to increase due to the improvement of the charge collection efficiency ηcc. sub-sensor / S TCE-unit The upper limit of is not particularly limited, and an example thereof is 100. sub-sensor / S TCE-unit The upper limit value of can be more preferably 85 or less, further preferably 65 or less, further preferably 50 or less, and particularly preferably 40 or less. sub-sensor / S TCE-uni Reducing t can reduce the size of the sub-pixel 44S, thereby reducing the visibility of the organic photodetector element, which is preferable.

[0092] In addition, it is preferred that S sub-sensor / S TCE-unit In addition, in the projection diagram, a portion of the sub-sensor region 44SS overlaps with at least two or more metal wirings 24 extending in the same direction. Figure 1 As shown in (B), the sub-sensor region 44SS may overlap with two metal wirings 24 extending in the vertical direction of the paper and overlap with three metal wirings 24 extending in the horizontal direction of the paper.

[0093] With such a structure, even if sub sensor region 44SS is offset in a direction perpendicular to the extending direction of metal wiring 24 , sub sensor region 44SS is overlapped with at least one metal wiring 24 , so that charge collection can be performed preferably.

[0094] As described above, in the organic photodetector element of this embodiment, the metal grid transparent electrode 20 is used as the cathode, the transparent electrode 60 is used as the anode, and at least the organic photoelectric conversion layer 44 is provided between the cathode and the anode.

[0095] As for the structures of the organic photoelectric conversion layer 44 , the anode, the cathode, and the like, conventionally known materials and structures generally used in organic photodetector elements can be applied.

[0096] For example, as the element configuration of the organic photodetector element, the following configurations can be applied to the present invention.

[0097] (A) Cathode / Organic Photoelectric Conversion Layer 44 / Anode

[0098] (B) cathode / electron transport layer 42 / organic photoelectric conversion layer 44 / anode

[0099] (C) cathode / organic photoelectric conversion layer 44 / hole transport layer 46 / anode

[0100] (D) cathode / electron transport layer 42 / organic photoelectric conversion layer 44 / hole transport layer 46 / anode

[0101] It should be noted that the symbol " / " shown in the above (A) to (D) indicates that the layers sandwiching the symbol " / " are stacked adjacently. This also applies to the following description. In addition, the organic photodetector element may be configured to have two or more organic photoelectric conversion layers 44.

[0102] Furthermore, the organic photodetector element of this embodiment can be a standard stack (cis element) in which light is incident from the anode, or a reverse stack (trans element) in which light is incident from the cathode. In addition, a metal grid transparent electrode such as the metal grid transparent electrode 20 can be used as the anode, and a transparent electrode such as the transparent electrode 60 can be used as the cathode.

[0103] Since the cathode and anode of the organic photodetector element of this embodiment are transparent electrodes, the optical input signal can be incident from the anode side or the cathode side. A transverse element in which light is incident from the cathode side of a metal grid transparent electrode is preferred.

[0104] The lower limit of the external quantum efficiency of the OPD element 10 at at least a portion of the wavelengths in the near-infrared wavelength region of 780 nm to 1200 nm is preferably 15% or more, more preferably 20% or more, further preferably 25% or more, and particularly preferably 30% or more. The upper limit of the external quantum efficiency is not particularly limited, and can be set, for example, preferably 100% or less, further preferably 90% or less, and more preferably 80% or less.

[0105] By setting the lower limit value of the external quantum efficiency at at least a part of the wavelength in the near-infrared wavelength region of 780 nm to 1200 nm to be 15% or more, the OPD element 10 can exhibit good light detection performance in the near-infrared wavelength region.

[0106] Here, the external quantum efficiency and the visible light transmittance of the organic photodetector element in the sub-pixel portion are in a trade-off relationship. Therefore, by making the external quantum efficiency below the above-mentioned upper limit value, there is a tendency to increase the visible light transmittance of the organic photodetector element in the sub-pixel portion and reduce the visual recognition of the sub-pixel portion.

[0107] Since near-infrared light is invisible to the human eye, even if it is irradiated to a display such as a display as an optical input signal, the visual recognizability of the display (the visual recognizability of the image displayed by the display) will not be suppressed. In addition, when the reflected light from an indicating component such as a finger is used as an optical input signal for a touchless user interface, it becomes a method of irradiating a person with light from a light source. In this case, since near-infrared light is invisible to the human eye, a person can view the image displayed by the display without paying attention to the reflected light from the indicating component.

[0108] Furthermore, as disclosed in MJ Mendenhall, ASNunez, and RK Martin, "Human skin detection in the visible and near infrared," Appl. Opt. 54 (35), 10559-10570 (2015), in the near-infrared wavelength region, human skin has a high reflectivity in the wavelength region of 780 nm to 1200 nm. In particular, the reflectivity is high in the wavelength region of 780 nm to 950 nm, and there are many commercial LEDs that can be used as light sources for optical input signals. Therefore, when using near-infrared light reflected from an indicating member such as a finger as an optical input signal for a touchless user interface, the organic photodetector element is preferably capable of efficiently detecting light of at least a portion of the wavelengths in the near-infrared wavelength region of 780 nm to 1200 nm.

[0109] The visible light transmittance in the stacking direction of the organic photodetector elements in the region including the sub-sensor region 44SS, i.e., Figure 1 In (A), the visible light transmittance that travels from the bottom to the top of the paper and passes through the metal grid transparent electrode 20, the sub-sensor area 44SS of the organic photoelectric conversion layer 44, and the sub-pixel 44S of the transparent electrode 60 is preferably 50% or less, more preferably 40% or less, further preferably 35% or less, further more preferably 30% or less, further preferably 25% or less, and particularly preferably 20% or less.

[0110] The lower limit of the visible light transmittance is not particularly limited, and can be set, for example, preferably more than 0%, more preferably 5% or more, and more preferably 10% or more. In order to obtain high external quantum efficiency for at least a portion of the near-infrared wavelength region of 780 nm to 1200 nm, the organic photodetector element of this embodiment preferably selects an organic photoelectric conversion layer 44 having a high extinction coefficient k (absorption coefficient α) in the wavelength region and / or increases the film thickness t of the organic photoelectric conversion layer 44. OPD On the other hand, such an organic photoelectric conversion layer 44 has a high light absorption rate also in the long wavelength region (550 nm or longer) of visible light.

[0111] Therefore, by setting the visible light transmittance to 50% or less, a high external quantum efficiency can be obtained in the above-mentioned near-infrared wavelength region. In addition, by setting the visible light transmittance to a value greater than the lower limit, the visibility of the sub-pixel 44S tends to be reduced.

[0112] The dark current density J of the organic photodetector element of this embodiment at an applied voltage of -2 V is dark Preferably 10 -4 mA / cm 2 Less than, more preferably 10 -5 mA / cm 2 Below, particularly preferably 5×10 -6 mA / cm 2 By making the dark current density equal to or less than the upper limit value, there is a tendency that an organic photodetector element having high detectivity can be obtained.

[0113] [1.1 Insulation layer 80: ECL, Edge Cover Layer]

[0114] The organic photodetector element of this embodiment includes an insulating layer 80 ( Figure 1 In this embodiment, the insulating layer 80 is stacked on the electron transport layer 42, and the electron transport layer is formed on the metal grid transparent electrode 20 in a manner covering the metal grid transparent electrode 20. The insulating layer 80 is formed with a plurality of openings OP (portions in which the insulating layer 80 is provided with openings) arranged at intervals. The electron transport layer 42 is exposed upward through the openings OP.

[0115] The sub-pixel 44S is arranged so as to cover the opening OP in the projection from the upper surface in the stacking direction, and the portion of the sub-pixel 44S overlapping with the opening OP corresponds to the sub-sensor region 44SS, and the portion surrounding the opening OP corresponds to the alignment region 44SA. The alignment region 44SA is shown in the cross-sectional view ( Figure 1 In (A)), the insulating layer 80 is provided. By providing the insulating layer 80, a short circuit between the cathode and the anode in a region other than the sub-pixel 44S can be suppressed.

[0116] The insulating layer 80 may be made of a conventionally known material and structure commonly used in organic photodetector elements and semiconductor elements. The insulating layer 80 is not particularly limited and may be made of, for example, silicon oxide (SiO X(0＜X≤2) ), silicon nitride (SiN X(0＜X≤4 / 3) ), silicon oxide nitride (SiO X N Y ), aluminum oxide (AlO X(0＜X≤3 / 2)), inorganic compound layers such as aluminum nitride (AlN); resin layers of phenolic resin, thermosetting epoxy resin, thermosetting polyimide, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, diallyl phthalate resin, silicone resin and other thermosetting resins; urethane acrylate, acrylic resin acrylate, epoxy acrylate, silicone acrylate, UV curing epoxy resin and other UV curing resins, commercially available coating agents, etc. The insulating layer 80 can be composed of one material or a stack of two or more materials.

[0117] As a method for forming the insulating layer 80 having the opening OP, a solid film of the material to be the insulating layer 80 can be first formed by dry film formation or wet film formation on the entire surface of the element, and then the opening OP can be formed on the insulating layer 80 using a known patterning method such as photolithography, nanoimprinting, sublimation, laser ablation, etc. In addition, the insulating layer 80 (especially the above-mentioned resin layer) having the opening OP can be formed by patterning printing using a known printing method such as gravure printing, gravure offset printing, relief printing, flexographic printing, inkjet printing, screen printing, etc. The formed insulating layer 80 can be cured by ultraviolet rays or heat as needed. In addition, the insulating layer 80 can be fixed by baking.

[0118] As a dry film-forming method for a solid film of an inorganic compound layer used as the insulating layer 80, vapor phase film-forming methods such as PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition) can be cited. From the purpose of forming a dense inorganic compound layer with few pinholes, it is preferred to form an inorganic compound layer by sputtering, PECVD, or ALD (Atomic Layer Deposition). The film thickness of the inorganic compound layer is preferably greater than 10nm and less than 2000nm, more preferably greater than 30nm and less than 1000nm, and further preferably greater than 50nm and less than 500nm. By making the film thickness of the inorganic compound layer greater than 10nm, the insulation is excellent. By making the film thickness of the inorganic compound layer less than 2000nm, the visible light transmittance is excellent. In addition, the generation of cracks caused by buckling can be suppressed, and the internal stress can be prevented from increasing during film formation, thereby preventing the generation of defects.

[0119] In addition, as a wet film-forming method of a solid film of the resin layer used as the insulating layer 80, a known coating method or a casting method such as slit coating or spin coating can be used. The film 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 further preferably 800 nm or more and 2000 nm or less. When the film thickness of the resin layer is 100 nm or more, excellent insulation is achieved. When the film thickness of the resin layer is 5000 nm or less, excellent visible light transmittance is achieved.

[0120] The insulating layer 80 having the opening OP is preferably formed by forming a solid film of a photocurable epoxy resin SU-8 (trade name) on the entire surface of the element, and performing soft baking, pattern exposure, and development.

[0121] In the present embodiment, the shapes of the sub-sensor region 44SS and the sub-pixel 44S are rectangular or square in a projection view formed by observing the OPD element 10 from above. However, the shapes of the sub-sensor region 44SS and the sub-pixel 44S are not particularly limited, and may be circular, square, rectangular, polygonal, substantially circular, substantially square, substantially rectangular, substantially polygonal, etc. in a projection view.

[0122] Figure 3 (A), (B), (C) and (D) show square, circular, rectangular and circular sub-sensor areas 44SS, respectively. For example, by providing a circular opening on the insulating layer 80, a circular sub-sensor area 44SS can be formed in the projection view, and a square sub-pixel 44S including the circular sub-sensor area 44SS can be formed. In addition, when there are multiple sub-pixels 44S, different shapes can be combined for each sub-pixel 44S. The shape of the sub-pixel 44S is preferably at least one selected from the group consisting of a square, a rectangle, a substantially square, and a substantially rectangular. Among them, a substantially square refers to a shape including four sides that are at right angles to adjacent sides and have equal lengths, including, for example, a shape having four sides that are at right angles to adjacent sides and have equal lengths, and a corner portion formed as an arc to connect two adjacent sides. A substantially rectangular refers to a shape including four sides that are at right angles to adjacent sides, including, for example, a shape having four sides that are at right angles to adjacent sides, and a corner portion formed as an arc to connect two adjacent sides.

[0123] [Sub-pixel 44S]

[0124] Here, S subOPD When the area of ​​a sub-pixel 44S is set, S subOPD Preferably 25 μm 2 Above and 10000μm 2 Below, more preferably 100 μm 2Above and 6400μm 2 Below, more preferably 225 μm 2 Above and 4900μm 2 Below, more preferably 400 μm 2 Above and 3600μm 2 Below, particularly preferably 1600 to 3000 μm 2 the following.

[0125] S subOPD 25μm 2 When it is above , the light detection current becomes larger, so it is preferable. subOPD 10000μm 2 When φ is less than φ, the visibility of the sub-pixel 44S having a low visible light transmittance to human eyes can be reduced, which is preferable.

[0126] In addition, the area of ​​one sub-pixel 44S is preferably at least one-tenth of the area of ​​a pixel of the OPD element 10 .

[0127] As described above, the OPD element 10 of this embodiment includes a plurality of sub-pixels 44S formed into island shapes at intervals. Figure 1 As shown in (B), each sub-pixel 44S is disposed on the electron transport layer 42 integrally formed in a manner to be electrically at the same potential, and is disposed under the hole transport layer 46 integrally formed in a manner to be electrically at the same potential, so that the plurality of sub-pixels 44S constituting the pixel are electrically joined or connected. In other words, a plurality of sub-pixels 44S electrically joined or connected constitute one pixel.

[0128] Here, the plurality of sub-pixels 44S may be arranged one-dimensionally or two-dimensionally as shown in the present embodiment in the OPD element 10. In addition, the plurality of sub-pixels 44S may be arranged randomly or in any regular arrangement pattern, or in an arrangement pattern combining multiple of these.

[0129] The OPD element 10 of this embodiment has a sub-pixel array, which is composed of a pattern in which a plurality of sub-pixels 44S are arranged at intervals. Figure 1 As shown in (B), the pattern structure is formed by arranging a plurality of sub-pixels 44S in two dimensions at equal intervals along two orthogonal coordinate axes in parallel planes of the sub-pixel array.

[0130] The following describes the significance of configuring a single pixel by electrically joining or connecting a plurality of sub-pixels 44S disposed at intervals from each other.

[0131] Generally, the current I(λ) detected by an organic photodetector element is expressed as follows.

[0132]

[0133] Here, EQE(λ) (%) is the external quantum efficiency of the organic photodetector element. P (λ)(mW / cm 2 ) is the light intensity irradiated to the organic photodetector element, S (cm 2 ) is the effective sensor area of ​​the organic photodetector element per unit pixel, λ is the wavelength of the irradiated light, q is the elementary quantity, h is the Planck constant, and c is the speed of light. That is, the detection current I is proportional to the effective sensor area S within the unit pixel.

[0134] On the other hand, the effective sensor area of ​​the organic photodetector element disclosed in Non-Patent Document 1 is as small as 100 μm 2 Therefore, the detection current I is also weak.

[0135] Furthermore, natural light, indoor light, and light emitted from displays such as displays, which are external disturbances, contain a lot of visible light, and this visible light becomes noise.

[0136] Furthermore, when the optical input signal propagates in space, the light intensity increases at a rate of 1 / d relative to the propagation distance d. 2 attenuation.

[0137] For the above reasons, it is difficult to use the photodetector array composed of organic photodetector elements disclosed in Non-Patent Document 1 for a touchless user interface from the viewpoint of the SN ratio in an actual use environment.

[0138] Therefore, the inventors of the present application focused on the following aspects: when used for a non-touch user interface, a high resolution (e.g., 164ppi (Pixel per inch)) like the photodetector array of non-patent document 1 is not required, for example, it is sufficient to set the pixel spacing in two-dimensional directions (e.g., orthogonal X-axis and Y-axis directions) to 4mm to 6mm (approximately 4 to 7ppi).

[0139] Furthermore, the inventors of the present application have conceived the following structure: in a single pixel, a photoelectric conversion layer of a sub-pixel smaller than the pixel is provided by patterning or the like. The photodetector element of such a structure has an island-shaped sub-pixel including an organic or inorganic photoelectric conversion layer with a relatively low visible light transmittance in a single pixel, so that the area of ​​the opening portion with a high visible light transmittance (the so-called region where the photoelectric conversion layer is not formed) can be relatively increased. Therefore, the visible light transmittance of the entire photodetector element can be improved.

[0140] The number of sub-pixels provided in a single pixel may be 1 or more. For example, by providing a plurality of sub-pixels including an organic photoelectric conversion layer at intervals within a single pixel, the area ratio of the opening portion having a high visible light transmittance can be relatively increased. Therefore, the visible light transmittance of the organic photodetector element and the organic photodetector array can be improved.

[0141] Here, a pixel is equivalent to a unit of spatial resolution of a photodetector array. Since one or more photoelectric conversion layers are provided in a single pixel, each photoelectric conversion layer can be provided for each sub-pixel smaller than one pixel. As described above, each photoelectric conversion layer can be formed, for example, by patterning.

[0142] Furthermore, the inventors of the present application have conceived a configuration in which, for a sub-sensor region within a sub-pixel, a region where the sub-sensor region is provided and a region where the metal grid transparent electrode is provided with metal wiring overlap at least in part when projected from the upper surface. Here, the sub-sensor region refers to a region in the photoelectric conversion layer formed in an island shape that functions as a sensor, and more specifically, refers to a region of a portion that is close to and opposite to the electrode.

[0143] With this structure, electrons generated in the photoelectric conversion layer above the opening of the metal grid transparent electrode can be transported to nearby metal wiring via the electron transport layer and collected, thereby improving the external quantum efficiency (light detection) of the photodetector element using the metal grid transparent electrode.

[0144] Furthermore, the area of ​​the sub-sensor region in the sub-pixel can be set to be equal to or greater than the area of ​​the repeating unit of the conductive pattern of the metal grid transparent electrode. Here, the area of ​​the sub-sensor region refers to the area of ​​the sub-sensor region when viewed from the top surface (planar view).

[0145] By setting such a configuration, even if the relative positions of the metal grid transparent electrode and the sub-pixel including the photoelectric conversion layer are offset during manufacturing (lamination process), it is possible to set the sub-sensor region in such a manner that at least a portion of the sub-sensor region overlaps the metal wiring. Therefore, due to the above reasons, the external quantum efficiency (light detectability) of the photodetector element using the metal grid transparent electrode can be more reliably improved.

[0146] Furthermore, in order to improve the SN ratio, the inventors have designed an OPD element 10 in which, for example, the pixel size is set to be less than 4 mm × 4 mm and a plurality of tiny island-shaped organic photoelectric conversion layers 44 are arranged in the pixel as sub-pixels 44S (array). This configuration can increase the area ratio of the sub-pixels 44S other than the sub-pixels 44S with low visible light transmittance, thereby enjoying the improvement of the visible light transmittance of the entire pixel and increasing the total effective sensor area in the pixel. In the case of the same pixel size and the same total effective sensor area, the method of arranging more sub-pixels 44S with a smaller area can reduce the visual recognition of the sub-pixels 44S, compared with arranging fewer sub-pixels 44S with a larger area, and is preferred.

[0147] Here, Γ subOPD When the area occupancy rate of the sub-pixel 44S in the repeated pattern unit of the sub-pixel array (for example, if a sub-pixel array of area Y is provided in each area X, the area occupancy rate is equivalent to "100×(Y / X)(%)".), Γ subOPD It is preferably 3% to 25%, more preferably 4% to 20%, further preferably 5% to 15%, further more preferably 5.5% to 12%, and particularly preferably 6% to 10%. subOPD When it is 3% or more, the total effective sensor area of ​​the sub-pixel array can be increased, which is preferred. subOPD When it is 25% or less, the total occupied area of ​​the sub-pixels 44S having a low visible light transmittance can be reduced, so the visible light transmittance of the entire organic photodetector element is improved, which is preferable.

[0148] [1.2 Metal grid transparent electrode 20: Metal grid TCE]

[0149] like Figure 1 As shown in FIG. 2A , the metal grid transparent electrode 20 of the present embodiment includes a transparent substrate 22 and an electrode portion including a conductive pattern 24P formed of metal wirings 24 provided on the transparent substrate 22 .

[0150] [1.2.1 Transparent substrate]

[0151] 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 further preferably 95% or more. Here, the visible light transmittance can be measured based on JIS K7361-1:1997.

[0152] The transparent substrate 22 may be composed of one material, or may be formed by stacking two or more materials. In addition, when the transparent substrate 22 is a multilayer body formed by stacking two or more materials, the transparent substrate 22 may be a transparent substrate formed by stacking the transparent organic substrate or transparent inorganic substrate listed as the core layer described later, or may be a transparent substrate formed by combining and stacking a transparent organic substrate and a transparent inorganic substrate. In addition, the transparent substrate 22 may be appropriately provided with a barrier layer, an intermediate layer, etc. on the core layer of a single layer or a multilayer body. As the form of such a transparent substrate 22, a core layer, a core layer / barrier layer, a core layer / barrier layer / intermediate layer, a core layer / intermediate layer / barrier layer, etc. may be listed. It is also possible to have both a barrier layer and an intermediate layer in one layer.

[0153] The material of the core layer is not particularly limited, and 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.

[0154] The intermediate layer is not particularly limited, and examples thereof include silicon compounds (e.g., (poly)siloxanes, silicon oxide, silicon nitride), aluminum compounds (e.g., aluminum oxide, etc.), magnesium compounds (e.g., magnesium fluoride), etc. The film thickness of the intermediate layer is preferably 0.01 μm or more and 100 μm or less, more preferably 0.01 μm or more and 10 μm or less, and further preferably 0.01 μm or more and 1 μm or less. By making the film thickness of the intermediate layer within the above range, in addition to further improving the above-mentioned adhesion, there is also a tendency to further improve the transparency and durability of the metal grid transparent electrode 20.

[0155] The barrier layer is a layer having high barrier properties against moisture and oxygen, and helps to suppress the degradation of the characteristics of the organic photodetector element caused by the intrusion of moisture and oxygen into the organic photodetector element. As the gas barrier property of the barrier layer, the water vapor transmission rate (25±0.5°C, relative humidity (90±2)%) measured by the method based on JIS K 7129-1992 is preferably 1×10 -7 g / (m 2 24hr)~1×10 -3 g / (m 2 ·24hr), more preferably 1×10 -7 g / (m 2 24hr)~1×10 - 4 g / (m 2 ·24hr), more preferably 1×10 -7 g / (m 2 24hr)~1×10 -5 g / (m2 When the water vapor permeability is within this range, it is possible to suppress the degradation of the characteristics such as the decrease in EQE and the increase in dark current of the organic photodetector element during long-term use. Furthermore, the oxygen permeability measured by the method based on JIS K 7126-1987 is preferably 1×10 -6 mL / m 2 24h atm~1×10 -2 mL / m 2 ·24h·atm, more preferably 1×10 -6 mL / m 2 24h atm~1×10 -3 mL / m 2 ·24h·atm, more preferably 1×10 -6 mL / m 2 24h atm~1×10 -4 mL / m 2 ·24h·atm.

[0156] The barrier layer can apply the existing well-known composition, structure and formation method generally used for organic photodetector elements. The barrier layer can be a single layer, or a stacked structure of two or more layers. In the case of a stacked structure, it can be a stacked structure of inorganic compound layers, organic compound layers or inorganic polymer layers, or a combination of inorganic compound layers, organic compound layers or inorganic polymer layers. In order to improve the fragility of the barrier layer, it is preferred to have a structure in which inorganic compound layers and organic compound layers are alternately stacked multiple times.

[0157] The inorganic compound layer of the barrier layer is not particularly limited, and 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. The film 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 further preferably 100 nm or more and 200 nm or less. By making the film thickness of the inorganic compound layer 30 nm or more, the gas barrier property is excellent. By making the film thickness of the inorganic compound layer 1000 nm or less, the transmittance of visible light is excellent.

[0158] The organic compound layer of the barrier layer is not particularly limited, and for example, thermosetting resins such as phenolic resins, UV curing resins such as urethane acrylates, acrylic resin acrylates, epoxy acrylates, silicone acrylates, and commercially available coating agents can be used. In addition, the organic compound layer can also have a structure in which particles as hygroscopic compounds are dispersed in the layer. Hygroscopic compounds can include, for example, metal oxides (such as calcium oxide), sulfates, metal halides, perchloric acids, etc. The film thickness of the organic compound layer is preferably greater than 0.5 μm and less than 100 μm, more preferably greater than 5 μm and less than 50 μm, and further preferably greater than 10 μm and less than 30 μm. By making the film thickness of the organic compound layer greater than 0.5 μm, the gas barrier property is excellent. By making the film thickness of the organic compound layer less than 100 μm, the transmittance of visible light is excellent.

[0159] The inorganic polymer layer of the barrier layer is not particularly limited. For example, silicon-containing polymers such as polysilazane, polysiloxane, and polysiloxysilazane can be used. The film thickness of the inorganic polymer layer is preferably 10 nm or more and 10 μm or less, more preferably 30 nm or more and 8 μm or less, and further preferably 50 nm or more and 5 μm or less. By making the film thickness of the inorganic polymer layer 10 nm or more, the gas barrier property is excellent. By making the film thickness of the inorganic polymer layer 10 μm or less, the transmittance of visible light is excellent.

[0160] As the barrier layer, it is particularly preferable to use the same material and structure as the thin film encapsulation layer (TFE: Thin Film Encapsulation) disclosed in Non-Patent Document 2.

[0161] [1.2.2 Electrode section]

[0162] The electrode portion is composed of a transparent electrode (hereinafter also referred to as a "metal grid transparent electrode" or "Metal grid TCE"), which has a conductive pattern 24P formed by fine metal wiring 24 on a transparent substrate 22. The metal grid transparent electrode achieves higher flexibility and lower sheet resistance through the higher ductility and higher electrical conductivity of the metal wiring. In addition, it also has the advantage of being able to arbitrarily change the visible light transmittance, sheet resistance and other characteristics by adjusting the line width, film thickness, gap of the conductive pattern, etc. of the metal wiring. In addition, although the metal wiring itself is opaque, by adjusting the line width of the metal wiring to less than 3μm, it can be made invisible to the human eye, and the transparency (transmittance) of the metal grid transparent electrode itself can be further improved.

[0163] In the electrode of the "metal grid", since a plurality of metal wirings 24 extending in different directions are provided, a plurality of areas surrounded by the metal wirings 24 are provided, with the points where the metal wirings 24 intersect as vertices. Here, each metal wiring 24 may extend in a straight line or in a curve. The area surrounded by the metal wirings 24 is called an opening, and the portion provided with the opening is sometimes referred to as an opening portion. As described later, a plurality of metal wirings 24 may be arranged periodically at a predetermined interval, but may also be arranged irregularly and randomly arranged in all or part of the area.

[0164] (Conductive pattern 24P)

[0165] The conductive pattern 24P may be a regular pattern or an irregular pattern. For example, a grid pattern formed by a plurality of metal wirings 24 extending in a straight line and crossing in a grid shape, a honeycomb pattern formed by setting metal wirings 24 in a manner that hexagonal openings are provided without gaps in the parts corresponding to the sides of each hexagon, and a line pattern formed by forming a plurality of substantially parallel metal wirings 24. In addition, the conductive pattern 24P may be a pattern formed by any combination of a grid pattern, a honeycomb pattern, and a line pattern. Furthermore, the conductive pattern 24P may be provided so that openings of polygons other than rectangles and hexagons are formed without gaps. For example, when the metal wiring 24 that specifies the opening of a polygon also specifies the opening of an adjacent polygon, a plurality of polygonal openings are formed without gaps. In addition, the conductive pattern 24P may be configured to have openings of different polygons. The grid of the grid pattern may be a square or a rectangle, or may be a rhombus, etc. The honeycomb pattern may be provided as a regular hexagon with a certain line width, but, for example, it may also be provided so that the line width of the part corresponding to the vertex is increased so that the vertex of each opening is rounded. The metal wiring 24 forming the line pattern may be a straight line or a curved line. Also, in the metal wiring 24 forming the mesh pattern or the honeycomb pattern, part or all of the metal wiring 24 may be curved lines.

[0166] Figure 3 (A) shows an embodiment in which a mesh pattern having square openings is provided as the conductive pattern 24P, a square sub-sensor region 44SS is provided as the sub-sensor region 44SS, and S corresponding to the area of ​​the sub-sensor region 44SS is sub-sensor and S corresponding to the repeating unit area of ​​the conductive pattern 24P TCE-unit With S sub-sensor / S TCE-unit ≥1. As shown in the figure, due to S sub-sensor >S TCE-unitTherefore, in the projection diagram, at least two metal wirings 24 extending in a predetermined direction (first direction) pass through the sub-sensor region 44SS, and at least two metal wirings 24 extending in a direction perpendicular to the predetermined direction (second direction) pass through the same sub-sensor region 44SS. Figure 3 As shown in (E) of FIG. 1 , even when the relative positions of the conductive pattern 24P and the sub-sensor area 44SS are offset during the stacking process, the sub-sensor area 44SS and the metal wiring 24 can still be overlapped in the projection image. Therefore, the electrons generated in the organic photoelectric conversion layer 44 can be transported to the nearest metal wiring 24 via the electron transport layer 42, so that the charges can be easily collected, thereby improving the external quantum efficiency.

[0167] Figure 3 (B) shows an embodiment in which a mesh pattern having square openings is provided as the conductive pattern 24P, a circular sub-sensor region 44SS is provided as the sub-sensor region 44SS, and a mesh pattern having square openings is provided as the conductive pattern 24P. sub-sensor / S TCE-unit ≥1 (for example, in this figure, S sub-sensor / S TCE-unit =1). Figure 3 (A) Similarly, even if the relative positions of the conductive pattern 24P and the sub-sensor region 44SS are offset during the stacking process, the sub-sensor region 44SS and the metal wiring 24 can still be overlapped in the projected view, thereby improving the external quantum efficiency.

[0168] Figure 3 (C) shows an embodiment in which a mesh pattern having rectangular (long) openings is provided as the conductive pattern 24P, and a rectangular (long) sub-sensor region 44SS is provided as the sub-sensor region 44SS. sub-sensor / S TCE-unit ≥1 relationship, Figure 3 (D) shows an embodiment in which a honeycomb pattern having hexagonal openings is provided as the conductive pattern 24P, a circular sub-sensor region 44SS is provided as the sub-sensor region 44SS, and a S sub-sensor / S TCE-unit In these implementations, the same technical effects can also be achieved.

[0169] (Line Width)

[0170] The line width W of the metal wiring 24 TCE The line width W of the metal wiring 24 when projected onto the surface of the transparent substrate 22 from the surface of the transparent substrate 22 where the conductive pattern 24P is arranged is TCE ( Figure 2). 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 .

[0171] W TCE It is preferably 0.25 μm to 5.0 μm, more preferably 0.25 μm to 4.0 μm, further preferably 0.25 μm to 3.0 μm, further preferably 0.25 μm to 2.0 μm, and particularly preferably 0.25 μm to 1.0 μm. TCE When the line width W of the metal grid transparent electrode 20 is 0.25 μm or more, the metal grid transparent electrode 20 can be made low-resistance, thereby suppressing the voltage drop caused by the detection current, and there is a tendency to increase the area of ​​the organic photodetector element. In addition, the increase in resistance caused by oxidation and corrosion of the metal wiring 24 surface can be fully suppressed. On the other hand, by reducing the line width W of the metal wiring 24 TCE The gap G of the conductive pattern 24P can be reduced while maintaining a high aperture ratio. TCE . Thus, the repeating unit area of ​​the conductive pattern 24P can be reduced, and the area of ​​the sub-sensor region 44SS can be designed to be smaller. As a result, there is a tendency to further improve the visible light transmittance of the organic photodetector element as a whole, and there is a tendency to improve the appearance at the same time. In addition, by reducing 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. Thus, even when the organic photodetector element is disposed on a display such as a display, the appearance and design of the display are not impaired.

[0172] (gap)

[0173] In this specification, the gap G of the conductive pattern 24P is TCE ( Figure 2 ) refers to the shortest (minimum) distance among the distances (intervals) between adjacent metal wirings 24 extending in the same direction and facing each other in a direction substantially perpendicular to the extending direction in the conductive pattern 24P (wherein, when the metal wiring 24 extends in a curved shape, the gap G is TCE This corresponds to the minimum distance between two adjacent metal wirings 24 whose straight lines approximating the curve are in substantially the same direction at least within a predetermined region).

[0174] Figure 4 For different line widths W TCE , showing the gap G of the conductive pattern 24P with the horizontal axis being TCE, a graph showing the simulation results of the external quantum efficiency (EQE) obtained by simulation, with the vertical axis being the vertical axis. As shown in the figure, G TCE The upper limit of is preferably 45 μm or less, more preferably 40 μm or less, further preferably 35 μm or less, further more preferably 30 μm or less, particularly preferably 25 μm or less.

[0175] in addition, Figure 5 For different line widths W TCE , showing the relative value of the gap and line width (G TCE / W TCE ), a graph in which the vertical axis is a simulation result of the external quantum efficiency (EQE) obtained by simulation.

[0176] As shown in the figure, (G TCE / W TCE ) has a lower limit of preferably 1.0 or more, more preferably 1.5 or more, further preferably 2.0 or more, further more preferably 3.0 or more, further preferably 5.0 or more, and particularly preferably 7.0 or more.

[0177] By making (G TCE / W TCE ) is greater than 1.0, thereby increasing the aperture ratio, suppressing the shading effect caused by the metal wiring 24, and improving the light receiving efficiency of the organic photoelectric conversion layer 44, thereby tending to improve the external quantum efficiency of the organic photodetector element.

[0178] On the other hand, by making G TCE When the gap is less than 45 μm, the surface potential distribution of the opening of the conductive pattern 24P tends to become uniform, and therefore, the external quantum efficiency of the organic photodetector element as a whole tends to be further improved. The inventors of the present application speculate that the reason why the external quantum efficiency of the organic photodetector element as a whole is improved by reducing the gap is as follows. Electrons generated by light excitation in the organic photoelectric conversion layer 44 provided on the opening of the conductive pattern 24P diffuse in the surface of the electron transport layer 42 with high sheet resistance and are transported to the metal wiring 24. Reducing the gap G TCE The diffusion distance of electrons from the center of the opening to the metal wiring 24 can be shortened, thereby reducing the voltage drop caused by the surface resistance of the electron transport layer 42 accompanying the in-plane diffusion of electrons. As a result, the surface potential distribution of the opening of the conductive pattern 24P tends to become uniform.

[0179] Regarding the charge collection efficiency η, one of the elements of external quantum efficiency ccAs disclosed in J.Xue et al., A Hybrid Planar-Mixed Molecular Heterojunction Photovoltaic Cell, Advanced Materials, January 2005, Vol.17, P.66-71, the greater the effective voltage (the difference between the surface potential of the cathode and the anode) applied to the organic photoelectric conversion layer 44, the greater the charge collection efficiency η cc Therefore, it is considered that by making the surface potential distribution of the opening of the conductive pattern 24P uniform due to the above reason, the external quantum efficiency of the entire organic photodetector element can be further improved.

[0180] (Aperture ratio)

[0181] The aperture ratio A of the conductive pattern 24P TCE It is preferably 25% or more and less than 100%, more preferably 35% or more and 99% or less, further preferably 47% or more and 98% or less, further more preferably 68% or more and 97% or less, and particularly preferably 71% or more and 95% or less. TCE 25% or more, the external quantum efficiency of the organic photodetector element can be improved due to the above reasons. In addition, there is a tendency to increase the visible light transmittance. TCE When the ratio is less than 100%, the occupancy rate of the metal wiring 24 per unit area increases, so the sheet resistance decreases, and there is a tendency that the area of ​​the organic photodetector element can be increased.

[0182] It should be noted that 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.

[0183] Aperture ratio = (1-area occupied by the conductive pattern 24P (metal wiring 24) / area of ​​the transparent substrate 22 where the conductive pattern 24P is formed) × 100

[0184] For example, the conductive pattern 24P is formed Figure 3 In the case of a mesh pattern of square openings as shown in (A), if the line width is set to 1 μm and the gap is set to 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 exposing the transparent substrate 22 is approximately 90%, so the opening ratio is approximately 90%.

[0185] Figure 6 For different line widths W TCE The horizontal axis is the gap G of the conductive pattern 24P. TCE With opening ratio ATCE The vertical axis is a graph showing the simulation results of the external quantum efficiency (EQE) obtained by simulation. TCE ·A TCE ) is an indicator of improving the external quantum efficiency of the organic photodetector element, and represents the diffusion distance (G) of electrons in the in-plane direction of the opening of the conductive pattern 24P. TCE ) is reduced, resulting in uniform surface potential distribution and aperture ratio (A TCE ) increases the light receiving efficiency of the organic photoelectric conversion layer 44. For example, under the same line width, reducing the gap will reduce the diffusion distance of electrons, and the surface potential distribution of the opening will become uniform, so that the charge collection efficiency η cc On the other hand, by reducing the aperture ratio, the light shielding effect brought by the opaque metal wiring 24 becomes greater, and the amount of light received by the organic photoelectric conversion layer 44 decreases. Therefore, the inventors of this application focus on adding (G TCE ·A TCE ) is adjusted to an appropriate range to improve the external quantum efficiency of the organic photodetector element having the metal grid transparent electrode 20. As shown in the figure, (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, further more preferably 1.0 μm·% or more and 35 μm·% or less, further preferably 2.0 μm·% or more and 30 μm·% or less, further preferably 4.0 μm·% or more and 25 μm·% or less, and particularly preferably 6.0 μm·% or more and 22 μm·% or less. By making (G TCE ·A TCE ) is 0.25 μm·% or more, the decrease in light reception due to the light shielding effect of the metal wiring 24 can be suppressed and the surface potential distribution of the opening portion can be made uniform, thereby improving the external quantum efficiency of the organic photodetector element. TCE ·A TCE ) is 45 μm·% or less, which can suppress the charge collection efficiency η associated with the voltage drop at the opening. cc The external quantum efficiency of the organic photodetector element can be improved by increasing the aperture ratio. TCE ·A TCE ) is expressed in units of μm·% to indicate the gap G TCE (μm) multiplied by the aperture ratio A TCE For example, the conductive pattern 24P has a gap G of 20 μm. TCE and 90% opening ratio A TCE When (GTCE ·A TCE ) is recorded as 20μm×0.9=18μm·%.

[0186] In this embodiment, the thickness t of the metal wiring 24 is TCE The thickness is preferably 30 nm to 200 nm, more preferably 50 nm to 170 nm, further preferably 60 nm to 150 nm, and further preferably 70 nm to 130 nm. TCE When the thickness is 30 nm or more, the resistance of the metal grid transparent electrode 20 can be reduced, and there is a tendency that the area of ​​the organic photodetector element can be increased. In addition, there is a tendency that the increase in resistance caused by oxidation and corrosion of the surface of the metal wiring 24 can be fully suppressed. On the other hand, by making t TCE When the thickness is 200 nm or less, the protruding metal wiring 24 can be fully covered within the appropriate film thickness adjustment range of the organic photoelectric conversion layer 44, and electrical short circuits with the counter electrode can be suppressed. In addition, there is a tendency to exhibit high transparency at a wide viewing angle.

[0187] t TCE The measurement can be performed 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 observing the plane of the metal grid transparent electrode 20 with a confocal laser microscope or the like. TCE It can also be confirmed by measuring the film thickness profile of the metal grid transparent electrode 20 using a stylus-type thin film height difference meter.

[0188] The line width W of the metal wiring 24 TCE and the gap G of the conductive pattern 24P TCE and opening ratio A TCE This can be confirmed by observing the surface or cross section of the metal grid transparent electrode 20 using an electron microscope, a laser microscope, an optical microscope, or the like. TCE The gap G between the conductive pattern 24P and the conductive pattern 24P TCE The method of adjusting the range to a desired range includes adjusting the grooves of a plate used in the method of manufacturing the metal grid transparent electrode 20 described later and adjusting the average particle size of metal particles in the ink.

[0189] The metal wiring 24 may include 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 metal component M exhibits conductivity is not particularly limited, and it is presumed to be the same mechanism as the free electron model of the metal. The metal component M is not particularly limited, and examples thereof include gold, silver, copper, and aluminum. Among them, copper, which is relatively cheap and highly conductive, is more preferred. By using such a metal component M, there is a tendency for the conductivity of the metal grid transparent electrode 20 to be more excellent.

[0190] The oxide of the metal component M is not particularly limited, but copper is preferably selected as the metal component M for the reasons described above, and therefore cuprous oxide, cupric oxide, cupric hydroxide, and the like are preferred.

[0191] In addition, the metal wiring 24 may contain a non-conductive component in addition to the metal component M responsible for conductivity. The non-conductive component is not particularly limited, and examples thereof include oxides and organic compounds of the metal component M. More specifically, examples of these non-conductive components include oxides and organic compounds of the metal component M that are derived from components contained in the ink described later and that remain in the metal wiring 24 after firing.

[0192] The content ratio of the metal component M in the metal wiring 24 is preferably 50 mass % or more, more preferably 60 mass % or more, and further preferably 70 mass % or more. The upper limit of the content ratio of the metal component M is not particularly limited, and is less than 100 mass %. In addition, the content ratio of the non-conductive component in the metal wiring 24 is preferably 50 mass % or less, more preferably 40 mass % or less, and further preferably 30 mass % or less. The lower limit of the content ratio of the non-conductive component is not particularly limited, and exceeds 0 mass %.

[0193] (Sheet resistance)

[0194] The sheet resistance R of the conductive pattern 24P of the metal grid transparent electrode 20 is s＿TCE It is preferably 0.1Ω / sq. or more and 100Ω / sq. or less. Sheet resistance R s＿TCE The upper limit value is more preferably 90Ω / sq. or less, further preferably 80Ω / sq. or less, further preferably 70Ω / sq. or less, and particularly preferably 60Ω / sq. or less. s＿TCE When the sheet resistance R is 100Ω / sq. or less, the voltage drop caused by the resistance of the metal grid transparent electrode 20 can be suppressed, and there is a tendency that the area of ​​the organic photodetector element can be increased. s＿TCE The following adjustments can be made to reduce the aperture ratio A of the conductive pattern 24P: TCE , increasing the film thickness t of the metal wiring 24 TCE, increase the content ratio of the metal component M in the metal wiring 24, select the metal component M with high conductivity, etc.

[0195] Sheet resistance R s＿TCE The portion where the conductive pattern 24P is arranged can be measured by a four-probe method based on JIS K7194: 1994. As a measuring instrument for the four-probe method, for example, "LORESTA-GP" (product name, manufactured by Mitsubishi Chemical Corporation) can be cited. s＿TCE The portion where the conductive pattern 24P is arranged may be measured by a non-contact method using eddy current based on ASTM F673-02.

[0196] (Visible light transmittance)

[0197] The visible light transmittance (VLT) of the region where the conductive pattern 24P of the metal grid transparent electrode 20 is arranged is TCE It is preferably 23% to 98%, more preferably 32% to 96%, further preferably 43% to 95%, further more preferably 55% to 94%, further preferably 62% to 93%, and particularly preferably 69% to 92%. By increasing the aperture ratio A of the conductive pattern 24P, TCE , has improved visible light transmittance VLT TCE Visible light transmittance VLT TCE The visible light transmittance VLT can be calculated based on JIS R 3106:2019 or ISO9050:2003 from the transmission spectrum of the region where the conductive pattern 24P of the metal grid transparent electrode 20 is arranged. TCE It can also be calculated by multiplying the visible light transmittance of the transparent base material 22 by the aperture ratio of the conductive pattern 24P.

[0198] [1.2.3 Method for manufacturing metal grid transparent electrode 20]

[0199] The method for manufacturing the metal grid transparent electrode 20 includes a method including a pattern forming step of forming a pattern on the transparent substrate 22 using ink containing the metal component M and a firing step of firing the ink to form the conductive pattern 24P.

[0200] [Pattern forming process]

[0201] The pattern forming step is a step of forming a pattern using ink containing a metal component M. The pattern forming 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, and for example, includes the following steps: a step of applying ink to the surface of a transfer medium; a step of making the surface of the transfer medium coated with ink face the surface of the convex portion of the relief plate face, press and contact, and transfer the ink on the surface of the transfer medium to the surface of the convex portion of the relief plate; and a step of making the surface of the transfer medium with the ink remaining face the surface of the transparent substrate 22 face, press and contact, and transfer the ink remaining on the surface of the transfer medium to the surface of the transparent substrate 22.

[0202] The ink used in the pattern forming step contains a metal component M and a solvent, and may contain a surfactant, a dispersant, a reducing agent, etc. as necessary. The metal component M may be contained in the ink in the form of metal particles or in the form of a metal complex.

[0203] The average primary particle size of the metal particles is preferably less than 100 nm, more preferably less than 50 nm, and further preferably less than 30 nm. In addition, the lower limit of the average primary particle size of the metal particles is not particularly limited, and 1 nm or more can be cited. By making the average primary particle size of the metal particles less than 100 nm, the line width of the obtained metal wiring 24 can be made thinner. It should be noted that the "average primary particle size" refers to the particle size of each metal particle (so-called primary particle), which is different from the particle size of the aggregate (so-called secondary particle) formed by the aggregation of multiple metal particles, that is, the average secondary particle size.

[0204] 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 constituent atoms, and core / shell particles having a core of a metal component M such as copper and a shell of a metal oxide containing a metal component M such as copper oxide as constituent atoms. The form of the metal particles can be appropriately determined from the viewpoints of dispersibility and sinterability.

[0205] The content of the metal particles in the ink is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, and further preferably 10% by mass to 35% by mass, relative to the total mass of the ink composition.

[0206] In the firing process, for example, the metal component M in the ink transferred to the surface of the transparent substrate 22 is sintered to form a conductive pattern 24P. There is no particular limitation on the firing method as long as it is a method that can melt the metal component M to form a metal component sintered film. The firing can be performed, for example, using a firing furnace, and can be performed using plasma, thermal catalyst, ultraviolet light, vacuum ultraviolet light, electron beam, infrared lamp annealing, flash lamp annealing, laser, etc. It should be noted that the obtained metal component sintered film contains a conductive component derived from the metal component M, and may also contain a non-conductive component depending on the components used in the ink and the firing temperature.

[0207] [1.3 Electron transport layer 42 (ETL: Electron transport layer)]

[0208] The electron transport layer 42 of this embodiment efficiently transports electrons generated by light excitation in the organic photoelectric conversion layer 44 to the metal grid transparent electrode 20 as a cathode. In addition, for the purpose of reducing dark current density, the electron transport layer 42 preferably also functions as a hole blocking layer. The electron transport layer 42 is formed in a manner covering the conductive pattern 24P of the metal grid transparent electrode 20.

[0209] From the perspective of electron transportability, the difference between the conduction band or LUMO (lowest unoccupied molecular orbital) of the electron transport layer 42 or at least any one of the defect energy level and doping energy level responsible for electron conduction and the LUMO of the organic acceptor material is preferably within 1.0 eV, more preferably within 0.5 eV, and further preferably within 0.3 eV. In addition, the conduction band or LUMO of the electron transport layer 42 or at least any one of the defect energy level and doping energy level responsible for electron conduction is preferably lower than the energy level determined by the work function of the metal grid transparent electrode 20 (4.65 eV in the case of copper). Furthermore, from the perspective of hole blocking properties, the valence band or HOMO (highest occupied molecular orbital) of the electron transport layer 42 is preferably an energy level that is 0.3 eV or more higher than the HOMO of the organic donor material, more preferably an energy level that is 0.5 eV or more higher, and further preferably an energy level that is 1.0 eV or more higher.

[0210] The electron transport layer 42 can be made of conventionally known materials and structures used in conventional organic photodetector elements and organic solar cells. The electron transport layer 42 is not particularly limited, and examples thereof include 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. In addition, the electron transport layer 42 is described in Boping Yang et al., Inorganic topelectron 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, P.2185-2207., etc., so those skilled in the art can understand.

[0211] From the viewpoint of electron transporting property and hole blocking property, a-IGZO (amorphous IGZO) is particularly preferred as the electron transporting layer 42 .

[0212] The film thickness of the electron transport layer 42 is preferably 5 nm or more and 100 nm or less, more preferably 8 nm or more and 80 nm or less, further preferably 10 nm or more and 60 nm or less, and particularly preferably 12 nm or more and 40 nm or less. From the viewpoint of electron transportability and hole blocking property, the film thickness of the electron transport layer 42 is preferably 5 nm or more. The film thickness of the electron transport layer 42 is preferably 100 nm or less, because the visible light transmittance is improved.

[0213] The electron transport layer 42 is preferably formed by a vapor phase film forming method such as PVD or CVD, and is particularly preferably formed by a sputtering method or a vacuum deposition method.

[0214] [1.4 Organic photoactive layer 44]

[0215] The organic photoelectric conversion layer 44 of the present embodiment is a (photoelectric conversion) layer that separates excitons formed by absorbing light containing an optical input signal and generating carriers of electrons and holes. The organic photoelectric conversion layer 44 preferably has at least one organic donor material and one or more organic acceptor materials. In addition, in order to improve the visible light transmittance of the organic photodetector element as a whole, the organic photoelectric conversion layer 44 of the present embodiment is an island-shaped sub-pixel 44S (or sub-pixel array) structure.

[0216] The organic photoelectric conversion layer 44 can use conventionally known materials, compositions, and structures generally used for organic photodetector elements and organic solar cells.

[0217] As the structure of the organic photoelectric conversion layer 44, for example, a planar heterojunction, a bulk heterojunction, and a hybrid type formed by combining these can be cited. A planar heterojunction is a structure having at least one PN junction formed by stacking a layer (P-type layer) formed by one or more organic donor materials and a layer (N-type layer) formed by one or more organic acceptor materials. In addition, a bulk heterojunction is a structure (i layer (intrinsic layer)) formed by mixing and bonding one or more organic donor materials (or a phase formed by one or more organic donor materials) and one or more organic acceptor materials (or a phase formed by one or more organic acceptor materials). The hybrid type may be a structure in which a P-type layer / i layer / N-type layer is stacked in sequence. In addition, the hybrid type may be a structure called an inter-impregnation type that has no layer boundaries and continuously transforms in the order of a P-type layer / i layer / N-type layer. From the viewpoint of obtaining a high external quantum efficiency, the organic photoelectric conversion layer 44 is preferably a structure having a bulk heterojunction that easily separates excitons.

[0218] For the reasons described above, the organic photoelectric conversion layer 44 of the present embodiment preferably performs photoelectric conversion on near-infrared light of at least a part of the wavelength in the near-infrared wavelength region of 780 nm to 1200 nm.

[0219] 〔Organic accepor material〕

[0220] The organic acceptor material is a material having the property of easily accommodating electrons, and more specifically, is a material having electron accommodating properties and having a high electron affinity when the organic acceptor material and the organic donor material are brought into contact with each other.

[0221] Based on the above-mentioned purpose of photoelectric conversion of near-infrared light, the optical band gap E of the organic acceptor material g optIt is preferably 1.65 eV or less, more preferably 1.60 eV or less, further preferably 1.50 eV or less, further more preferably 1.45 eV or less, further more preferably 1.40 eV or less, further more preferably 1.35 eV or less, and particularly preferably 1.30 eV or less. It should be noted that the optical band gap E in this specification is g opt As is the common definition in this technical field, this is a value calculated using the longest wavelength (light absorption edge) at which a material starts to absorb light.

[0222] The organic acceptor material may be a conventionally known material generally used in an organic photodetector element or an organic solar cell. The organic acceptor material is not particularly limited, and examples thereof include C 60 , C 70 , C 84 Fullerene; PC 61 BM, PC 71 BM, IC 60 Fullerene derivatives such as BA, non-fullerene acceptors (NFA), etc. From the perspective of the above-mentioned purpose of photoelectric conversion of near-infrared light, it is preferable to use a non-fullerene acceptor (NFA) as the organic acceptor material.

[0223] The non-fullerene acceptor (NFA) is not particularly limited.Examples include 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, ITVfIC, IEICS-4F, etc.

[0224] In addition, those skilled in the art will appreciate that non-fullerene acceptors (NFA) can use, for example:

[0225] Dong Meng et al., Near-infrared Materials: The Turning Point of OrganicPhotovoltaics, Advanced Materials, 2021, Accepted Author Manuscript2107330,

[0226] Hao-Wen Cheng et al., Toward High-Performance Semitransparent OrganicPhotovoltaics with Narrow-Bandgap Donors and Non-Fullerene Acceptors, AdvanceEnergy Materials, 2021, P.2102908,

[0227] Yiwen Wang et al., Recent Progress and Challenges toward Highly StableNonfullerene Acceptor-Based Organic Solar Cells, Advance Energy Materials, 2021, Vol.11, P.2003002,

[0228] 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, ChemicalSociety Reviews, 2019, Vol.48, P.1596-1625,

[0229] Cenqi Yan et al., Non-fullerene acceptors for organic solar cells, Nature Reviews Materials, 2018, Vol.3, P.18003,

[0230] 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,

[0231] Guangye Zhang et al., Non-fullerene Acceptor Molecules for Bulk Heterojunction Organic Solar Cells, Chemical Reviews, 2018, Vol.118, P.3447 - 3507,

[0232] Pei Cheng et al., Next-generation organic photovoltaics based on non-fullerene acceptors, Nature Photonics, 2018, Vol.12, P.131 - 142,

[0233] Lichun Chang et al., Ternary organic solar cells based on non-fullerene acceptors: A review, Organic Electronics, March 2021, Vol.90, P.106063,

[0234] Huiting Fu et al., Advances in Non-Fullerene Acceptor Based Ternary Organic Solar Cells, Solar RRL, December 2017, Vol.2, P.1700158, etc.

[0235] From the viewpoint of obtaining high external quantum efficiency in the above-mentioned near-infrared region, the organic acceptor material is preferably selected from at least one of 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. In addition, from the same point of view, the organic acceptor material is particularly preferably 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, COi8DFIC, FOIC, F8IC, F10IC, SiOTIC-4F, and P3.

[0236] [Organic donor material]

[0237] The organic donor material is a material having a property of easily donating electrons, and more specifically, is a material having electron donating property with a low ionization potential when an organic acceptor material and an organic donor material are brought into contact with each other for use.

[0238] Based on the above-mentioned purpose of photoelectric conversion of near-infrared light, the optical band gap E g of the organic donor material is opt It is preferably 1.65 eV or less, more preferably 1.63 eV or less, further preferably 1.62 eV or less, further more preferably 1.61 eV or less, and particularly preferably 1.60 eV or less.

[0239] The organic donor material can use the existing known materials generally used for organic photodetector elements and organic solar cells. The organic donor material is not particularly limited, and examples thereof include PTB7-Th (alias: 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 , PSBT-BT, C3-DPPTT-T, C3-DPPTT-Se, C3-DPPTT-Te, PDPP-DTS, DPPTBI, DPPTDTSffBzDTST, ZnP2-DPP, P3, P(ffDITDQx-BT), PDFDPSe-C18, CS-DP, BDP-OMe, P2-Bronstei n, PFDQ, PTBEHT, PDPPTDTPT, PDPPSDTPS, PDTTDPP, PDTP-DTDPP(Bu), P2-Aso, PTTDTP, APFO-Green1, P1-Ying, P1-Iraqi, F2, CDTDOP, CEHTP, TTV2, TBDPTV, PPor1, P3TPQ, etc.

[0240] In addition, those skilled in the art will appreciate that the organic donor material may use, for example, Dong Meng et al., Near-infrared Materials: The Turning Point of Organic Photovoltaics, Advanced Materials, 2021, Accepted Author Manuscript 2107330,

[0241] Hao-Wen Cheng et al., Toward High-Performance Semitransparent OrganicPhotovoltaics with Narrow-Bandgap Donors and Non-Fullerene Acceptors, AdvanceEnergy Materials, 2021, P.2102908,

[0242] 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,

[0243] 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,

[0244] Cenqi Yan et al., Non-fullerene acceptors for organic solar cells, Nature Reviews Materials, 2018, Vol.3, P.18003,

[0245] 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,

[0246] Guangye Zhang et al., Non-fullerene Acceptor Molecules for BulkHeterojunction Organic Solar Cells, Chemical Reviews, 2018, Vol.118, P.3447-3507,

[0247] Pei Cheng et al., Next-generation organic photovoltaics based on non-fullerene acceptors, Nature Photonics, 2018, Vol.12, P.131-142,

[0248] Lichun Chang et al., Ternary organic solar cells based on non-fullerene acceptors:A review, Organic Electronics, March 2021, Vol.90, P.106063,

[0249] 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.

[0250] From the viewpoint of obtaining high external quantum efficiency and low dark current density in the near-infrared region mentioned above, the organic donor material is preferably selected from at least one of the group consisting of PTB7-Th (alias: 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.

[0251] When the film thickness of the organic photoelectric conversion layer 44 in the sub-sensor region 44SS provided on the metal wiring 24 is set to t OPD When (tOPD -t TCE ), that is, the difference between the thickness of the organic photoelectric conversion layer 44 in the sub-sensor region 44SS and the thickness of the metal wiring 24 is preferably 50 nm to 500 nm, more preferably 100 nm to 450 nm, further preferably 140 nm to 380 nm, further more preferably 160 nm to 330 nm, and particularly preferably 180 nm to 280 nm. By making (t OPD -t TCE ) is 50 nm or more, the protruding metal wiring 24 can be fully covered by the organic photoelectric conversion layer 44 of the sub-sensor region 44SS, and the relative distance from the anode can be sufficiently ensured, thereby suppressing electrical short circuits. OPD increases exponentially, so as t OPD On the other hand, by increasing (t OPD -t TCE ) is 500 nm or less, the charge collection efficiency η caused by the thickening of the organic photoelectric conversion layer 44 in the sub-sensor region 44SS can be suppressed. cc As disclosed in J.Xue et al., A Hybrid Planar-Mixed Molecular Heterojunction Photovoltaic Cell, Advanced Materials., January 2005, Vol.17, P.66-71., the charge collection efficiency η cc In the region where the organic photoelectric conversion layer 44 is sufficiently thick, OPD In addition, by making (t OPD -t TCE ) is less than 500 nm, which tends to increase the visible light transmittance of the organic photodetector in the sub-pixel 44S and reduce the visual visibility of the sub-pixel 44S.

[0252] About t OPD , as long as (t OPD -t TCE ) is adjusted to the above range without particular limitation, but is preferably 80 nm to 700 nm, more preferably 150 nm to 500 nm, further preferably 200 nm to 400 nm, and particularly preferably 250 nm to 350 nm. OPD The above range is preferred for the reasons described above.

[0253] t OPDIt can be a value obtained by using a standard curve of the process conditions and film thickness of the organic photoelectric conversion layer 44 and according to the process conditions of dry film formation, wet film formation or patterned printing. In addition, it can be confirmed by observing the cross section of the organic photodetector element with an electron microscope (SEM, TEM, STEM). In addition, EDX (energy dispersive X-ray analysis) can be 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 area with a large EDX intensity of the carbon atom C between the metal wiring 24 and the relative electrode (such as the anode) is taken as the organic photoelectric conversion layer 44 and the film thickness is measured.

[0254] The method for forming the organic photoelectric conversion layer 44 can use the existing known methods generally used for organic photodetector elements and organic solar cells. As such a method, for example, the 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. In addition, a predetermined amount of one or more organic donor materials and one or more organic acceptor materials can be dissolved in a suitable solvent, and the organic photoelectric conversion layer forming ink prepared in this way can be wet-filmed by a known coating method such as slit die coating and spin coating, or a casting method, and then dried and annealed as needed, thereby forming the organic photoelectric conversion layer 44 having a bulk heterojunction structure. Through the drying and annealing conditions of the organic photoelectric conversion layer forming ink, it is also possible to adjust the nano-level phase separation structure of the phase formed by the one or more organic donor materials and the phase formed by the one or more organic acceptor materials, and adjust the morphology of the bulk heterojunction.

[0255] As the solvent for the ink for forming the organic photoelectric conversion layer, the existing well-known solvents commonly used for organic photodetector elements and organic solar cells can be used, and examples thereof include aromatic solvents such as toluene, xylene, mesitylene, and cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1, Ether solvents such as aromatic ethers such as 3-dimethoxybenzene, anisole, ethoxybenzene, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole; aliphatic ester solvents such as ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate; ester solvents such as aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, n-butyl benzoate; etc.

[0256] In order to adjust the morphology of the bulk heterojunction, additives such as naphthalene chloride and 1,8-diiodooctane may be appropriately added to the ink for forming the organic photoelectric conversion layer.

[0257] As a method for forming sub-pixel 44S, first, dry film formation or wet film formation of a solid film of organic photoelectric conversion layer 44 can be performed on the entire surface of the element using the above-mentioned method. Next, the solid film of organic photoelectric conversion layer 44 is formed into sub-pixel 44S using a known patterning method such as photolithography, nanoimprinting, sublimation, laser ablation, etc. As a patterning method, the method disclosed in non-patent document 3 is particularly preferred. In addition, the ink for forming the organic photoelectric conversion layer can be patterned and printed using a known printing method such as gravure printing, gravure offset printing, letterpress printing, flexographic printing, inkjet printing, screen printing, etc., dried, and annealed as needed, thereby forming sub-pixel 44S.

[0258] [1.5 Hole transport layer 46 (HTL)]

[0259] 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.

[0260] 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 energy level and doping energy 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. In addition, from the viewpoint of electron blocking property, the conduction band or LUMO of the hole transport layer 46 is preferably an energy level lower than the LUMO of the organic acceptor material by 0.3 eV or more, more preferably an energy level lower by 0.5 eV or more, and further preferably an energy level lower by 1.0 eV or more.

[0261] The hole transport layer 46 can be made of conventionally known materials and structures generally used in organic photodetector elements and organic solar cells. The hole transport layer 46 is not particularly limited, and examples thereof include 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)In addition, the hole transport layer 46 is described in, for example, Arumugam, GM et al., Inorganic hole transport layers in inverted perovskite solar cells: A review, Nano Select., June 2021, Vol. 2, P. 1081-1116., etc., and thus can be understood by those skilled in the art. From the viewpoint of hole transport and electron blocking properties, the hole transport layer 46 is particularly preferably MoO X(2≤X≤3) .

[0262] The thickness of the hole transport layer 46 is preferably 5 nm or more and 300 nm or less, more preferably 10 nm or more and 200 nm or less, further preferably 30 nm or more and 100 nm or less, and particularly preferably 50 nm or more and 80 nm or less. When the thickness of the hole transport layer 46 is 5 nm or more, it is preferred from the viewpoint of hole transport and electron blocking properties. When the thickness of the hole transport layer 46 is 300 nm or less, the visible light transmittance is improved, so it is preferred.

[0263] The hole transport layer 46 is preferably formed by a vapor phase film forming method such as PVD or CVD, and is particularly preferably formed by a sputtering method or a vacuum deposition method.

[0264] [1.6 Transparent electrode 60 (anode)]

[0265] The transparent electrode 60 of this embodiment can be used as an anode of the organic photodetector element, contributes to improving the transparency of the organic photodetector element, and collects charges of holes generated in the organic photoelectric conversion layer 44 .

[0266] The transparent electrode 60 of the present embodiment can use the existing well-known materials and structures commonly used in organic photodetector elements and organic solar cells without special restrictions, and examples thereof include the above-mentioned metal grid transparent electrode 20 (or only metal grid), transparent conductive inorganic compounds, conductive polymers such as PEDOT:PSS, metal nanowires such as silver nanowires, carbon materials such as graphene, etc. These can be used alone or in combination. From the viewpoint of having high visible light transmittance and low sheet resistance, the transparent electrode 60 of the present embodiment is preferably the above-mentioned metal grid transparent electrode 20 (or only metal grid) or transparent conductive inorganic compound, and more preferably a transparent conductive inorganic compound. In addition, from the viewpoint of improving the flexibility of the organic photodetector element, the transparent electrode 60 of the present embodiment is preferably a metal grid transparent electrode 20 (or only metal grid) or a conductive polymer.

[0267] The material used in the transparent conductive inorganic compound is not particularly limited as long as it is an inorganic compound with high transmittance in the visible light region and exhibits conductivity, and examples thereof include In2O3 systems such as ITO, SnO2 systems such as ATO and FTO, ZnO systems such as AZO and GZO, (ZnO-In2O3) systems such as Zn2In2O5 and Zn3In2O2, In4Sn3O 12 Other known materials that can be used for transparent conductive oxides can be used. Among these, ITO (indium oxide) is preferably used, which has the widest application and excellent transparency and conductivity.

[0268] 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, further preferably 10 nm or more and 300 nm or less, and particularly preferably 10 nm or more and 200 nm or less. By making the film thickness of the transparent conductive inorganic compound 10 nm or more, there is a tendency to reduce the sheet resistance of the transparent conductive inorganic compound and increase the area of ​​the organic photodetector element. On the other hand, by making the film thickness of the transparent conductive inorganic compound 1000 nm or less, there is a tendency to suppress the decrease in the visible light transmittance of the transparent conductive inorganic compound.

[0269] The upper limit of the sheet resistance of the transparent conductive inorganic compound is preferably 500Ω / sq. or less, more preferably 200Ω / sq. or less, further preferably 100Ω / sq. or less, and particularly preferably 50Ω / sq. or less. By making the sheet resistance of the transparent conductive inorganic compound 500Ω / sq. or less, there is a tendency to increase the area of ​​the organic photodetector element. The lower limit of the sheet resistance of the transparent conductive inorganic compound layer is not particularly limited, and for example, 0.1Ω / sq. can be cited.

[0270] The lower limit of the visible light transmittance of the transparent conductive inorganic compound is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 90% or more. By making the visible light transmittance of the transparent conductive inorganic compound layer 60% or more, there is a tendency to improve the transparency of the organic photodetector element. The upper limit of the visible light transmittance of the transparent conductive inorganic compound is not particularly limited, and for example, it can be 100% or less.

[0271] The transparent conductive inorganic compound is preferably formed into a film by a vapor phase film forming method such as PVD or CVD, and is particularly preferably formed into a film by a sputtering method or a vacuum deposition method.

[0272] [1.7 Sealing layer]

[0273] The sealing layer is a layer with high barrier properties against moisture and oxygen, just like the above-mentioned barrier layer. By setting the sealing layer, it is helpful to suppress the degradation of the characteristics of the organic photodetector element caused by the intrusion of moisture and oxygen into the organic photodetector element. The sealing layer is arranged on the anode, and further, it can be formed in a manner that covers the organic photodetector element or the organic photodetector array except for a part of the collector 110 exposed for connection to the external terminal. The sealing layer can apply the existing known composition, structure and formation method commonly used for organic photodetector elements and organic solar cells, and preferably uses the same composition and structure as the above-mentioned barrier layer. As a sealing layer, it is particularly preferred to use the thin film sealing layer (TFE) disclosed in non-patent document 2. In addition, a barrier laminated film can be used in which the above-mentioned barrier layer, the thin film sealing layer disclosed in non-patent document 2 and the adhesive layer with gas barrier properties are sequentially stacked on the material of the core layer used as the above-mentioned transparent substrate 22. When using a barrier laminated film as a sealing layer, it is stacked in a manner that the adhesive layer is bonded to the anode, and a known lamination method using heat, pressure, light, etc. can be used for sealing.

[0274] [2. Organic photodetector array]

[0275] Figure 7 (A) is a schematic diagram of an organic photodetector array (hereinafter, sometimes referred to as an "OPD array"), Figure 7 (B) is Figure 7 The OPD array includes a plurality of OPD elements 10 , a collector portion 110 , a wiring portion 120 for electrically connecting the collector portion 110 and each OPD element 10 , and a dummy pattern portion 130 .

[0276] The OPD array of the present embodiment comprises a plurality of OPD elements 10 which are arranged two-dimensionally and spaced apart from each other along two orthogonal coordinate axes (the vertical direction of the paper and the horizontal direction of the paper) in parallel planes. In each direction, a plurality of OPD elements 10 are regularly arranged at equal intervals. However, the present invention is not limited thereto, and the OPD array may also comprise a plurality of OPD elements 10 which are arranged one-dimensionally, or a plurality of OPD elements 10 which are arranged randomly. Furthermore, as described above, each OPD element 10 may respectively comprise a sub-pixel array composed of a plurality of sub-pixels 44S which are arranged two-dimensionally and spaced apart from each other along two orthogonal coordinate axes (the vertical direction of the paper and the horizontal direction of the paper) in parallel planes.

[0277] The organic photodetector element is an element that applies a voltage (usually a reverse bias voltage) from an external circuit and extracts the carriers of electrons and holes generated by light excitation in the organic photoelectric conversion layer 44 to the external circuit in the form of a photodetection current. Each organic photodetector element constitutes each individual pixel of the organic photodetector array. The organic photodetector element can have the configuration of the OPD element 10 and other organic photodetector elements described above.

[0278] The organic photodetector array of this embodiment may include a collector 110 connected to a terminal from an external circuit, and the collector 110 transmits a voltage signal applied by the external circuit to the organic photodetector element and transmits a light detection current to the external circuit. In addition, the organic photodetector array of this embodiment may include a wiring portion 120 that electrically connects the organic photodetector element and the collector 110.

[0279] [Wiring section 120]

[0280] The organic photodetector array of this embodiment may include a wiring portion 120 having a second conductive pattern provided on the transparent substrate 22 and electrically connected to the conductive pattern 24P (metal wiring 24). The wiring portion 120 may be independently provided for each pixel. That is, the wiring of the wiring portion 120 connected to the metal wiring 24 of the first OPD element 10 provided in the OPD array and the wiring of the wiring portion 120 connected to the metal wiring 24 of the second OPD element 10 are configured in a manner that allows electrical insulation. Therefore, each OPD element 10 can function as an independent pixel.

[0281] Here, in order to make the visible light transmittance of the entire organic photodetector array uniform, A wire When the aperture ratio of the second conductive pattern is set to -10%≤(A wire -A TCE )≤10%. More preferably -8%≤(A wire -A TCE )≤8%, more preferably -6%≤(A wire -A TCE )≤6%, particularly preferably -4%≤(A wire -A TCE )≤4%.

[0282] By setting such a configuration, the deviation of the visible light transmittance between the region where the conductive pattern 24P is provided and the region where the second conductive pattern is provided can be suppressed. Therefore, when the organic photodetector array is arranged on the screen of a display such as a monitor, the deviation of the visibility of the image displayed on the screen of the display can be suppressed.

[0283] (Line width, gap)

[0284] The line width W of the metal wiring 24 constituting the second conductive pattern is wire The thickness of W is preferably 0.25 μm to 5.0 μm, more preferably 0.25 μm to 4.0 μm, further preferably 0.25 μm to 3.0 μm, further more preferably 0.25 μm to 2.0 μm, and particularly preferably 0.25 μm to 1.0 μm. In addition, in order to make the visible light transmittance of the entire organic photodetector array and the visual recognition of the metal wiring 24 uniform, W wire Preferably with W TCE The same line width value. wire When the line width W of the metal wiring 24 is 0.25 μm or more, the wiring resistance can be reduced, and there is a tendency to increase the area of ​​the organic photodetector array. In addition, the increase in resistance caused by oxidation and corrosion on the surface of the metal wiring 24 can be fully suppressed. On the other hand, by making the line width W of the metal wiring 24 wire When the line width W of the metal wiring 24 is 5.0 μm or less, the visibility of the opaque metal wiring 24 can be reduced. wire By adjusting the thickness to 3.0 μm or less, the opaque metal wiring 24 can be made invisible to the human eye. Thus, when the organic photodetector array is arranged on a display such as a display, the appearance and design of the display will not be affected. wire The aperture ratio A wire The method of achieving the above range is based on the second conductive pattern and W wire For the purpose of making the visible light transmittance of the entire organic photodetector array and the visual recognition of the metal wiring 24 uniform, G wire Preferably with G TCE Same gap value.

[0285] [Electricity collecting unit 110]

[0286] The organic photodetector array of this embodiment may include a collector 110 having a third conductive pattern provided on the transparent substrate 22 and electrically connected to the second conductive pattern. The collector 110 is a portion for collecting the light detection current detected by the OPD element 10 constituting each pixel and supplying it to an external circuit. The collector 110 may include, for example, a contact pad (joining area) for connecting to an external FPC (Flexible Printed Circuits).

[0287] In the pad When the area ratio of the third conductive pattern per unit area is Γ padIt is preferably 50% or more and less than 100%. Γ pad The lower limit of is more preferably 60% or more, and further preferably 70% or more. By making the area ratio of the third conductive pattern Γ pad In the above range, the electrical connection with the external terminal is further improved, the resistance of the collector 110 can be reduced, and there is a tendency that a voltage drop of the applied voltage can be suppressed.

[0288] It should be noted that the “occupancy area ratio” of the conductive pattern 24P can be calculated by the following formula with respect to the region on the transparent substrate 22 where the conductive pattern 24P is formed.

[0289] Occupancy ratio = (area occupied by the conductive pattern 24P / area of ​​the transparent substrate 22 where the conductive pattern 24P is formed) × 100

[0290] For example, the third conductive pattern is Figure 3 In the case of a square mesh pattern as shown in (A), if the line width is set to 5 μm and the gap is set to 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 area occupied ratio Γ pad It is about 56%.

[0291] (Line width, gap)

[0292] The line width W of the metal wiring 24 constituting the third conductive pattern is pad It is preferably 0.25 μm or more and 10 μm or less, more preferably 0.5 μm or more and 8 μm or less, and still more preferably 1 μm or more and 6 μm or less. pad In the above range, the connectivity with the external terminal is further improved and the sheet resistance of the collector 110 can be reduced, which tends to suppress the voltage drop of the applied voltage. pad The occupied area ratio Γ pad In the above range, the third conductive pattern and W pad Set appropriately.

[0293] [Dummy pattern portion 130]

[0294] The organic photodetector array of this embodiment may include a dummy pattern portion 130, which is configured to be electrically insulated from the conductive pattern 24P and the second to third conductive patterns 24P. The dummy pattern portion 130 may be provided between two adjacent OPD elements 10. For example, the plurality of OPD elements 10 provided in the organic photodetector array may be arranged at equal intervals (including the two orthogonal coordinate axes) along two orthogonal coordinate axes. Figure 7In the two-dimensional arrangement, the dummy pattern portion 130 may be arranged between two adjacent OPD elements 10 at equal intervals along two orthogonal coordinate axes.

[0295] Figure 7 The dummy pattern portion 130 disposed between two adjacent OPD elements 10 on the first coordinate axis (horizontal direction of the paper) and the dummy pattern portion 130 disposed between two adjacent OPD elements 10 on the second coordinate axis (vertical direction of the paper) are shown.

[0296] The dummy pattern portion 130 may have the same structure as the metal grid transparent electrode 20 of the OPD element 10. By having the same structure, the manufacturing process of the metal grid transparent electrode 20 of the OPD element 10 and the dummy pattern portion 130 can be made common.

[0297] By providing the dummy pattern portion 130 in the region where the OPD element 10 is not provided, the difference in visible light transmittance between the two regions can be suppressed. dummy When the aperture ratio of the dummy pattern is set to -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 dummy -A TCE )≤4%.

[0298] (Line width, gap)

[0299] The line width W of the metal wiring 24 constituting the dummy pattern portion 130 is dummy The thickness of W is preferably 0.25 μm to 5.0 μm, more preferably 0.25 μm to 4.0 μm, further preferably 0.25 μm to 3.0 μm, further more preferably 0.25 μm to 2.0 μm, and particularly preferably 0.25 μm to 1.0 μm. In addition, in order to make the visible light transmittance of the entire organic photodetector array and the visual recognition of the metal wiring 24 uniform, W dummy Preferably with W TCE The same line width value. dummy When the line width W of the metal wiring 24 is 0.25 μm or more, the increase in resistance due to oxidation and corrosion of the surface of the metal wiring 24 can be sufficiently suppressed.dummy When the line width W of the metal wiring 24 is 5.0 μm or less, the visibility of the opaque metal wiring 24 can be reduced. dummy By adjusting the thickness to less than 3.0 μm, the opaque metal wiring 24 can be made invisible to the human eye. Thus, when the organic photodetector array is arranged on a display such as a display, the appearance and design of the display will not be affected. dummy The aperture ratio A dummy The method within the above range is based on the pattern of the dummy pattern part 130 and W dummy For the purpose of making the visible light transmittance of the entire organic photodetector array and the visual recognition of the metal wiring 24 uniform, G dummy Preferably with G TCE Same gap value.

[0300] [Dummy sub-pixel]

[0301] Figure 8 Show Figure 7 4 is a cross-sectional view and a projection view of a dummy sub-pixel 44SD provided in the area AR3 on the dummy pattern portion 130. It should be noted that, Figure 7 The cross-sectional view and projection view of the sub-pixel 44S provided in the area AR2 within the OPD element 10 are similar to Figure 1 quite.

[0302] like Figure 8 As shown, the organic photodetector array 100 of the present embodiment may include an insulating layer 80 disposed on the dummy pattern portion 130 and an organic photoelectric conversion layer (dummy sub-pixel 44SD) disposed on the insulating layer 80 and insulated from the dummy pattern portion 130. Here, the insulating layer 80 on the dummy pattern portion 130 may have substantially the same thickness and the same composition as the insulating layer 80 of the OPD element 10. By setting the insulating layer 80 to substantially the same thickness and the same composition, the manufacturing process of the two insulating layers 80 can be made common, that is, the insulating layer 80 of the OPD element 10 and the insulating layer 80 on the dummy pattern portion 130 can be formed at the same time. With respect to the insulating layer 80 on the metal grid transparent electrode 20 of the OPD element 10, the opening OP can be provided by further patterning.

[0303] The organic photoelectric conversion layer (dummy sub-pixel 44SD) on the dummy pattern portion 130 is different from the organic photoelectric conversion layer 44 of the OPD element 10. Figure 8(A)) is arranged at a position approximately the same distance as the electron transport layer 42 separated by the insulating layer 80. Therefore, the organic photoelectric conversion layer (dummy sub-pixel 44SD) on the dummy pattern portion 130 is insulated from the dummy pattern portion 130. Therefore, the current is not detected in the dummy pattern portion 130. It should be noted that the thickness of the organic photoelectric conversion layer (dummy sub-pixel 44SD) on the dummy pattern portion 130 is approximately the same as the thickness of the alignment area 44SA of the OPD element 10, thereby making the manufacturing process of the two organic photoelectric conversion layers universal, that is, the organic photoelectric conversion layer 44 of the OPD element 10 and the organic photoelectric conversion layer (dummy sub-pixel 44SD) on the dummy pattern portion 130 can be simultaneously formed. It should be noted that the dummy sub-pixel 44SD is not limited to the dummy pattern portion 130 and the insulating layer 80 arranged on the electron transport layer 42. For example, the transparent substrate 22, the metal grid transparent electrode 20 other than the OPD element 10 area, and the insulating layer 80 arranged on the wiring portion 120 can also be provided.

[0304] Since the organic photodetector array 100 (OPD array 100) of the present embodiment further includes a dummy sub-pixel 44SD provided in a region between the OPD elements 10 and the OPD elements 10, it is possible to suppress the region where the OPD elements 10 are provided and the region between the OPD elements 10 and the OPD elements 10 (the region where the dummy pattern portion 130 is provided). Figure 7 ) difference in visible light transmittance. Moreover, by providing the dummy sub-pixel 44SD, the generation of interference fringes can be suppressed compared to when the dummy sub-pixel 44SD is not provided. Therefore, as will be described later, Fig. 9 As described above, when the OPD array 100 is provided on the screen of a display or a display body, interference fringes based on light emitted by the display or the display body can be suppressed, and the visual recognition of the display or the display body can be improved. Therefore, the organic photodetector array composed of the organic photodetector elements disclosed in this embodiment can be suitably used in a non-touch user interface.

[0305] It should be noted that the reason why it is considered that the interference fringes are less likely to be observed when the device is applied to a touchless user interface by providing the dummy sub-pixel 44SD is as follows.

[0306] When the organic photodetector array 100 of the present embodiment is applied to an existing display, the luminescent pixel of the display is about 200 to 300 μm, and the distance between the luminescent pixel and the organic photodetector array 100 (the distance in the direction perpendicular to the screen) is about several mm. Therefore, the visibility of the interference fringes caused by the OPD element 10 of the organic photodetector array 100 or the sub-pixel 44S in the OPD element 10 is as shown in the following formula. Therefore, the generated interference fringes become smaller, and such interference fringes are not easily visually recognized.

[0307] V=(Imax-Imin) / (Imax+Imin)

[0308] =|sin(πad / λL) / (πad / λL)|

[0309] Here, 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 part of the interference fringes. a is the width of the light source. λ is the emission wavelength. d is the spacing of the OPD elements 10 (e.g., the center-to-center distance of adjacent photodetector elements 10) or the spacing of the sub-pixels 44S in the OPD element 10 (e.g., the center-to-center distance of adjacent sub-pixels 44S). L is the distance from the light-emitting pixel of the display to the organic photodetector array 100.

[0310] The pitch of the interference fringes is expressed as follows: Therefore, the pitch of the interference fringes caused by the OPD element 10 of the organic photodetector array 100 or the sub-pixel 44S in the OPD element 10 is reduced to several 100 μm, making it difficult to visually recognize.

[0311] X=mDλ / d

[0312] Here, X is the pitch of the interference fringes, m is the number of interferences (an integer), and D is the distance from the organic photodetector array 100 to the observer.

[0313] As described above, the interference fringes caused by the OPD elements 10 of the organic photodetector array 100 and the interference fringes caused by the sub-pixels 44S in the OPD elements 10 themselves have low visual recognition. However, it is known that the OPD elements 10 are arranged at intervals from each other ( Figure 7 ) and the sub-pixels 44S are arranged at intervals from each other in each OPD element 10 ( Figure 1 ) in which the interference fringes overlap, resulting in interference fringes of visually discernible intensity and spacing.

[0314] Therefore, the organic photodetector array 100 of the present embodiment includes a dummy sub-pixel 44SD provided in a region between the OPD elements 10 and the OPD elements 10. By providing the dummy sub-pixel 44SD, the generation of interference fringes accompanying the OPD elements 10 arranged at intervals from each other can be suppressed, and thus the generation of interference fringes of visually recognizable intensity and spacing due to the overlap of the interference fringes of the OPD elements 10 of the organic photodetector array 100 and the interference fringes of the sub-pixels 44S in the OPD elements 10 can be suppressed.

[0315] 〔Dummy sub-pixel array〕

[0316] Here, the arrangement structure of the plurality of organic photoelectric conversion layers (sometimes each organic photoelectric conversion layer is referred to as a "dummy sub-pixel 44SD" and the arrangement structure composed of the plurality of dummy sub-pixels 44SD is referred to as a "dummy sub-pixel array") that are isolated from each other in the projection diagram and the arrangement structure of the plurality of organic photoelectric conversion layers 44 that are spaced apart in the OPD element 10 in the projection diagram may be the same pattern structure. For example, both may be two-dimensional arrangement structures in the projection diagram. Furthermore, the spacing in the first direction and / or the second direction of the dummy sub-pixel array may be the same as the spacing in the first direction and / or the second direction of the sub-pixel array.

[0317] [Materials and Processes of Wiring Portion 120 , Collecting Portion 110 , and Dummy Pattern Portion 130 ]

[0318] The wiring portion 120 and the collector portion 110 are not particularly limited as long as they can be electrically connected to the conductive pattern 24P, and conventionally known materials and structures generally used for organic photodetector elements can be applied. As materials used for the wiring portion 120, the collector portion 110, and the dummy pattern portion 130, metals such as gold, silver, copper, aluminum, and molybdenum, metal laminates such as molybdenum / aluminum / molybdenum, or metal alloys thereof can be cited.

[0319] In addition, the second conductive pattern, the third conductive pattern and the dummy pattern portion 130 can use the same constituent materials, structures, and design adjustment ranges as the conductive pattern 24P of the [metal grid transparent electrode 20]. In addition, for the purpose of simplifying the manufacturing process, the second conductive pattern, the third conductive pattern and the dummy pattern portion 130 are preferably formed together with the conductive pattern 24P using the above-mentioned [method for manufacturing the metal grid transparent electrode 20]. In addition, from the perspective of suppressing the decrease in external quantum efficiency caused by the voltage drop of the collector 110, the above-mentioned metal, metal laminate, or metal alloy can be further stacked on the third conductive pattern using a vacuum evaporation method, a sputtering method, or the like.

[0320] 〔Pixel〕

[0321] The pixel size of the organic photodetector array of this embodiment is preferably 1 mm 2 Above and 25mm 2 Below, more preferably 2mm 2 Above and 21mm 2 Below, more preferably 4mm 2 Above and 16mm 2 Below, more preferably 6mm 2 Above and 13mm 2 Below, particularly preferably 7mm 2 Above and 11mm 2By making the pixel size 1 mm 2 As a result, the total effective sensor area in the pixel can be increased, and there is a tendency to increase the light detection current. On the other hand, by making the pixel size 25mm 2 The pixel density described below can be sufficiently increased, and the non-touch user interface device using the organic photodetector array of this embodiment can achieve the same operational feel as a touch user interface device using a conventional touch panel, which is preferred.

[0322] The pixel density of the organic photodetector array of the present embodiment is preferably greater than 2ppi and less than 15ppi, more preferably greater than 3ppi and less than 10ppi, further preferably greater than 3.5ppi and less than 9ppi, further preferably greater than 3.8ppi and less than 8ppi, and particularly preferably greater than 4ppi and less than 7ppi. By making the pixel density greater than 2ppi, the non-touch user interface device using the organic photodetector array of the present embodiment can fully achieve a smooth sense of operation. By making the pixel density less than 15ppi, the pixel size can be increased, and there is a tendency to increase the light detection current for the above reasons, so it is preferred. It should be noted that the ppi in this specification is pixels per inch (Pixel PerInchi).

[0323] The pixel density can be calculated using a known calculation method based on the arrangement pattern of the organic photodetector array. Figure 7 When the two-dimensional arrangement pattern is shown, it can be easily calculated using the following formula.

[0324]

[0325] Here, P Pixel-x (mm) and P Pixel-y (mm) are the distances between pixels in the X-axis direction (left and right on the paper) and the Y-axis direction (up and down on the paper). Figure 7 Organic photodetector array P Pixel-x =P Pixel-y =6.24 (mm), the pixel density is about 4ppi.

[0326] [3. Non-touch user interface]

[0327] Fig. 9 1 is a schematic diagram of a non-touch user interface device (hereinafter sometimes referred to as a “UI device”) according to the present embodiment. Fig.102 is a functional block diagram of the 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 the position of an input optical input signal based on an electrical output signal output from the OPD array 100. For example, the OPD array 100 is attached to the screen of the display D or the display body ( Fig. 9 In the figure, the two are shown separated for the sake of explanation. 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 be able to detect the position of the input optical input signal (the position irradiated by the incident light IL) by receiving the electrical output signal from a specific pixel.

[0328] Here, the display D corresponds to a portion 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. In addition to the display D, a display body also corresponds to a portion such as a wall surface or a screen that projects or displays an image by a projector.

[0329] The OPD array 100 is provided on such a display D or a display body. Therefore, the user can view the image displayed by the display body over the OPD array. In addition, the user can make the incident light IL incident on a specific position of the image displayed by the display body (for example, (1) the position where a menu icon is displayed in the image, (2) the position on the map displayed as an image), thereby causing the OPD array 100 to detect the incident light IL and output it as an electrical output signal.

[0330] The position detection unit 210 of the UI device 200 can detect that the incident light IL has been irradiated to a specific position on the image. For example, the position detection unit 210 of the UI device 200 can be composed of a storage medium that contains a computer program for receiving the electrical output signal output from the OPD array 100 in a non-volatile manner and a processor (GPU, CPU and other computing devices) for executing the computer program. Furthermore, the processor of the position detection unit 210 can be implemented, for example, by a processor (GPU, CPU and other computing devices) that constitutes an image generation unit P for generating an image signal that is possessed by a display device. In this case, the processor can be configured to receive the electrical output signal output from the OPD array 100 and generate an image signal displayed on the display D based on the electrical output signal (for example, (1) it is configured to generate an image signal for displaying a detailed menu of a menu icon on the display based on the incident light incident on the display position of the menu icon, (2) it is configured to generate an image signal of an enlarged map centered on the position on the map displayed in an image format based on the incident light incident on the position).

[0331] As described above, an OPD array 100 can be set on the display D or the display body, and the optical input signal is converted into an electrical output signal in the OPD element 10 at the position where the optical input signal as the incident light IL is irradiated, and the position where the optical input signal is irradiated is detected, thereby performing input operations on the screen of the display D or the display body.

[0332] 〔Optical input signal〕

[0333] Here, the optical input signal preferably includes light of at least a portion of the 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, so even if it is irradiated onto a display such as a monitor as an optical input signal, the visual recognizability of the display (the visual recognizability of the image displayed by the display, etc.) will not be suppressed.

[0334] The light intensity of the optical input signal at the irradiation surface of the OPD element 10 (for example, the lower surface of the transparent substrate 22 where the incident light IL is incident) is not particularly limited, and examples thereof include 10 -4 mW / cm 2 Above and 10mW / cm 2 The light intensity is more preferably 10 -3 mW / cm 2 Above 1mW / cm 2 Below, more preferably 10 -2 mW / cm 2 Above and 0.5mW / cm 2 By making the light intensity 10 -4 mW / cm 2 As described above, light detection becomes easy using the organic photodetector element of this embodiment. On the other hand, by setting the light intensity to 10 mW / cm 2 Next, there is a tendency that the influence on the human body can be further reduced.

[0335] Here, the optical input signal may be a signal having a predetermined frequency such as a pulse signal, a signal having a phase variation, or a signal having an amplitude variation, etc. For example, by configuring the optical signal having a certain output to be modulated and inputted as a pulse signal, it is easy to extract a detection signal of the optical input signal as a detection object from the entire optical detection signal including natural light, indoor light, and light generated by a display such as a display as external interference.

[0336] Signal modulation can use a known modulation method, without particular limitation, and frequency modulation, phase modulation, amplitude modulation, etc. can be cited. Frequency modulation is preferred, and the modulation frequency is preferably 0.5kHz or more and 20kHz or less, more preferably 0.6kHz or more and 10kHz or less, further preferably 0.7kHz or more and 5kHz or less, and particularly preferably 0.8kHz or more and 3kHz or less. By making the modulation frequency above 0.5kHz, it is easy to extract the detection signal of the optical input signal (for example, a continuous pulse signal of a rectangular wave of 1kHz) from the entire optical detection signal including the signal obtained by detecting the natural light, indoor light, and light emitted by the display body such as the detection display as external interference. On the other hand, by making the modulation frequency below 20kHz, there is a tendency for the modulation frequency 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, so it is easy to extract the detection signal of the optical input signal, which is preferred. The method of extracting the detection signal of the optical input signal modulated by the signal from the entire optical detection signal can use a known signal processing method. 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-stop filter, a lock-in amplifier, etc. may be used, or these may be used in combination.

[0337] The UI device 200 may further include a pointer PD as a pointer for outputting an optical input signal. Fig. 9 Here, the indicating part PD may be equipped with a modulation unit for generating a frequency modulation, phase modulation or amplitude modulation signal as described above. The OPD array can detect the position of the light input signal irradiated by the indicating part PD, so that the screen input operation can be performed.

[0338] Alternatively, the UI device may be configured to cause a hand or finger as the indicating part PD to reflect light outputted by the light source LS and detect the reflected light as an optical input signal. Here, the light source LS may be configured to form a planar projection beam (surface light source LS2) formed in space. Fig. 9 (A) shows an embodiment of forming a surface light source LS2 parallel to the display in space based on the light output by the point light source LS. The user can extend a hand or finger as an indicating member PD at a predetermined position on the surface light source LS2. The light at the extended position becomes reflected light and enters the OPD array 100, so the UI device 200 can detect the position irradiated by the optical input signal.

[0339] The UI device may further include a detection position determination means for determining the detection position based on the detection signal (electrical output signal) of the optical input signal obtained by the OPD array. As such a detection position determination means, a conventionally known detection position determination means mounted on a touch panel or the like may be used. For example, the detection position determination means may be composed of a computer program for executing the following calculation processing and a processor for executing the computer program, wherein the calculation processing respectively calculates Figure 7 The signal center of gravity position in the X-axis direction (left-right direction of the paper) and the signal center of gravity position in the Y-axis direction (up-down direction of the paper) shown, and the signal center of gravity position is determined as the detection position. The computer program may also include commands for executing part or all of the various calculation processes described in this embodiment. In addition, the computer program can be contained in a recording medium such as a semiconductor element that can record information non-transitory. In addition to the method of determining the detection position based on the signal center of gravity, a method of fitting the detection signal in the X-axis direction and the detection signal in the Y-axis direction of the figure by Gaussian functions, Lorentz functions, etc., respectively, and calculating the peak position and determining the detection position can also be used.

[0340] Example

[0341] The present invention will be described in more detail below using Examples and Comparative Examples. The present invention is not limited to the following Examples.

[0342] <<Example A>>

[0343] The optical characteristics and optical model of an organic photodetector element using a metal grid transparent electrode are described in detail below.

[0344] [Example A1]

[0345] 《Fabrication of Metal Grid Transparent Electrodes》

[0346] [Preparation of transparent substrate]

[0347] As a transparent substrate, alkali-free glass (manufactured by Corning Incorporated, product name: EAGLE XG, thickness 1.1 mm) was used.

[0348] [ink]

[0349] Cuprous oxide nanoparticles with a particle size of 21 nm, a dispersant (manufactured by BYK, product name: Disperbyk-145), a surfactant (manufactured by Seimei Chemical Co., Ltd., product name: S-611), and ethanol were mixed and dispersed to prepare an ink containing 20 mass % of cuprous oxide nanoparticles.

[0350] [Manufacturing of Metal Grid Transparent Electrode 20]

[0351] First, ink is applied to the surface of the transfer medium. Then, the surface of the transfer medium coated with ink is placed opposite to a plate having grooves with a conductive pattern, and pressed to make them contact, so that a portion of the ink on the surface of the transfer medium is transferred to the surface of the convex portion of the plate. After that, the surface of the transfer medium coated with the remaining ink is placed opposite to a transparent substrate, and pressed to make them contact, so that the desired conductive pattern-shaped ink is transferred to the transparent substrate. Next, the coating film (dispersion coating film) of the conductive pattern-shaped ink on the transparent substrate is irradiated with 1.2kW plasma for 496 seconds in a reducing atmosphere, and the cuprous oxide in the dispersion coating film is reduced to copper. A metal grid transparent electrode with a conductive pattern having a mesh pattern is obtained by a sintering process to form a copper metal component sintered film.

[0352] 《Evaluation of Metal Grid Transparent Electrodes》

[0353] [Measurement of line width, gap, and film thickness, and calculation of repeating unit area and aperture ratio]

[0354] The line width W of the metal wiring of the conductive pattern was measured using a plan view photograph obtained by confocal laser microscopy for the obtained metal grid transparent electrode. TCE and film thickness t TCE , and the gap G of the conductive pattern TCE In addition, these values ​​are used to calculate the repeating unit area S of the conductive pattern. TCE-unit and opening ratio A TCE The results are shown in Table 1.

[0355] [Calculation of visible light transmittance]

[0356] Multiply the visible light transmittance of the transparent substrate (92%) by the aperture ratio A of the conductive pattern. TCE The visible light transmittance VLT of the metal grid transparent electrode is calculated TCE The results are shown in Table 1.

[0357] [Table 1]

[0358]

[0359] a) Pass A TCE The calculated value was multiplied by the visible light transmittance (92%) of the substrate.

[0360] [Measurement of Sheet Resistance]

[0361] Conductivity and film thickness of metal wiring used TCE and opening ratio A TCECalculate the sheet resistance of the conductive pattern of the metal grid transparent electrode. The conductivity of the metal wiring is calculated by the following method. First, the sheet resistance of the inspection area composed of the conductive pattern formed simultaneously with the metal grid transparent electrode is measured using LORESTA-GP (product name, manufactured by Mitsubishi Chemical Corporation). Next, the conductivity of the metal wiring is calculated based on the obtained sheet resistance using the film thickness and aperture ratio measured from the planar photograph of the conductive pattern of the inspection area based on a confocal laser microscope. The results of the calculated sheet resistance of the metal grid transparent electrode are shown in Table 1.

[0362] Fabrication of organic photodetector elements

[0363] [Formation of Electron Transport Layer]

[0364] On the metal grid transparent electrode, a-IGZO (film thickness 16 nm) as an electron transport layer was deposited by sputtering. Next, in order to remove unnecessary portions of a-IGZO, a-IGZO was patterned by photolithography and wet etching.

[0365] [Formation of insulating layer]

[0366] Next, SU-8 as an insulating layer was applied by spin coating, and soft baking, pattern exposure, and development were performed to form an insulating layer (film thickness: 1.8 μm) having an opening OP corresponding to a sub-sensor region described later.

[0367] [Formation of solid-state film of organic photoelectric conversion layer]

[0368] PTB7-Th (also known as PCE-10, E g opt =1.60 eV, HOMO = -5.20 eV, LUMO = -3.59 eV) 8 mg and IEICO-4F (E g opt =1.24eV, HOMO=-5.44eV, LUMO=-4.19eV) 12mg. Next, 40μL of naphthalene chloride was added to each 1mL 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 wet-filmed by spin coating, dried at room temperature, and annealed at 60°C for 20 minutes to form a dry film with a thickness of t OPD It is a 300nm solid film of an organic photoelectric conversion layer having a bulk heterojunction structure.

[0369] [Formation of Sub-Pixels and Sub-Pixel Arrays]

[0370] Next, using a known photolithography patterning technique for organic semiconductor materials as described in Non-Patent Document 3, etc., the solid film of the obtained organic photoelectric conversion layer is patterned into a sub-pixel array having a pattern structure in which substantially square sub-pixels are two-dimensionally arranged at equal intervals along the orthogonal coordinate axes of the X-axis and the Y-axis. The design of the formed sub-pixel array is as follows.

[0371] <Design of organic photodetector elements>

[0372] (X-axis direction, Y-axis direction)

[0373] Sub-pixel: 60μm×60μm, S subOPD : 3600μm 2

[0374] Sub-sensor area: 50μm×50μm, S sub-sensor : 2500μm 2

[0375] Pattern pitch P subOPD :240μm×240μm

[0376] Sub-pixel area occupancy within the pattern unit Γ subOPD : 6.25%

[0377] [Formation of hole transport layer and anode]

[0378] As a hole transport layer, MoO was formed on the entire organic photodetector element by vacuum evaporation. x (Thickness: 60 nm) Next, ITO (thickness: 100 nm, sheet resistance: 40 Ω / sq.) was deposited as a transparent electrode of the anode by sputtering so as to be stacked on the hole transport layer.

[0379] [Formation of sealing layer]

[0380] Finally, as a sealing layer, a PET film (125μmm, Melinex(R) ST504 TM ) is a barrier laminate film (total film thickness 160 μm) formed by sequentially laminating a known thin film sealing layer as described in Non-Patent Document 2 and an adhesive layer having gas barrier properties. The barrier laminate film is laminated in such a way that the adhesive layer is in contact with the anode, and is laminated by pressing, thereby sealing the organic photodetector element.

[0381] 《Evaluation of optical properties of organic photodetector elements》

[0382] The visible light transmittance of the organic photodetector element was calculated by the following method. The light transmission spectrum of the organic photodetector element was measured using an ultraviolet-visible-near infrared spectrometer (UV-vis-NIR spectroscopy, Cary5000 manufactured by Agilent). Based on the obtained light transmission spectrum, the visible light transmittance was calculated based on JIS R 3106:2019 or ISO9050:2003. The results are shown in Table 1.

[0383] [Comparative Example A1]

[0384] The [formation of sub-pixels and sub-pixel arrays] of Example A1 was not performed, but a solid-state film organic photoelectric conversion layer was used. In addition, a metal grid transparent electrode and an organic photodetector element using the same were prepared and evaluated by the same operation as Example A1. The results are shown in Table 1.

[0385] According to Example A1 and Comparative Example A1, it can be seen that by setting the organic photoelectric conversion layer to an island-shaped sub-pixel or a sub-pixel array structure formed by arranging two or more such sub-pixels, even when using a near-infrared detection type organic photoelectric conversion layer with low visible light transmittance, visible light can be efficiently transmitted from the portion where the sub-pixel is not formed, thereby improving the visible light transmittance of the organic photodetector element as a whole. Specifically, the visible light transmittance of the organic photodetector element in the sub-pixel portion of Example A1 in the stacking direction is about 17%, which is the same as that of Comparative Example A1. In Example A1, by increasing the area occupancy of the sub-pixel portion Γ subOPD Adjusted to 6.25%, visible light transmittance increased to 64%.

[0386] Optical modeling of light transmission spectra of organic photodetector elements

[0387] The light transmission spectrum T(λ) of an organic photodetector element of a sub-pixel (or sub-pixel array) having an organic photoelectric conversion layer and using a metal grid transparent electrode as a cathode can be modeled using the following equation.

[0388] T(λ)={Γ subO PD ·T OPD (λ)+(1-Γ subOPD )·T open (λ)}×{(1-A TCE )·T Cu (λ)+A TCE}

[0389] Here, T OPD(λ) is the light transmission spectrum of the multilayer body of transparent substrate / electron transport layer / organic photoelectric conversion layer / hole transport layer / anode / sealing layer based on the above materials and structures, and is a model of the light transmission spectrum of the organic photodetector element in the stacking direction of the sub-pixel part excluding the conductive pattern. In addition, similarly, T OPEN (λ) is the light transmission spectrum of the multilayer body composed of the above materials and structures of transparent substrate / electron transport layer / insulating layer / hole transport layer / anode / sealing layer, which is a model of the light transmission spectrum in the stacking direction of the organic photodetector element in the part where the sub-pixels are not formed except for the conductive pattern. Cu (λ) is the light transmission spectrum of the metal wiring itself. OPD (λ) and T OPEN (λ) The simulation was performed using Setfos, an optoelectronic electrical and optical properties simulation software manufactured by FLUXiM AG, using an optical calculation method based on the Transfer Matrix formalism. 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 above-mentioned film thickness were used as input parameters for the optical simulation. Cu (λ), a stacked structure simulating the distribution of copper and cuprous oxide and the distribution of voids in metal wiring is used as a model, and optical simulation is performed on this model using the same method. Based on the calculated light transmission spectrum, the visible light transmittance is calculated based on JIS R 3106:2019 or ISO9050:2003. OPD The visible light transmittance of (λ) is 22%, T OPEN The visible light transmittance of (λ) is 80%, T Cu The visible light transmittance of (λ) is 10%.

[0390] Fig.11 The light transmission spectrum of the organic photodetector element of Example A1 is compared with the light transmission spectrum calculated using the above optical model. Fig.11 It can be seen 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 is 64%, which is a value close to the measured value (64%) of Example A1. In addition, for Comparative Example A1, it is also possible to reproduce the light transmission spectrum of the organic photodetector element of the present invention represented by Example A1 by using Γ subOPD The same modeling was performed by setting it to 100%. Fig.12 Comparison of the light transmission spectrum obtained by modeling the comparative example A1 is shown. Fig.12It is clear that the optical model can also reproduce the measured light transmission spectrum of Comparative Example A1. In addition, the visible light transmittance (18%) calculated by the optical model is also close to the measured value (17%) of Comparative Example A1.

[0391] <<Example B>>

[0392] The electrical characteristics of an organic photodetector element using a metal grid transparent electrode are described in detail below.

[0393] [Example B1]

[0394] By changing the pattern of the grooves of the plate used in the pattern forming step, the line width W in the conductive pattern of the metal grid transparent electrode was changed as shown in Table 2. TCE and gap G TCE . In addition, the firing process of the metal grid transparent electrode is changed to irradiate 1.2kW plasma for 540 seconds. In addition, slit die coating is used instead of spin coating in [Film formation of solid film of organic photoelectric conversion layer], and the drying and annealing steps are changed to be performed at 60°C for 5 minutes. Furthermore, in the [Formation of sub-pixels and sub-pixel arrays] of Example A1, the design changes are made as described below. In addition, the metal grid transparent electrode and the organic photodetector element using the same are produced by the same operation as Example A1.

[0395] <Design of organic photodetector elements>

[0396] (X-axis direction, Y-axis direction)

[0397] Sub-pixel: 70μm×70μm, S subOPD : 4900μm 2

[0398] Sub-sensor area: 50μm×50μm, S sub-sensor : 2500μm 2

[0399] Pattern pitch P subOPD :240μm×240μm

[0400] Number of sub-pixels N subOPD : 9 × 9, 81

[0401] Sub-pixel area occupancy within the pattern unit Γ subOPD :8.5%

[0402] Total effective sensor area S total-sensor :0.2025mm 2

[0403] Pixel size: 1.99mm×1.99mm, approximately 4.0mm 2

[0404] The metal grid transparent electrode was evaluated in the same manner as in Example A1.

[0405] The optical microscope image of the organic photodetector element of Example B1 is shown in Fig.13 (It should be noted that the same symbols are used to indicate the structures having the same functions as those in other embodiments, and detailed descriptions are omitted).

[0406] 《Characteristics evaluation of organic photodetector elements》

[0407] [Evaluation of current density-voltage characteristics (JV characteristics)]

[0408] The current density-voltage characteristics were evaluated at room temperature in a glove box with a nitrogen atmosphere. First, external terminals from a semiconductor parameter analyzer (Agilent 4155C) were connected to the collectors electrically connected to the cathode and anode of the organic photodetector element, respectively. Next, a voltage scan was performed at a scan rate of 5 mV / s from -3 V to +2 V to measure the current of the organic photodetector element. Finally, the measured current was divided by the total effective sensor area S total-sensor The dark current density (J dark )-voltage (V) characteristics were measured by performing the above operation in a dark room. In addition, the photocurrent density (J photo )-V characteristics by illuminating the light intensity (I P ) is about 0.30 mW / cm 2 The above operation is performed while measuring the optical input signal with a wavelength (λ) of 850 nm. Fig.14 Show J dark -V Characteristics and J photo In addition, the dark current density when the applied voltage was -2 V is summarized in Table 2.

[0409] [Evaluation of external quantum efficiency (EQE) characteristics]

[0410] The external quantum efficiency was measured using a custom-made installation device comprising the following configuration. Configuration: tungsten halogen lamp, monochromator (Oriel, Cornerstone 130), preamplifier (Stanford Research Systems SR570) and lock-in amplifier (Stanford Research Systems SR830 DSP). The organic photodetector element was measured in a box set in a nitrogen atmosphere sealed by a quartz window. While applying a voltage of -2V to the organic photodetector element, the wavelength of the optical input signal was scanned within 300nm to 1100nm in steps of 10nm, while the optical input signal was irradiated to the organic photodetector element through an opening of a circle with a diameter of 1mm, and the photodetection current was measured. The external quantum efficiency of the organic photodetector element at each wavelength is calculated as follows: the measured photodetection current is divided by the total effective sensor area of ​​the sub-pixel array in the irradiation area, and the calculated photocurrent density is converted into an external quantum efficiency based on a standard curve of a Si photodiode for calibration measured under the same conditions, and thus calculated. Fig.15 The wavelength (λ) dependence of the external quantum efficiency (EQE) when the applied voltage is −2 V is shown.

[0411] [Light intensity (I P )'s responsiveness evaluation]

[0412] Using the same device as the current density-voltage characteristic measurement, under the same environment, the -4 mW / cm 2 ~7.5×10 -1 mW / cm 2 The light intensity (I P ) to measure the photocurrent density (J) of the organic photodetector element photo ) light intensity (I P It should be noted that the wavelength of the optical input signal is 850nm, and the voltage applied to the organic photodetector element is -2V. Fig.16 Shows the light intensity (I P )-photocurrent density (J photo )’s picture.

[0413] [Calculation of visible light transmittance]

[0414] Based on the above optical model, the visible light transmittance of the organic photodetector element was calculated using the parameters described in Table 2. Table 2 shows the results.

[0415] [Table 2]

[0416]

[0417] a) Pass A TCE The calculated value was multiplied by the visible light transmittance (92%) of the substrate.

[0418] b) Using the simulated values ​​of the optical model

[0419] [Examples B2 to B4]

[0420] By changing the pattern of the grooves of the plate used in the pattern forming step as shown in Table 2, the line width W in the conductive pattern of the metal grid transparent electrode is changed. TCE and gap G TCE Except for the above, 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.

[0421] like Fig.13 As shown, in the projection diagram when projected from the upper surface, the area where the sub-sensor area 44SS is provided overlaps at least partially with the area where at least one metal wiring 24 is provided. In other words, the sub-sensor area 44SS is formed on at least a portion of at least one (for example, two or more than three) metal wirings 24. At least one (for example, two or more than three) metal wirings 24 extend in a manner intersecting two different sides of the sub-sensor area 44SS. In addition, at least one (for example, two or more than three) metal wirings 24 extend in a manner intersecting two different sides of the first sub-sensor area 44SS, and extend in a manner intersecting two different sides of the second sub-sensor area 44SS.

[0422] Moreover, in Fig.13 In the embodiment, at least one (eg, two or more) second metal wirings 24 extending in a direction different from that of the first metal wiring 24 (eg, a vertical direction) also satisfy the same relationship as the first metal wiring 24.

[0423] Therefore, in the projection image when projected from the upper surface, the area where the sub-sensor area 44SS is provided overlaps with the area where at least one first metal wiring 24 is provided in at least a portion, and the area where the same sub-sensor area 44SS is provided overlaps with the area where at least one second metal wiring 24 extending in a direction different from the first metal wiring 24 is provided in at least a portion.

[0424] Thus, according to Fig.13 It can be seen that, in at least one direction, a sub-sensor region 44SS is formed on at least one of the metal wirings 24 extending in the same direction within the conductive pattern 24P and facing a direction substantially perpendicular to the extending direction.sub-sensor / S TCE-unit 2 to 25, and 1 or more, so that even if the relative positions of the conductive pattern 24P and the sub-pixel 44S are offset during the lamination process, a portion of the sub-sensor region 44SS is provided in a manner overlapping the metal wiring 24. As can be seen from this, a high external quantum efficiency of 15% or more is obtained in at least a portion of the near-infrared wavelength range of 780 nm to 1200 nm (see Tables 2 and 3). Fig.15 ). Furthermore, as shown in Table 2, it can be seen that these organic photodetector elements show 10 -5 mA / cm 2 The extremely low dark current density is as follows: In addition, the organic photodetector elements of Examples B1 to B4 exhibited high visible light transmittance of 60% or more.

[0425] As can be seen from the above, the organic photodetector element of the present invention exhibits high light detectability due to high external quantum efficiency and extremely low dark current density, and can simultaneously exhibit high visible light transmittance (see Tables 2 and Fig.14 ).

[0426] Furthermore, if Fig.16 As shown, it can be seen that the organic photodetector element of Example B1 has a -4 mW / cm 2 Up to 1mW / cm 2 The photodetection current responds linearly over a wide range of light intensities.

[0427] <<Example C>>

[0428] The following specifically describes the appropriate range of design of the metal grid transparent electrode that contributes to improving the external quantum efficiency (EQE) of the organic photodetector element using the metal grid transparent electrode.

[0429] 《Simulation of External Quantum Efficiency (EQE)》

[0430] 〔simulation〕

[0431] The simulation of the organic photodetector element using the metal grid transparent electrode was performed using both Setfos, an optoelectronic electrical and optical characteristics simulation software manufactured by FLUXIMA AG, and LAOSS, a large-area organic semiconductor simulation software manufactured by FLUXIMA AG.

[0432] Setfos is a software that uses the optical properties (especially light absorption properties) of a multilayer organic photodetector element obtained through simulation based on the Transfer matrix formalism to calculate the carrier distribution of electrons and holes generated by light excitation, and simulates the charge transport process of the electrons and holes based on the mathematical model of Drift-diffusion, thereby simulating the electrical properties of the organic photodetector element such as photocurrent density.

[0433] The multilayer bodies of the organic photodetector elements provided on the metal wiring and the openings of the conductive pattern were modeled using Setfos, and J was simulated for each multilayer body. photo -V characteristics. The multilayer body on the metal wiring is transparent substrate / metal wiring / electron transport layer / organic photoelectric conversion layer / hole transport layer / anode / sealing layer, and the multilayer body on the opening is transparent substrate / pseudo-completely transparent electrode / electron transport layer / organic photoelectric conversion layer / hole transport layer / anode / sealing layer.

[0434] Here, the pseudo-fully transparent electrode refers to a pseudo-electrode without light absorption added for the calculation program of Setfos. As input parameters for the optical property simulation, the wavelength dependence and film thickness of the optical constants (refractive index: n, extinction coefficient: k) used in the "Optical Model of Light Transmission Spectra of Organic Photodetector Elements" are used. In addition, the input parameters for the electrical property simulation, i.e., the mobility of electrons and holes in each layer, the energy level, etc., are set with reference to the literature values.

[0435] Next, LAOSS was used to calculate the surface potential distribution and current density distribution of the electron transport layer / metal grid transparent electrode using two-dimensional finite element modeling (2D FEM). Specifically, the surface potential distribution and current density distribution were calculated until the differential equations expressing the surface potential of each element and J calculated by Setfos were converged in the entire system. photo The relationship between the local current density calculated from the -V characteristics and the voltage drop in accordance with Ohm's law during the diffusion of the local current density along the plane direction of the electron transport layer / metal grid transparent electrode. The current density J of the entire system is calculated from the current density distribution s (λ), and the external quantum efficiency (EQE) was calculated using the following formula.

[0436]

[0437] Here, λ is the wavelength of light, I P (λ) is the light intensity, 1.05 mW / cm 2 In addition, q is the charge base, h is Planck's constant, and c is the speed of light.

[0438] The input parameters of the 2D FEM for simulating Example B1 are as follows.

[0439] ·Conductive pattern setting: mesh pattern, W TCE 1μm, G TCE 19μm

[0440] Sheet resistance of the metal wiring portion of the metal grid transparent electrode: 2.6Ω / sq.

[0441] Sheet resistance of electron transport layer: 35×10 9 Ω / sq.

[0442] Applied voltage: -2V

[0443] [Comparison between simulation and measured values]

[0444] Fig.17 Comparison between simulated external quantum efficiency (EQE) and actual measurement (Example B1) is shown. It was confirmed that the measured external quantum efficiency can be reproduced by simulation.

[0445] [Optimizing the design of metal grid transparent electrodes through simulation]

[0446] Using this simulation, the line width W of the metal wiring is calculated by simulation. TCE The gap G of the conductive pattern is set to 0.5 μm to 10 μm. TCE In (G TCE / W TCE ) is 1.0 or more and (W TCE +G TCE ) when the external quantum efficiency (EQE) varies within the range below 80μm. Figure 4 The gap G of the external quantum efficiency (EQE) simulated for each line width is shown. TCE Dependency. Similarly, Figure 5 The external quantum efficiency (EQE) simulated for each line width is shown in (G TCE / W TCE ) dependency. Similarly, Figure 6 The external quantum efficiency (EQE) simulated for each line width is shown in (G TCE ·A TCE )dependency.

[0447] Depend on Figure 4 and Figure 5 It can be seen that by changing the line width W of the metal wiring of the metal grid transparent electrode TCE The gap of the conductive pattern is set to G TCE And (G TCE / W TCE) to above 1.0 and G TCE Adjusting to below 45 μm can improve the external quantum efficiency (EQE) of organic photodetector elements using metal grid transparent electrodes. Figure 6 It can be seen that when the aperture ratio of the conductive pattern is set to A TCE When (G TCE ·A TCE ) is adjusted to 0.25 μm·% or more and 45 μm·% or less, the external quantum efficiency (EQE) of the organic photodetector element using the metal grid transparent electrode can be further improved. It is believed that this indicates that by reducing the diffusion distance (G) of the electrons generated in the organic photoelectric conversion layer provided on the opening of the conductive pattern in the electron transport layer in the plane direction, TCE ), thereby making the surface potential distribution uniform and improving the charge collection efficiency η cc , while reducing the metal wiring W TCE , increase the aperture ratio (A TCE ) can suppress the light-shielding effect of the metal wiring and improve the light receiving efficiency of the organic photoelectric conversion layer, thereby improving the external quantum efficiency (EQE) of the organic photodetector element.

[0448] <<Example D>>

[0449] An organic photodetector array including organic photodetector elements using a metal grid transparent electrode and a touchless user interface device using the same will be described in detail below.

[0450] [Example D]

[0451] Based on the results of Example B and Example C, the same metal grid transparent electrode design as that of Example B1 was installed in the organic photodetector array. In addition, the organic photodetector array has a structure having a pattern in which pixels composed of the organic photodetector elements described below are 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.

[0452] <Design of organic photodetector elements (pixels)>

[0453] (X-axis direction, Y-axis direction)

[0454] Sub-pixel: 70μm×70μm, S subOPD : 4900μm 2

[0455] Sub-sensor area: 50μm×50μm, S sub-sensor : 2500μm 2

[0456] Pattern pitch PsubOPD :240μm×240μm

[0457] Number of sub-pixels N subOPD : 14 x 14, 196

[0458] Sub-pixel area occupancy within the pattern unit Γ subOPD :8.5%

[0459] Total effective sensor area S total-sensor : 0.49mm 2

[0460] Pixel size: 3.19mm×3.19mm, approximately 10.2mm 2

[0461] <Design of organic photodetector array>

[0462] (X-axis direction, Y-axis direction)

[0463] Sensor area: 96.77mm×96.77mm,

[0464] Pixel pitch: 6.24mm×6.24mm

[0465] Number of pixels: 16×16, 256

[0466] Pixel density: 4.2ppi

[0467] 《Manufacturing of metal grid transparent electrode, wiring part, current collecting part and dummy pattern part》

[0468] The metal grid transparent electrode 20, the wiring portion 120, the collector portion 110 and the dummy pattern portion 130 are formed together by the following printing and firing process. The metal grid transparent electrode 20 provided in each pixel is formed into a conductive pattern with a line width W similar to that of Example B1. TCE and gap G TCEThe corresponding groove pattern is arranged on the plate in a manner. In addition, for the wiring portion 120 and the dummy pattern portion 130, the corresponding groove pattern is arranged on the above-mentioned plate in a manner to become the aperture ratio described later. Similarly, for the collector portion 110, the corresponding groove pattern is arranged on the above-mentioned plate in a manner to become the occupancy area ratio described later. Using the above-mentioned plate, a conductive pattern-shaped ink coating film (dispersion coating film) corresponding to the metal grid transparent electrode 20, the wiring portion 120, the collector portion 110 and the dummy pattern portion 130 is printed on the transparent substrate by the same pattern forming operation as in Example B1. Then, 1.2kW plasma is irradiated for 590 seconds under a reducing atmosphere, and 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 collector portion 110, and the dummy pattern portion 130 are manufactured by the same firing process operation as in Example B1. It should be noted that the conductive pattern 24P, the second and third conductive patterns, and the dummy pattern portion are all mesh patterns.

[0469] Each wiring portion and each collector portion are electrically independent structures provided in each pixel. In addition, the second conductive pattern of each wiring portion is a structure that electrically connects the conductive pattern 24P of each pixel and the third conductive pattern of each collector portion.

[0470] 《Evaluation of metal grid transparent electrode, wiring part, current collection part, and dummy pattern part》

[0471] For the metal grid transparent electrode 20, the wiring portion 120, the collector portion 110, and the dummy pattern portion 130, the gaps between the conductive pattern 24P, the second and third conductive patterns, and the dummy pattern portion, as well as the line width and film thickness of the metal wiring are measured using representative plan photographs obtained using a confocal laser microscope. These values ​​are used to calculate the repeating unit area S of the conductive pattern 24P. TCE-unit and opening ratio A TCE The results are shown in Table 3.

[0472] [Table 3]

[0473]

[0474] In addition, for the second conductive pattern and the dummy pattern portion, the respective aperture ratios A are calculated using these numerical values. wire and opening ratio A dummy The results are shown below.

[0475] <Wiring portion (second conductive pattern)>

[0476] Line width: 1μm

[0477] Gap: 15μm

[0478] Aperture ratio A wire : 88%

[0479] <Dummy pattern section>

[0480] Line width: 1μm

[0481] Gap: 15μm~19μm

[0482] Aperture ratio A wire : 88%~90%

[0483] As shown in Table 3, the aperture ratio A of the conductive pattern of Example D is TCE is 87%. Therefore, wire and A dummy All in A TCE Within ±10%. As a result, the area outside the pixel is also adjusted to have the same visible light transmittance as the pixel, making the visibility uniform.

[0484] In addition, for the third conductive pattern, the occupied area ratio Γ is calculated using these values. pad The results are shown below.

[0485] <Current collecting portion (third conductive pattern)>

[0486] Line width: 5μm

[0487] Gap: 10μm

[0488] ·Occupancy rate Γ pad : 55.6%

[0489] Fabrication of organic photodetector arrays

[0490] By the same operation as in Example B1, an electron transport layer and an insulating layer are sequentially formed on the obtained metal grid transparent electrode. The opening OP of the insulating layer on the metal grid transparent electrode is formed as follows: on each pixel, it is patterned in a manner corresponding to the sub-sensor area of ​​the above-mentioned <Design of the organic photodetector element (pixel)>. Next, by the same operation as in Example B1, the above-mentioned organic photoelectric conversion layer forming ink is used to form a solid film of the organic photoelectric conversion layer on the entire surface of the organic photodetector array by slit coating. Then, the organic photoelectric conversion layer is patterned by the same operation as in Example B1 except that the organic photoelectric conversion layer is changed to the <Design of the organic photodetector element (pixel)> described in [Formation of sub-pixels and sub-pixel array] of Example B1, and a sub-pixel array is formed on each pixel. When the above-mentioned organic photoelectric conversion layer is patterned, for the entire surface of the organic photodetector array, in the area outside the pixel (the so-called area where the opening OP of the insulating layer is not provided), a dummy sub-pixel array with the same design as the sub-pixel array is formed on the insulating layer. The dummy sub-pixel array is separated from the metal grid transparent electrode 20, the wiring portion 120, and the dummy pattern portion 130 by an insulating layer, and therefore is a structure that does not function as an organic photodetector element. In addition, by the same operation as in Example B1, an organic photodetector array is produced in a manner to become <Design of an organic photodetector array>, in which 16 pixels in the X-axis direction and 16 pixels in the Y-axis direction are arranged two-dimensionally at equal intervals along the orthogonal coordinate axes, for a total of 256 pixels formed by organic photodetector elements.

[0491] 《Evaluation of organic photodetector arrays》

[0492] A flexible printed circuit board was crimped onto the collector 110 of the organic photodetector array and connected to an external control circuit. The organic photodetector array and the external control circuit were then assembled into a housing in such a way that only the array sensor region of the organic photodetector array was exposed. In addition, the external control circuit was connected to a personal computer for control via a USB to evaluate the organic photodetector array.

[0493] The dark current density (J) of each pixel was measured in a dark room when the applied voltage was -2V. dark ). In addition, in the same dark room, the array sensor area of ​​the organic photodetector array was irradiated with a wavelength of 850 nm and a light intensity of 46 μW / cm 2 The photocurrent density (J) of each pixel was measured when the applied voltage was -2V. photo ). Fig.18 A bar graph showing the dark current density and photocurrent density of the organic photodetector array is shown. Based on the bar graph, the mode values ​​of the dark current density and the photocurrent density are calculated, respectively. The results are shown in Table 3.

[0494] In addition, the external quantum efficiency (EQE) was calculated from the obtained mode value of the photocurrent density.

[0495] As can be seen from Table 3, in the case of the organic photodetector array, the same electrical characteristics as those of the organic photodetector element of Example B1 were obtained. This shows that the organic photodetector array of the present invention can be mass-produced on a large scale and industrialized.

[0496] 《Composition and evaluation of touchless user interface devices》

[0497] [Configuration of non-touch user interface device]

[0498] The organic photodetector array housed in the housing is arranged on the display of the above-mentioned personal computer for control.

[0499] In addition, as the optical input signal, a laser pointer that can emit three types of rectangular wave continuous pulse optical signals with a wavelength of 850nm and frequencies of 1202Hz, 962Hz, and 801Hz is used. The laser pointer has two buttons, a transmission button A and a transmission button B, and has a mechanism that can change the frequency by operating these buttons. The details are as follows.

[0500] When no transmitting button is pressed: 1202Hz rectangular wave continuous pulse light signal

[0501] When the transmitting button A is pressed: 962Hz rectangular wave continuous pulse light signal

[0502] When the launch button B is pressed: 801Hz rectangular wave continuous pulse light signal

[0503] It should be noted that the light intensity of the laser pointer emitting surface is about 18mW / cm at each frequency. 2 .

[0504] [Signal processing of light detection signals]

[0505] The light detection signal of the organic photodetector array passes through a digital bandpass filter corresponding to each of the three frequencies, thereby extracting only the detection signal of the light input signal from the entire light detection signal including the signal of detecting natural light, indoor light, and light emitted by a display such as a display as external interference. In addition, the following signal processing is simultaneously performed: only the largest light detection signal is selected from the three frequencies, and it is taken out as a signal for the detection position determination means described later.

[0506] In addition, the obtained detection signal is fitted with Gaussian functions in the X-axis direction and the Y-axis direction, and the signal center of gravity position in the X-axis direction and the signal center of gravity position in the Y-axis direction are calculated based on the peak position. A detection position determination means is used to determine the detection position using these signal center of gravity positions.

[0507] [Screen operation using non-touch user interface devices]

[0508] Using the determined detection position, software that enables movement of the mouse, scrolling up and down, left and right, and zooming in and out on a map of a map operation application (Google Earth manufactured by Google Inc.) is installed by the means described below.

[0509] Regarding the movement of the mouse on the map, the movement of the mouse is controlled using the detection position of the light detection signal in response to the continuous pulse light signal of the 1202 Hz rectangular wave.

[0510] Regarding the scrolling operation of the map, a light detection signal of a continuous pulse light input signal of a 962 Hz rectangular wave emitted in response to pressing the emission button A is detected, and the scrolling operation is controlled using the displacement of the detection position.

[0511] Regarding the zooming operation of the map, a light detection signal is detected in response to a continuous pulse light input signal of an 801Hz rectangular wave emitted by pressing the emission button B, and a decrease (increase) in the spot diameter of the light detection position when the distance between the laser pointer and the organic photodetector array is shortened (lengthened), thereby controlling the zooming-in (zooming-out) operation.

[0512] Fig.19 a. is a photograph of a map of a map operation application being scrolled left and right using the non-touch user interface device of the present invention. Fig.19 b. is a photograph of a map of a map operation application being zoomed in using the non-touch user interface device of the present invention.

[0513] In addition, as another method, a non-touch user interface device is constructed as follows: a surface light source is used to form a continuous pulse signal of a rectangular wave with a wavelength of 850nm and a frequency of 1202Hz using a plurality of near-infrared LED light sources arranged in a manner surrounding the periphery of the array sensor area, and reflected light generated by touching the surface light source with a finger as an indicating member is used as an optical input signal. The surface light source is adjusted to project onto a parallel plane separated from the organic photodetector array.

[0514] The optical input signal is detected by the organic photodetector array, and the detection position is determined by the same operation as the above-mentioned [Signal Processing of the Optical Detection Signal]. The detection position is used to install software control that can select the button displayed on the display.

[0515] Fig. 20 This is a photograph of a user operating a button on a simulated ATM screen on a display by touching a near-infrared light source formed in space with a finger using the non-touch user interface device of the present invention.

[0516] according to Fig.19 and Fig. 20 An organic photodetector array formed by arranging two or more organic photodetector elements using the metal grid transparent electrode of the present invention which has both high visible light transmittance and high external quantum efficiency can detect light input signals without suppressing the visual recognizability of a display such as a display, and is suitable for use as a non-touch user interface device.

[0517] [Second embodiment]

[0518] Different embodiments of the present invention are described below. Among them, for those skilled in the art, it can be understood that the components that play the same or similar functions as other embodiments are appropriately marked with the same or similar names or symbols, and the description is omitted or simplified, and the description is centered on the different parts.

[0519] Fig.21 This is a schematic diagram of the OPD array 300 viewed from the top surface in order to explain the arrangement structure of the pixels 300P and the dummy pixels 300DP of the OPD array 300 according to the present embodiment.

[0520] The OPD array 300 includes a transparent substrate 322 and a plurality of pixels 300P disposed on the transparent substrate 322 at intervals from each other.

[0521] Each pixel 300P is configured to detect incident light and has 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 arranged on the first transparent electrode 320 at intervals, and a second transparent electrode 360 ​​formed on the plurality of organic semiconductor layers 344. According to such a configuration, electrons and positive holes (holes) are generated in the organic semiconductor layer 344 by utilizing incident light, and photovoltaic power is generated between the first transparent electrode 320 and the second transparent electrode 360 ​​to flow current. Therefore, the OPD element of each pixel 300P is configured to detect incident light. The OPD element of each pixel 300P of the OPD array 300 only needs to have a configuration that can detect incident light, for example, it may have a configuration that is the same as or similar to the OPD element 10, or it may have a configuration that is different from the OPD element 10.

[0522] The first transparent electrode 320 may have a known structure. For example, the first transparent electrode 320 may be the metal grid transparent electrode 20 or a transparent electrode having a different structure.

[0523] The organic semiconductor layers (sometimes also referred to as "organic semiconductor films") 344 are arranged on the same first transparent electrode 320 at intervals. In this embodiment, 3×3, i.e., 9 organic semiconductor layers 344 are arranged on the same first transparent electrode 320 at intervals. By arranging a plurality of organic semiconductor layers at intervals in this way, light can pass through adjacent organic semiconductor layers even when the transmittance of the organic semiconductor layers is low. Therefore, even when the OPD array 300 is arranged on the screen of a display or a display body, the visual recognition of the display or the display body can be suppressed from decreasing.

[0524] The organic semiconductor layer 344 may have a known structure. For example, the organic semiconductor layer 344 may have the same structure as the organic photoelectric conversion layer 44, for example, Fig.21 The organic semiconductor layer 344 may be formed of a material that can be used for the organic photoelectric conversion layer 44 shown in other embodiments, or may be formed of other materials.

[0525] The second transparent electrode 360 ​​is provided on the plurality of organic semiconductor layers 344 provided on the same first transparent electrode 320 at intervals. The second transparent electrode 360 ​​may have the same structure as the transparent electrode 60, for example, may be formed as Fig.21 The flat film shown.

[0526] like Fig.21 As shown, the plurality of pixels 300P are arranged in a checkerboard pattern. That is, the pixels 300P are arranged at intervals in the first direction (the horizontal direction of the paper of the figure) and at intervals in the second direction (the vertical direction of the paper of the figure), and the pixels 300P are also arranged at positions corresponding to the middle positions of the pixels 300P adjacent to each other in the first direction and the middle positions of the pixels 300P adjacent to each other in the second direction.

[0527] By adopting a structure in which the pixels 300P are spaced apart from each other, the detection resolution can be improved compared to the case in which pixels are arranged in the middle of adjacent pixels 300P in the first direction and the second direction and the pixels are arranged densely. That is, when the pixels are arranged densely, the possibility that multiple pixels detect incident light for the same optical input signal increases, and thus the detection resolution may be reduced. On the other hand, in the case in which the pixels 300P are spaced apart from each other, the possibility that multiple pixels detect incident light for the same optical input signal decreases, and thus the detection resolution can be suppressed from decreasing.

[0528] The distance between adjacent pixels 300P may be, for example, greater than or equal to the length of a single pixel 300P. For example, the distance between adjacent pixels 300P in the first direction may be greater than or equal to the length of the pixel 300P in the first direction. In addition, the distance between adjacent pixels 300P in the first direction may be less than or equal to the length of the pixel 300P in the first direction. Similarly, the distance between adjacent pixels 300P in the second direction perpendicular to the first direction may be greater than or equal to the length of the pixel 300P in the second direction. In addition, the distance between adjacent pixels 300P in the second direction may be less than or equal to the length of the pixel 300P in the second direction.

[0529] Furthermore, the plurality of pixels 300P of the present embodiment may be arranged in a checkerboard pattern. Thus, the pixels 300P are evenly arranged, thereby reducing the possibility that any pixel does not detect incident light.

[0530] Furthermore, a dummy pixel 300DP is provided between adjacent pixels 300P on the transparent substrate 322. Here, the dummy pixel 300DP refers to a region where an organic semiconductor layer 344D having no function of detecting incident light due to insulation is provided.

[0531] Each dummy pixel 300DP has a plurality of organic semiconductor layers 344D that are spaced apart from each other and insulated on the transparent substrate 322. In the present embodiment, 3×3, i.e., 9 organic semiconductor layers 344D are spaced apart from each other on the transparent substrate 322. Here, as shown in the figure, the organic semiconductor layer 344D of each dummy pixel 300DP is not electrically connected to either the first transparent electrode 320 or the second transparent electrode 360, and thus no current flows, and thus the dummy pixel 300DP is configured not to detect incident light.

[0532] It should be noted that an insulating film (not shown) may be formed on the organic semiconductor layer 344D, and the second transparent electrode 360 ​​may also be formed.

[0533] The dummy pixel 300DP is not limited to the structure shown in this embodiment. For example, the dummy pixel 300DP can be insulated by having the same structure as the pixel 300P, but without providing a wiring connecting the collector 110 and the dummy pixel 300DP. According to such a structure, at least a part of the manufacturing process of the pixel 300P and the dummy pixel 300DP can be shared. Fig.21 In the illustrated configuration, the organic semiconductor layer 344 and the organic semiconductor layer 344D are made of the same material and are provided at the same height from the surface of the transparent substrate 322 , so that at least a portion of the film formation process of the organic semiconductor layer 344 and the organic semiconductor layer 344D can be made common.

[0534] It should be noted that the number, size and shape of the organic semiconductor layer 344D of the pixel 300P and the dummy pixel 300DP may be different. For example, the pixel 300P may have two organic semiconductor layers 344 in the first direction and two in the second direction, that is, 2×2 equals 4. On the other hand, the dummy pixel 300DP may have two organic semiconductor layers 344D in the first direction and one in the second direction, that is, 2×1 equals 2.

[0535] like Fig.21 As shown, a plurality of dummy pixels 300DP are arranged in a checkerboard pattern. That is, the pixels 300P and the dummy pixels 300DP are arranged alternately in the first direction (the left-right direction of the paper of the figure), and are arranged alternately in the second direction (the up-down direction of the paper of the figure). 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.

[0536] According to the OPD array 300 constructed as described above, by setting a dummy pixel 300DP between adjacent pixels 300P, the occurrence of interference fringes associated with the OPD elements of the pixels 300P being arranged at intervals from each other can be suppressed, thereby suppressing the generation of visually recognizable interference fringes caused by the overlap of the interference fringes caused by the OPD elements and the interference fringes caused by the organic semiconductor layer 344 formed at intervals.

[0537] Therefore, if you use Fig. 9 As described above, when the OPD array 300 is provided on the screen of a display or a display body, interference fringes based on light emitted from the display or the display body can be suppressed, and the visual recognition of the display or the display body can be improved.

[0538] Industrial Applicability

[0539] The organic photodetector element using a metal grid transparent electrode of this embodiment, which can achieve both high visible light transmittance and high external quantum efficiency, can detect light input signals without inhibiting the visual recognizability of a display such as a display, and is suitable for use in non-touch user interface devices and has industrial applicability.

[0540] As described above, the organic photodetector element using the metal grid transparent electrode of the present embodiment is provided with a sub-pixel 44S including at least one organic photoelectric conversion layer 44 in the organic photodetector element. The sub-pixel 44S has a sub-sensor area 44SS in at least a portion. It is arranged in such a manner that the area where the sub-sensor area 44SS is provided and the area where the metal wiring 24 is provided overlap at least a portion in the projection image when the organic photodetector element is projected from the upper surface. By setting it as such a structure, it is possible to realize a structure in which the electrons generated in the organic photoelectric conversion layer 44 are easily transported to the nearby metal wiring 24 via the electron transport layer 42, and the external quantum efficiency can be improved. Moreover, by such a structure, even when a near-infrared detection type material with low visible light transmittance is used as the organic photoelectric conversion layer 44, the area ratio of the area with high visible light transmittance (the area other than the sub-pixel 44S) can be relatively increased. Therefore, the visible light transmittance of the organic photodetector element and the organic photodetector array as a whole can be improved. Furthermore, by setting the area of ​​the sub-sensor region 44SS to be equal to or greater than the repeating unit area of ​​the conductive pattern 24P of the metal grid transparent electrode 20, even if the relative positions of the two are temporarily offset during manufacturing (lamination process), the region where the sub-sensor region 44SS is provided can be overlapped with the region where the metal wiring 24 is provided in at least a portion. As a result, the organic photodetector element of the present invention can exhibit high light detectability due to high external quantum efficiency and extremely low dark current density, and can also exhibit high visible light transmittance.

[0541] In addition, the metal wiring 24 of the metal grid transparent electrode 20 can be manufactured by a printing method. By forming the metal wiring 24 by a printing method, it is easy to set the metal wiring 24 with a thickness of more than 30nm. Moreover, the gap between the metal wirings, the line width, etc. can be easily changed. The inventors of this application focus on the fact that if the gap between the metal wirings is too small, the metal wiring 24 will block the light, and the light receiving efficiency of the organic photoelectric conversion layer 44 will decrease. On the contrary, when the gap is too large, the diffusion distance of the electrons in the opening to the metal wiring 24 in the in-plane direction of the electron transport layer 42 becomes larger, which will in turn reduce the charge collection efficiency η. cc As described above, the range of the product value of the gap and the aperture ratio for improving the external quantum efficiency is derived.

[0542] In addition, the inventors of the present application have discovered an organic photodetector array formed by arranging two or more organic photodetector elements that can achieve both the high visible light transmittance and high external quantum efficiency of the present invention, and a light input signal and signal processing method suitable therefor, thereby constructing a new form of non-touch user interface device.

[0543] In addition, the present invention may be modified in various ways without departing from its main purpose. For example, a part of the constituent elements in one embodiment may be added to another embodiment within the scope of the ordinary creative ability of those skilled in the art. In addition, a part of the constituent elements in one embodiment may be replaced with corresponding constituent elements in other embodiments.

[0544] Regarding the above implementation modes, the following appendix is ​​further disclosed.

[0545] (Appendix 1)

[0546] A photodetector element comprising:

[0547] A metal grid transparent electrode, which is a first electrode; a transparent electrode, which is a second electrode, the second electrode is opposite to the metal grid transparent electrode; and a sub-pixel, which includes at least one organic semiconductor layer and is located between the metal grid transparent electrode and the transparent electrode, wherein:

[0548] The metal grid transparent electrode comprises a transparent substrate and a conductive pattern, wherein the conductive pattern has metal wiring arranged on the transparent substrate.

[0549] The sub-pixel has a sub-sensor area at least in a portion.

[0550] When projected from the upper surface, the region where the sub sensor region is provided overlaps at least partially with the region where the metal wiring is provided.

[0551] (Appendix 2)

[0552] The photodetector element according to Appendix 1, wherein

[0553] In S TCE-unit Assume that the repeating unit area of ​​the conductive pattern and S sub-sensor When S is set as the area of ​​the sub-sensor region, sub-sensor / S TCE-unit is 1 or more.

[0554] (Appendix 3)

[0555] The photodetector element according to Appendix 1 or 2, characterized in that

[0556] At least a portion of the sub-sensor region of the photodetector element when projected from the upper surface overlaps with two or more of the metal wirings extending in the same direction in at least any one direction.

[0557] (Appendix 4)

[0558] A photodetector element according to any one of Appendices 1 to 3, wherein

[0559] An insulating layer having an opening is provided between the metal grid transparent electrode and the transparent electrode,

[0560] The sub-pixel is configured to cover the opening when projected onto the surface from the upper surface in the stacking direction,

[0561] The sub sensor region corresponds to a region where the sub pixel and the opening overlap when projected from the upper surface onto the surface in the stacking direction.

[0562] (Appendix 5)

[0563] A photodetector element according to any one of Appendixes 1 to 4 wherein:

[0564] The shape of the region where the sub-pixels are provided when projected from the upper surface is at least one shape selected from the group consisting of a square, a rectangle, a substantially square, and a substantially rectangular shape.

[0565] (Appendix 6)

[0566] A photodetector element according to any one of Appendices 1 to 5, wherein

[0567] The photodetector element includes a sub-pixel array including a plurality of the sub-pixels arranged at intervals.

[0568] (Appendix 7)

[0569] The photodetector element according to Appendix 6, wherein

[0570] The sub-pixel array has a pattern in which the sub-pixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the sub-pixel array.

[0571] (Appendix 8)

[0572] A photodetector element according to any one of Appendixes 1 to 7, wherein

[0573] In S subOPD When is set to the area of ​​the sub-pixel,

[0574] S subOPD 25μm 2 Above and 10000μm 2 the following.

[0575] (Appendix 9)

[0576] A photodetector element according to any one of Appendices 1 to 8, wherein

[0577] The photodetector element has an external quantum efficiency of 15% or more at at least a portion of the wavelength in the near-infrared wavelength region of 780 nm to 1200 nm,

[0578] The visible light transmittance in the stacking direction of the photodetector elements in a region including the sub-sensor region is 50% or less.

[0579] (Appendix 10)

[0580] A photodetector element according to any one of Appendices 1 to 9, wherein

[0581] In the TCE Assume the thickness of the metal wiring and t OPD When the film thickness of the sub-sensor region is set to

[0582] t TCE is greater than 30 nm and less than 200 nm,

[0583] (t OPD -t TCE ) is greater than 50nm and less than 500nm.

[0584] (Appendix 11)

[0585] A photodetector element according to any one of Appendices 1 to 10, wherein

[0586] In the W TCE Set the line width of the metal wiring of the metal grid transparent electrode and set G TCE When the gap between the adjacent metal wirings extending in the same direction is set,

[0587] W TCE is 0.25 μm or more and 5.0 μm or less,

[0588] G TCE is less than 45 μm, and (G TCE / W TCE ) is greater than 1.0.

[0589] (Appendix 12)

[0590] A photodetector element according to Appendix 11 wherein,

[0591] In the A TCE When the aperture ratio of the conductive pattern is set to

[0592] (G TCE ·A TCE ) is greater than or equal to 0.25 μm·% and less than or equal to 45 μm·%.

[0593] (Appendix 13)

[0594] The photodetector element according to appendix 12, wherein

[0595] The opening ratio A of the conductive pattern TCE It is 25% or more and less than 100%.

[0596] (Appendix 14)

[0597] A photodetector element according to any one of Appendices 1 to 13, wherein

[0598] The organic semiconductor layer is an organic semiconductor layer configured to be capable of photoelectric conversion.

[0599] (Appendix 15)

[0600] The photodetector element according to Appendix 14, wherein

[0601] In E g opt When the optical band gap is set to

[0602] The organic semiconductor layer has a bulk heterojunction structure, and the bulk heterojunction structure has at least E g opt Organic donor materials with a voltage below 1.65 eV and E g opt It is an organic acceptor material with a V below 1.65 eV.

[0603] (Appendix 16)

[0604] The photodetector element according to appendix 15, wherein

[0605] The organic acceptor material is at least one material 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.

[0606] (Appendix 17)

[0607] The photodetector element according to appendix 15 or 16, wherein

[0608] The organic donor material is at least one material selected from the group consisting of PTB7-Th (alias: 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.

[0609] (Appendix 18)

[0610] A photodetector element according to any one of Appendixes 1 to 17, wherein

[0611] The metal wiring includes a metal and an oxide of the metal.

[0612] (Appendix 19)

[0613] A photodetector element according to any one of Appendices 1 to 18, wherein

[0614] The conductive pattern has a mesh pattern.

[0615] (Appendix 20)

[0616] A photodetector array having two or more pixels arranged therein each comprising a photodetector element as described in any one of Appendices 1 to 19.

[0617] (Appendix 21)

[0618] The photodetector array according to Appendix 20 comprises a wiring portion having a second conductive pattern provided on the transparent substrate and electrically connected to the conductive pattern, wherein the wiring portion is provided for each pixel.

[0619] In A TCE Assume that the aperture ratio of the conductive pattern is wire When the aperture ratio of the second conductive pattern is set to

[0620] -10%≤(A wire -A TCE )≤10%.

[0621] (Appendix 22)

[0622] The photodetector array according to Appendix 21 has a collector having a third conductive pattern provided on the transparent substrate and electrically connected to the second conductive pattern,

[0623] In the pad When the area occupied by the third conductive pattern per unit area is denoted as:

[0624] Γ pad It is 50% or more and less than 100%.

[0625] (Appendix 23)

[0626] The photodetector array according to one of Appendixes 20 to 22, comprising a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern.

[0627] (Appendix 24)

[0628] The photodetector array according to Appendix 23, wherein:

[0629] In A TCE Assume that the aperture ratio of the conductive pattern is dummy When the aperture ratio of the dummy pattern is set to

[0630] -10%≤(A dummy -A TCE )≤10%.

[0631] (Appendix 25)

[0632] A photodetector array according to any one of Appendix 20 to 24, comprising:

[0633] A dummy sub-pixel array includes a plurality of dummy sub-pixels, wherein the dummy sub-pixels include an insulating layer disposed on the metal grid transparent electrode; and an organic semiconductor layer disposed on the insulating layer; and

[0634] A sub-pixel array, comprising a plurality of sub-pixels,

[0635] The dummy sub-pixel array and the sub-pixel array have the same pattern structure when projected from the upper surface.

[0636] (Appendix 26)

[0637] A photodetector array according to any one of Appendix 20 to 25, wherein

[0638] The pixel size of the photodetector array is 1 mm 2 Above and 25mm 2 the following.

[0639] (Appendix 27)

[0640] A photodetector array according to any one of Appendix 20 to 26, wherein

[0641] The pixel density of the photodetector array is greater than or equal to 2 ppi and less than or equal to 15 ppi.

[0642] (Appendix 28)

[0643] A photodetector array according to any one of Appendix 20 to 27, wherein

[0644] 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.

[0645] (Appendix 29)

[0646] A non-touch user interface device comprising a photodetector array as described in any one of Appendixes 20 to 28 for being arranged on a screen of a display or a display body,

[0647] The non-touch user interface device detects a position irradiated with the optical input signal by converting the optical input signal irradiated with the photodetector array into an electrical output signal by using the photodetector elements of the photodetector array,

[0648] The non-touch user interface device is configured to enable input operation to be performed on the screen of the display or the display body through the position detection.

[0649] (Appendix 30)

[0650] The non-touch user interface device according to Appendix 29, wherein:

[0651] The optical input signal includes light having a wavelength of at least a part of a near-infrared wavelength region of 780 nm to 1200 nm.

[0652] (Appendix 31)

[0653] The non-touch user interface device according to Appendix 29 or 30, wherein:

[0654] The optical input signal is frequency modulated, and the modulation frequency is greater than or equal to 0.5 kHz and less than or equal to 20 kHz.

[0655] (Appendix 32)

[0656] A non-touch user interface device according to any one of Appendixes 29 to 31, wherein:

[0657] The optical input signal is an optical signal emitted from a laser pointer.

[0658] (Appendix 33)

[0659] A non-touch user interface device according to any one of Appendixes 29 to 31, wherein:

[0660] The optical input signal is reflected light from the indicating component.

[0661] (Appendix 34)

[0662] The non-touch user interface device according to Appendix 33, wherein:

[0663] The optical input signal is reflected light from the pointing member generated by bringing the pointing member into contact with a planar projection beam formed in space.

[0664] (Appendix 35)

[0665] A photodetector array comprising:

[0666] Transparent substrate,

[0667] A plurality of pixels are arranged on the transparent substrate at intervals and each pixel has a photodetector element.

[0668] A plurality of dummy pixels are provided on the transparent substrate at intervals and two of the pixels are insulated from each other.

[0669] The photodetector elements each include a first transparent electrode formed on the transparent substrate, a plurality of organic semiconductor layers spaced apart from each other on the first transparent electrode, and a second transparent electrode formed on the plurality of organic semiconductor layers.

[0670] The dummy pixels each include a plurality of organic semiconductor layers provided on the transparent substrate at intervals from each other.

[0671] (Appendix 36)

[0672] The photodetector array according to Appendix 35, wherein:

[0673] The plurality of pixels and the plurality of dummy pixels are alternately arranged in a first direction, and

[0674] The layers are alternately arranged in a second direction perpendicular to the first direction.

[0675] (Appendix 37)

[0676] A photodetector array according to Appendix 35 or 36, wherein the multiple organic semiconductor layers possessed by the above-mentioned pixels and the multiple organic semiconductor layers possessed by the above-mentioned dummy pixels are made of the same material and are arranged at the same height based on the surface of the above-mentioned transparent substrate.

[0677] (Appendix 38)

[0678] A photodetector array according to any one of Appendices 35 to 37, wherein the first transparent electrode comprises a metal grid transparent electrode comprising a conductive pattern having metal wiring disposed on the transparent substrate.

[0679] Description of Reference Numerals

[0680] 10Organic photodetector element (OPD element)

[0681] 20 Metal grid transparent electrode

[0682] 22 Transparent substrate

[0683] 24 Metal wiring

[0684] 24P Conductive Pattern

[0685] 42 Electron transport layer

[0686] 44 Organic photoelectric conversion layer

[0687] 44S sub-pixel

[0688] 44SS sub-sensor area

[0689] 44SA Alignment Area

[0690] 44SC connection

[0691] 46 Hole transport layer

[0692] 60 Transparent Electrode

[0693] 80 Insulation layer

[0694] 100 organic photodetector array (OPD array)

[0695] 110 Current collecting part

[0696] 120 Wiring Department

[0697] 130 dummy pattern section

[0698] 200 Non-touch user interface device (UI device)

[0699] OP opening

[0700] D Display

[0701] IL incident light (optical input signal)

[0702] PD indicator component

[0703] LS light source (point light source)

[0704] LS2 is a planar projection beam (surface light source).

Claims

1. A photodetector element comprising: A metal grid transparent electrode, which is a first electrode; a transparent electrode, which is a second electrode, the second electrode being opposite to the metal grid transparent electrode; and a sub-pixel, which comprises at least one organic semiconductor layer and is located between the metal grid transparent electrode and the transparent electrode, wherein: The metal grid transparent electrode comprises a transparent substrate and a conductive pattern, wherein the conductive pattern comprises metal wiring provided on the transparent substrate. The sub-pixel has a sub-sensor area in at least a portion. When projected from the upper surface, the region where the sub-sensor region is provided overlaps at least partially with the region where the metal wiring is provided.

2. The photodetector element according to claim 1, wherein In the S TCE -unit is set as the repeating unit area of ​​the conductive pattern and S sub-sensor When S is set as the area of ​​the sub-sensor region, sub-sensor / S TCE -unit is 1 or more.

3. The photodetector element according to claim 1, wherein At least a portion of the sub-sensor region of the photodetector element when projected from the upper surface overlaps with two or more of the metal wirings extending in the same direction in at least any one direction.

4. The photodetector element according to claim 1 , wherein An insulating layer having an opening is provided between the metal grid transparent electrode and the transparent electrode. The sub-pixel is configured to cover the opening when projected onto the surface from the upper surface in the stacking direction. The sub-sensor region corresponds to a region where the sub-pixel overlaps with the opening when projected onto the surface from the upper surface in the stacking direction.

5. The photodetector element according to claim 1 , wherein The shape of the region where the sub-pixels are provided when projected from the upper surface is at least one shape selected from the group consisting of a square, a rectangle, a substantially square, and a substantially rectangular shape. 6 . The photodetector element according to claim 1 , comprising a sub-pixel array including a plurality of the sub-pixels arranged at intervals.

7. The photodetector element according to claim 6, wherein The sub-pixel array has a pattern in which the sub-pixels are two-dimensionally arranged at equal intervals along two orthogonal coordinate axes in parallel planes of the sub-pixel array.

8. The photodetector element according to claim 1, wherein In the S subOPD When is set to the area of ​​the sub-pixel, S subOPD 25μm 2 Above and 10000μm 2 the following.

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

10. The photodetector element according to claim 1, wherein In the t TCE Set the thickness of the metal wiring and t OPD When the film thickness of the sub-sensor region is set to t TCE is greater than or equal to 30 nm and less than or equal to 200 nm, (t OPD -t TCE ) is greater than 50 nm and less than 500 nm.

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

0.

12. The photodetector element according to claim 11, wherein In the A TCE When the aperture ratio of the conductive pattern is set to (G TCE ·A TCE ) is 0.25 μm·% or more and 45 μm·% or less.

13. The photodetector element according to claim 12, wherein The aperture ratio A of the conductive pattern TCE It is 25% or more and less than 100%.

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

15. The photodetector element according to claim 14, wherein In the E g opt When the optical band gap is set, The organic semiconductor layer has a bulk heterojunction structure, and the bulk heterojunction structure has at least E g opt Organic donor materials with a voltage below 1.65 eV and E g opt It is an organic acceptor material with a wavelength below 1.65 eV.

16. The photodetector element according to claim 15, wherein The organic acceptor material is at least one material 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.

17. The photodetector element according to claim 15 or 16, wherein The organic donor material is at least one material selected from the group consisting of PTB7-Th (alias: PCE-10), PDTP-DFBT, PDPP3T, PDPP3T-O14, PDPP3T-O16, PDPP3T-O20, PDPP3T-C20, PD PP4T, DPPTfQxT, DPPTQxT, DPPBTQxBT, DPPBTffQxBT, FLP030, PBDTT-SeDPP, PBDTT-DPP, PBDTT-FDPP, PDPP2T-TT (PTT-DTDPP), PCDTBT, PCPDTBT, PCPDTFBT, and Si-PCPDTBT.

18. The photodetector element according to claim 1, wherein The metal wiring includes a metal and an oxide of the metal.

19. The photodetector element according to claim 1, wherein The conductive pattern has a mesh pattern.

20. A photodetector array comprising two or more pixels each comprising the photodetector element according to claim 1.

21. The photodetector array according to claim 20, comprising a wiring portion having a second conductive pattern provided on the transparent substrate and electrically connected to the conductive pattern, wherein the wiring portion is provided for each pixel. In the A TCE Assume that the aperture ratio of the conductive pattern is wire When the aperture ratio of the second conductive pattern is set to -10%≤(A wire -A TCE )≤10%。 22. The photodetector array according to claim 21, comprising a collector portion having a third conductive pattern provided on the transparent substrate and electrically connected to the second conductive pattern. In the Γ pad When the area occupied by the third conductive pattern per unit area is Γ pad It is 50% or more and less than 100%. 23 . The photodetector array according to claim 20 , further comprising a dummy pattern provided on the transparent substrate and electrically insulated from the conductive pattern.

24. The photodetector array of claim 23, wherein: In the A TCE Assume that the aperture ratio of the conductive pattern is dummy When the aperture ratio of the dummy pattern is set to -10%≤(A dummy -A TCE )≤10%。 25. The photodetector array according to claim 20, comprising: A dummy sub-pixel array includes a plurality of dummy sub-pixels, each dummy sub-pixel comprising an insulating layer disposed on the metal grid transparent electrode and an organic semiconductor layer disposed on the insulating layer; and A sub-pixel array comprising a plurality of said sub-pixels, The dummy sub-pixel array and the sub-pixel array have the same pattern structure when projected from the upper surface.

26. The photodetector array of claim 20, wherein: The pixel size of the photodetector array is 1 mm 2 Above and 25mm 2 the following.

27. The photodetector array of claim 20, wherein: The pixel density of the photodetector array is greater than or equal to 2 ppi and less than or equal to 15 ppi.

28. The photodetector array of claim 20, wherein: 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.

29. A touchless user interface device comprising the photodetector array according to claim 20 for arrangement on a screen of a display or a display body. The touchless user interface device detects a position irradiated with the light input signal by converting the light input signal irradiated with the photodetector array into an electrical output signal using the photodetector elements of the photodetector array. The non-touch user interface device is configured to enable input operations on the display or the screen of the display body through the position detection.

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

31. The touchless user interface device according to claim 29, wherein: The optical input signal is frequency modulated, and the modulation frequency is greater than or equal to 0.5 kHz and less than or equal to 20 kHz.

32. The touchless user interface device according to claim 29, wherein: The optical input signal is an optical signal emitted from a laser pointer.

33. The touchless user interface device according to claim 29, wherein: The optical input signal is reflected light from the indicating component.

34. The touchless user interface device according to claim 33, wherein: The optical input signal is reflected light from the pointing member generated by bringing the pointing member into contact with a planar projection beam formed in space.

Images