Manufacturing method of photoelectric conversion element and optical sensor

Abstract

This invention relates to a method for manufacturing a photoelectric conversion element and an optical sensor. A method for manufacturing a photoelectric conversion element having an active layer with high photoelectric effect sensitivity is provided. An optical sensor having a photoelectric conversion element with high photoelectric effect sensitivity having an active layer is provided. The method for manufacturing the photoelectric conversion element includes an active layer forming step for forming an active layer having repeating units represented by Chemical Formula 1. The active layer forming step includes: a first layer forming step, coating a first liquid containing polyamic acid to form a first layer; a first heating step, heating the first layer at 120°C for 20 to 60 minutes; and a second heating step, heating the first layer at 230°C to 280°C for 10 minutes. The optical sensor includes a substrate; a sensor portion laminated on the substrate, the sensor portion having a detection electrode, an electron transport layer, an active layer, a hole transport layer, and a counter electrode, and a photoelectric conversion element laminated on the substrate, the active layer being formed of a polyimide-based material having repeating units represented by the following Chemical Formula 5.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing photoelectric conversion elements and an optical sensor. Background Technology

[0002] Optical sensors have photoelectric conversion elements such as photodiodes. The photoelectric conversion element disclosed in Non-Patent Document 1 has an active layer (polyimide layer) made of polyimide. Furthermore, Non-Patent Document 1 discloses that, in order to crystallize the polyimide and manufacture the active layer (polyimide layer) that exerts the photoelectric effect, polyamic acid, a precursor of polyimide, is subjected to a heat treatment at 300°C for 2 hours.

[0003] Existing technical documents

[0004] Patent documents

[0005] Non-patent literature 1: Akio Takimoto et al., “Electrophotographic and structural studies on novel photoconductive polyimide films”, Journal of Applied Physics, Vol. 70 (No. 5), 1991, p. 2799. Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The photoelectric effect sensitivity of the active layer obtained from non-patent literature 1 is low.

[0008] The purpose of this disclosure is to provide a method for manufacturing a photoelectric conversion element with high sensitivity due to the photoelectric effect of the active layer. Furthermore, the purpose is to provide an optical sensor with a photoelectric conversion element having high sensitivity due to the photoelectric effect of the active layer.

[0009] Methods for solving problems

[0010] The first aspect of this disclosure relates to a method for manufacturing a photoelectric conversion element, comprising an active layer forming step for forming an active layer having repeating units as shown in Chemical Formula 1. The active layer forming step comprises the following steps: a first layer forming step, wherein polyamic acid as a precursor is coated to form a first layer; a first heating step, wherein the first layer is heated at 120°C for 20 to 60 minutes; and a second heating step, wherein the first layer is heated at 230°C to 280°C for 10 minutes.

[0011] [Chemical Formula 1]

[0012]

[0013] The second aspect of this disclosure relates to a method for manufacturing a photoelectric conversion element, comprising an active layer forming step for forming an active layer having repeating units as shown in Chemical Formula 2 below. The active layer forming step comprises the following steps: a first layer forming step, wherein a polyamic acid solution having a precursor as Chemical Formula 2 is coated to form a first layer; a first heating step, wherein the first layer is heated at 120°C for 20 to 60 minutes; and a second heating step, wherein the first layer is heated at 180°C to 280°C for 10 minutes.

[0014] [Chemical Formula 2]

[0015]

[0016] The third aspect of this disclosure relates to a method for manufacturing a photoelectric conversion element, comprising an active layer forming step for forming an active layer having repeating units as shown in Chemical Formula 3. The active layer forming step comprises the following steps: a first layer forming step, wherein a polyamide carboxylic acid, as a precursor and having repeating units as shown in Chemical Formula 4, is coated to form a first layer; a first heating step, wherein the first layer is heated at 120°C for 20 to 60 minutes; and a second heating step, wherein the first layer is heated at 180°C to 280°C for 10 minutes.

[0017] [Chemical Formula 3]

[0018]

[0019] X: -O-, -S-, >CO, >C-R2, >SO2, -C(=O)-O-, -C(=O)-O-Φ-OC(=O)-

[0020] Here, R is -H, -CH3, or -CF3.

[0021] Y: S, Se, Te

[0022] m: 2, 4, 6, 8, 10

[0023] n: 3 or more oligomers or polymers

[0024] [Chemical Formula 4]

[0025]

[0026] X: -O-, -S-, >CO, >C-R2, >SO2, -C(=O)-O-, -C(=O)-O-Φ-OC(=O)-

[0027] Here, R is -H, -CH3, or -CF3.

[0028] Y: S, Se, Te

[0029] m: 2, 4, 6, 8, 10

[0030] n: 3 or more oligomers or polymers

[0031] One aspect of this disclosure relates to an optical sensor comprising: a substrate, and a sensor portion stacked on the substrate. The sensor portion includes a detection electrode, an electron transport layer, an active layer, a hole transport layer, and a counter electrode, and also includes a photoelectric conversion element stacked on the substrate. The active layer is formed of a polyimide-based material having repeating units represented by the following chemical formula 5.

[0032] [Chemical Formula 5]

[0033] Attached Figure Description

[0034] [ Figure 1A ] Figure 1A This is a cross-sectional view of the optical sensor according to Embodiment 1.

[0035] [ Figure 1B ] Figure 1B This is a cross-sectional view of the optical sensor involved in Modification Example 1.

[0036] [ Figure 1C ] Figure 1C This is a cross-sectional view of the optical sensor involved in Modification Example 2.

[0037] [ Figure 1D ] Figure 1D This is a cross-sectional view of the optical sensor involved in Modification Example 3.

[0038] [ Figure 2 ] Figure 2 A top view of the sensor substrate according to Embodiment 1 is shown.

[0039] [ Figure 3 ] Figure 3 A block diagram illustrating an example configuration of the detection device according to Embodiment 1.

[0040] [ Figure 4 ] Figure 4 A circuit diagram of the detection device according to Embodiment 1 is shown.

[0041] [ Figure 5 ] Figure 5 The circuit diagram illustrates multiple detection areas of Embodiment 1.

[0042] [ Figure 6 ] Figure 6 This is a cross-sectional view showing the approximate cross-sectional structure of the sensor section.

[0043] [ Figure 7 ] Figure 7 A diagram illustrating the manufacturing process of the photodiode according to Embodiment 1.

[0044] [ Figure 8 ] Figure 8 A diagram illustrating the manufacturing process of the active layer according to Embodiment 1.

[0045] [ Figure 9 ] Figure 9 A cross-sectional view showing the approximate cross-sectional configuration of the sensor section according to Embodiment 2.

[0046] [ Figure 10 ] Figure 10 A diagram illustrating the manufacturing process of the active layer according to Embodiment 2.

[0047] [ Figure 11 ] Figure 11 A cross-sectional view showing the approximate cross-sectional configuration of the sensor section according to Embodiment 3.

[0048] [ Figure 12 ] Figure 12 A diagram illustrating the manufacturing process of the active layer according to Embodiment 3.

[0049] [ Figure 13 ] Figure 13 A cross-sectional view showing the approximate cross-sectional configuration of the sensor section according to Embodiment 4.

[0050] [ Figure 14 ] Figure 14 A diagram illustrating the manufacturing process of the active layer according to Embodiment 4.

[0051] [ Figure 15 ] Figure 15 A cross-sectional view showing a modified example of the active layer in Embodiment 4.

[0052] [ Figure 16 ] Figure 16 A cross-sectional view showing a modified example of the photoelectric conversion element.

[0053] [ Figure 17 ] Figure 17 This is a graph showing the X-ray diffraction analysis results of samples 1 to 8.

[0054] [ Figure 18 ] Figure 18 A graph showing the relationship between the half-width of the X-ray spectrum of samples 2, 3, 4, 5, 6, 7, and 8 and the substrate temperature during film formation.

[0055] [ Figure 19 ] Figure 19 A graph showing the X-ray diffraction analysis results of samples 11 to 16.

[0056] [ Figure 20 ] Figure 20 A graph showing the relationship between the half-width of the X-ray spectra of samples 11 to 16 and the substrate temperature during film formation. Detailed Implementation

[0057] The embodiments (implementations) for carrying out this disclosure will be described in detail with reference to the accompanying drawings. This disclosure is not limited to the content described in the following embodiments. Furthermore, the constituent elements described below include constituent elements readily conceived by those skilled in the art and substantially the same elements. Moreover, the constituent elements described below can be appropriately combined. It should be noted that this disclosure is merely an example, and appropriate modifications and readily conceived content while maintaining the spirit of this disclosure are naturally included within the scope of this disclosure. Furthermore, for clearer explanation, the drawings sometimes schematically show the width, thickness, shape, etc., of various parts compared to the actual embodiments, but this is merely an example and does not limit the interpretation of this disclosure. Furthermore, in this disclosure and the various drawings, elements identical to those described in previously presented drawings are given the same reference numerals, and detailed descriptions are sometimes appropriately omitted.

[0058] In this specification and claims, when describing the manner of configuring other structures on a certain structure, the use of "on" alone, unless otherwise specified, includes both the case of configuring other structures on top of a certain structure in a manner connected to the structure, and the case of configuring other structures above a certain structure through another structure.

[0059] (Implementation Method 1)

[0060] Figure 1A This is a cross-sectional view of the optical sensor according to Embodiment 1. Figure 1B This is a cross-sectional view of the optical sensor involved in Modification Example 1. Figure 1C This is a cross-sectional view of the optical sensor involved in Modification Example 2. Figure 1D This is a cross-sectional view of the optical sensor involved in Modification Example 3.

[0061] In the description of the implementation method, the case where a photoelectric conversion element (referred to as a photodiode 30 in the embodiment) is applied to the optical sensor 120 will be used as an example. Figure 1AAs shown, the optical sensor 120 is a detection device with an illumination device, including a detection device 1 and an illumination device 121. The detection device 1 includes a sensor substrate 2, a filter 7, an adhesive layer 125, and a cover member 122. Furthermore, the sensor substrate 2, the filter 7, the adhesive layer 125, the cover member 122, and the illumination device 121 are sequentially stacked in a direction perpendicular to the surface of the sensor substrate 2.

[0062] The adhesive layer 125 bonds the filter 7 and the masking member 122. It should be noted that the adhesive layer 125 does not need to bond the entire surface of the filter 7 and the masking member 122 to each other. For example, it can be a structure where only the area corresponding to the detection area AA is bonded, without bonding the area corresponding to the detection area AA. The masking member 122 is a component used to protect the sensor substrate 2 and the filter 7, covering the sensor substrate 2 and the filter 7. The masking member 122 is, for example, a glass substrate.

[0063] The lighting device 121 may include a light source such as a light-emitting diode (LED) or a display panel. The display panel may be, for example, an organic EL display panel (OLED, Organic Light-Emitting Diode) or an inorganic EL display (micro-LED, mini-LED). Alternatively, the display panel may be a liquid crystal display panel (LCD, Liquid Crystal Display) using liquid crystal elements as display elements, or an electrophoretic display panel (EPD, Electrophoretic Display) using electrophoretic elements as display elements.

[0064] In this optical sensor 120, light L1 emitted from the illumination device 121 is reflected by a finger Fg. The detection device 1 detects the light L2 reflected from the finger Fg to detect the surface irregularities of the finger Fg (e.g., fingerprints). In addition to detecting fingerprints, the detection device 1 can also detect light L2 reflected from the interior of the finger Fg to detect biological information. Biological information includes, for example, images of blood vessels such as veins, pulse, and pulse waves. The color of the light L1 emitted from the illumination device 121 can vary depending on the object being detected.

[0065] It should be noted that the optical sensor 120 is not limited to... Figure 1A The example shown. For example... Figure 1BAs shown, the lighting device 121 can, for example, be a so-called side-light type front light source that uses the masking member 122 as a light guide plate positioned corresponding to the detection area AA of the detection device 1, and has multiple light sources 123 arranged at one or both ends of the masking member 122. That is, the masking member 122 has a light irradiation surface 121a, which is a component of the lighting device 121. According to this lighting device 121, light L1 is irradiated from the light irradiation surface 121a of the masking member 122 onto the finger Fg, which is the object to be detected. As a light source, for example, an LED that emits light of a predetermined color is used.

[0066] In addition, such as Figure 1C As shown, the lighting device 121 can also be placed to the side or above the masking member 122 to illuminate the finger Fg with light L1 from the side or above.

[0067] In addition, such as Figure 1D As shown, the lighting device 121 can also be a so-called direct-lit backlight that is installed on the back of the detection device 1.

[0068] In addition, although not specifically illustrated, the lighting device 121 itself can also serve as a masking component 122. Alternatively, the lighting device 121 may be omitted, and sunlight reflected from the finger Fg may be detected.

[0069] Figure 2 This is a top view showing the sensor substrate according to Embodiment 1. It should be noted that... Figure 2 As shown below, the first direction Dx is a direction within a plane parallel to the substrate 21. The second direction Dy is a direction within a plane parallel to the substrate 21, and it is orthogonal to the first direction Dx. It should be noted that the second direction Dy may intersect the first direction Dx, but not be orthogonal to it. The third direction Dz is a direction orthogonal to both the first direction Dx and the second direction Dy, and it is the normal direction of the substrate 21.

[0070] like Figure 2 As shown, the sensor substrate 2 includes a substrate 21, a sensor section 10, a scan line drive circuit 15, a signal line selection circuit 16, a detection circuit 48, a control circuit 102, and a power supply circuit 103.

[0071] Substrate 21 has various wirings such as switching elements Tr (TFT, Thin Film Transistor), gate lines GCL, and signal lines SGL, and serves as the driving circuit substrate for driving the sensor unit 10. Substrate 21 is also referred to as a backplane or array substrate. Control substrate 101 is electrically connected to substrate 21 via wiring substrate 110. Wiring substrate 110 is, for example, a flexible printed circuit board or a rigid substrate. Wiring substrate 110 is provided with detection circuit 48. Control substrate 101 is provided with control circuit 102 and power supply circuit 103. Control circuit 102 is, for example, an FPGA (Field Programmable Gate Array). Control circuit 102 supplies control signals to sensor unit 10, scan line driving circuit 15, and signal line selection circuit 16. Power supply circuit 103 supplies sensor power signal VDDSNS (reference) to sensor unit 10, scan line driving circuit 15, and signal line selection circuit 16. Figure 5 Voltage signals such as ) should be noted. It should be noted that in this embodiment, the detection circuit 48 is illustrated as being disposed on the wiring substrate 110, but the detection circuit 48 may also be disposed on the substrate 21.

[0072] The substrate 21 has a detection area AA and a peripheral area GA. Each element (detection element 3) of the sensor unit 10 is disposed within the detection area AA. The peripheral area GA is the area outside the detection area AA, and is the area where no elements (detection elements 3) are disposed. A scan line drive circuit 15 and a signal line selection circuit 16 are disposed within the peripheral area GA.

[0073] The sensor unit 10 includes multiple detection elements 3 as light sensors. Each detection element 3 is a photodiode 30. The photodiode 30 is a photoelectric conversion element and outputs an electrical signal corresponding to the light it emits. More specifically, the photodiode 30 is an OPD (Organic Photo Diode). The detection elements 3 (photodiodes 30) are arranged in a matrix on the detection area AA. The photodiodes 30 are detected according to gate drive signals (e.g., reset control signal RST, readout control signal RD) supplied by the scan line drive circuit 15. The multiple photodiodes 30 output an electrical signal corresponding to the light they emit as a detection signal Vdet to the signal line selection circuit 16. The detection device 1 detects information related to a biological organism based on the detection signals Vdet from the multiple photodiodes 30.

[0074] Figure 3 A block diagram illustrating an example configuration of the detection apparatus according to Embodiment 1. For example... Figure 3As shown, the detection device 1 also includes a detection control circuit 11 and a detection unit 40. Some or all of the functions of the detection control circuit 11 are included in the control circuit 102. Furthermore, some or all of the functions of the detection unit 40, other than the detection circuit 48, are included in the control circuit 102.

[0075] The detection control circuit 11 supplies control signals to the scan line drive circuit 15, the signal line selection circuit 16, and the detection unit 40, respectively, and controls their operation. The detection control circuit 11 supplies various control signals such as the start signal STV and the clock signal CK to the scan line drive circuit 15. Furthermore, the detection control circuit 11 supplies various control signals such as the selection signal ASW to the signal line selection circuit 16.

[0076] The scan line drive circuit 15 drives multiple scan lines (gate lines GCL) based on various control signals. Figure 4 The scan line drive circuit 15 selects multiple scan lines sequentially or simultaneously, supplying gate drive signals to the selected scan lines. Thus, the scan line drive circuit 15 selects multiple photodiodes 30 connected to the scan lines.

[0077] Signal line selection circuit 16 selects multiple signal lines SGL sequentially or simultaneously (reference). Figure 4 The switching circuit of the signal line selection circuit 16 is, for example, a multiplexer. Based on the selection signal ASW supplied from the detection control circuit 11, the signal line selection circuit 16 connects the selected output signal line SL to the detection circuit 48. Thus, the signal line selection circuit 16 outputs the detection signal Vdet of the photodiode 30 to the detection unit 40.

[0078] The detection unit 40 includes a detection circuit 48, a signal processing circuit 44, a coordinate extraction circuit 45, a storage circuit 46, and a detection timing control circuit 47. The detection timing control circuit 47 controls the detection circuit 48, the signal processing circuit 44, and the coordinate extraction circuit 45 to operate synchronously based on the control signal supplied from the detection control circuit 11.

[0079] The detection circuit 48 is, for example, an analog front-end circuit (AFE). The detection circuit 48 is a signal processing circuit that at least has the functions of a detection signal amplification circuit 42 and an A / D conversion circuit 43. The detection signal amplification circuit 42 is a circuit that amplifies the detection signal Vdet, for example, an integrating circuit. The A / D conversion circuit 43 converts the analog signal output from the detection signal amplification circuit 42 into a digital signal.

[0080] The signal processing circuit 44 is a logic circuit that detects a specified physical quantity input to the sensor unit 10 based on the output signal of the detection circuit 48. When the finger Fg contacts or approaches the detection surface, the signal processing circuit 44 can detect the surface irregularities of the finger Fg and the palm based on the signal from the detection circuit 48. Furthermore, the signal processing circuit 44 can detect biologically related information based on the signal from the detection circuit 48. Biologically related information includes, for example, vascular images of the finger Fg and the palm, pulse waves, pulse, and blood oxygen saturation.

[0081] The storage circuit 46 temporarily stores the signal calculated by the signal processing circuit 44. The storage circuit 46 can be, for example, RAM (Random Access Memory), a register circuit, etc.

[0082] The coordinate extraction circuit 45 is a logic circuit that calculates the detection coordinates of the surface irregularities of the finger Fg when the signal processing circuit 44 detects contact or proximity of the finger Fg. Furthermore, the coordinate extraction circuit 45 is also a logic circuit that calculates the detection coordinates of the finger Fg and the blood vessels in the palm. The coordinate extraction circuit 45 combines the detection signals Vdet output from each detection element 3 of the sensor unit 10 to generate two-dimensional information representing the shape of the surface irregularities of the finger Fg. It should be noted that the coordinate extraction circuit 45 may also output the detection signal Vdet as the sensor output Vo without calculating the detection coordinates.

[0083] Next, an example of the circuit configuration of the detection device 1 will be explained. Figure 4 A circuit diagram of the detection device according to Embodiment 1 is shown. Figure 4 As shown, the sensor unit 10 has multiple partial detection areas PAA arranged in a matrix. Each of the multiple partial detection areas PAA is provided with a photodiode 30.

[0084] Gate lines GCL extend along a first direction Dx and are connected to multiple partial detection areas PAA arranged along the first direction Dx. Additionally, multiple gate lines GCL(1), GCL(2), ..., GCL(8) are arranged along a second direction Dy and are connected to the scan line drive circuit 15. It should be noted that in the following description, unless it is necessary to distinguish between multiple gate lines GCL(1), GCL(2), ..., GCL(8), they will only be referred to as gate lines GCL. Furthermore, in... Figure 4 For ease of understanding, eight gate lines GCL are shown in the diagram, but this is just one example. M gate lines GCL can also be arranged (M is 8 or more, for example, M = 256).

[0085] Signal line SGL extends along the second direction Dy and is connected to photodiodes 30 of multiple partial detection areas PAA arranged along the second direction Dy. Furthermore, multiple signal lines SGL(1), SGL(2), ..., SGL(12) are arranged along the first direction Dx and are connected to signal line selection circuit 16 and reset circuit 17, respectively. It should be noted that in the following description, unless it is necessary to distinguish between multiple signal lines SGL(1), SGL(2), ..., SGL(12), they will only be referred to as signal line SGL.

[0086] Furthermore, for ease of explanation, 12 signal lines SGL are shown, but this is just one example; there can also be N signal lines SGL (N is 12 or more, for example, N = 252). Additionally, Figure 4 In this configuration, a sensor section 10 is provided between the signal line selection circuit 16 and the reset circuit 17. However, it is not limited to this; the signal line selection circuit 16 and the reset circuit 17 may also be connected to the ends of the signal line SGL in the same direction, respectively. Furthermore, the actual area of ​​a single sensor is, for example, substantially 50 × 50 μm. 2 The resolution of the detection area AA is, for example, 508 ppi, the number of sensors configured in the detection area AA is, for example, 252 units × 256 units, and the area of ​​the detection area AA is, for example, 12.6 × 12.8 mm. 2 .

[0087] Scan line drive circuit 15 is controlled by control circuit 102 (reference) Figure 2 The scan line drive circuit 15 receives various control signals such as the start signal STV, clock signal CK, and reset signal RST1. Based on these control signals, the scan line drive circuit 15 sequentially selects multiple gate lines GCL(1), GCL(2), ..., GCL(8) in a time-division manner. The scan line drive circuit 15 supplies a gate drive signal Vgcl to the selected gate line GCL. As a result, a gate drive signal is supplied to multiple first switching elements Tr connected to the gate line GCL, and multiple partial detection regions PAA arranged along the first direction Dx are selected as detection targets.

[0088] It should be noted that the scan line driving circuit 15 can also perform different driving according to the detection modes of fingerprint detection and various biological information (pulse wave, pulse, vascular image, blood oxygen concentration, etc.). For example, the scan line driving circuit 15 can drive multiple gate lines GCLs bundled together.

[0089] The signal line selection circuit 16 has multiple selection signal lines Lsel, multiple output signal lines Lout, and third switching elements TrS. The multiple third switching elements TrS are respectively configured to correspond to multiple signal lines SGL. Six signal lines SGL(1), SGL(2), ..., SGL(6) are connected to a common output signal line Lout1. Six signal lines SGL(7), SGL(8), ..., SGL(12) are connected to a common output signal line Lout2. Output signal lines Lout1 and Lout2 are respectively connected to the detection circuit 48.

[0090] Here, signal lines SGL(1), SGL(2), ..., SGL(6) are designated as the first signal line block, and signal lines SGL(7), SGL(8), ..., SGL(12) are designated as the second signal line block. Multiple selection signal lines Lsel are each connected to the gate of the third switching element TRS contained in one signal line block. Furthermore, one selection signal line Lsel is connected to the gate of the third switching element TRS of multiple signal line blocks.

[0091] Control circuit 102 (reference) Figure 2 The selection signal ASW is sequentially supplied to the selection signal line Lsel. Thus, the signal line selection circuit 16, through the operation of the third switching element TRS, sequentially selects the signal lines SGL in a time-division multiplexing manner within a single signal line block. Furthermore, the signal line selection circuit 16 selects one signal line SGL from each of multiple signal line blocks. With this configuration, the detection device 1 can reduce the number of ICs (integrated circuits) or the number of IC terminals included in the detection circuit 48. It should be noted that the signal line selection circuit 16 can also bundle multiple signal lines SGL together and connect them to the detection circuit 48.

[0092] like Figure 4 As shown, the reset circuit 17 has a reference signal line Lvr, a reset signal line Lrst, and a fourth switching element TrR. The fourth switching element TrR is configured to correspond to a plurality of signal lines SGL. The reference signal line Lvr is connected to one of the sources or drains of the plurality of fourth switching elements TrR. The reset signal line Lrst is connected to the gate of the plurality of fourth switching elements TrR.

[0093] Control circuit 102 supplies a reset signal RST2 to the reset signal line Lrst. This turns on multiple fourth switching elements TrR, and electrically connects multiple signal lines SGL to the reference signal line Lvr. Power supply circuit 103 supplies a reference signal COM to the reference signal line Lvr. This, in turn, powers the capacitor elements Ca (reference) contained in multiple partial detection areas PAA. Figure 5 ) Supply reference signal COM.

[0094] Figure 5 The circuit diagram illustrates the multiple detection areas of Embodiment 1. It should be noted that... Figure 5 The circuit configuration of the detection circuit 48 is also shown in the diagram. Figure 5 As shown, the detection area PAA includes a photodiode 30, a capacitor element Ca, and a first switching element Tr. The capacitor element Ca is a capacitor (sensor capacitor) formed in the photodiode 30, and is equivalently connected in parallel with the photodiode 30.

[0095] Figure 5 The diagram shows two gate lines GCL(m) and GCL(m+1) arranged along the second direction Dy out of a plurality of gate lines GCL. Additionally, two signal lines SGL(n) and SGL(n+1) arranged along the first direction Dx out of a plurality of signal lines SGL are shown. The partial detection region PAA is the area surrounded by the gate lines GCL and the signal lines SGL.

[0096] The first switching element Tr is provided corresponding to the photodiode 30. The first switching element Tr is a device composed of a thin film transistor, and in this example, it is composed of an n-channel MOS (Metal Oxide Semiconductor) type TFT (Thin Film Transistor).

[0097] The gate of the first switching element Tr, belonging to the multiple partial detection regions PAA arranged along the first direction Dx, is connected to the gate line GCL. The source of the first switching element Tr, belonging to the multiple partial detection regions PAA arranged along the second direction Dy, is connected to the signal line SGL. The drain of the first switching element Tr is connected to the cathode of the photodiode 30 and the capacitor element Ca.

[0098] A sensor power signal VDDSNS is supplied from the power supply circuit 103 to the anode of the photodiode 30. Furthermore, a reference signal COM, which serves as the initial potential of the signal line SGL and the capacitor element Ca, is supplied from the power supply circuit 103 to the signal line SGL and the capacitor element Ca.

[0099] When light is irradiated onto a portion of the detection area PAA, a current corresponding to the amount of light flows through the photodiode 30, thereby storing charge in the capacitor element Ca. When the first switching element Tr is turned on, current flows through the signal line SGL according to the charge stored in the capacitor element Ca. The signal line SGL is connected to the detection circuit 48 via the third switching element TRS of the signal line selection circuit 16. Thus, the detection device 1 can detect the signal corresponding to the amount of light irradiated onto the photodiode 30 for each portion of the detection area PAA or each block unit PAG.

[0100] During the reading process, switch SSW is turned on, and detection circuit 48 is connected to signal line SGL. Detection signal amplification circuit 42 of detection circuit 48 converts the current variation supplied from signal line SGL into a voltage variation and amplifies it. A reference potential (Vref) with a fixed potential is input to the non-inverting input (+) of detection signal amplification circuit 42, and signal line SGL is connected to the inverting input terminal (-). In this embodiment, a signal identical to the reference signal COM is input as the reference potential (Vref) voltage. Signal processing circuit 44 (reference) Figure 2 The difference between the detection signal Vdet under illumination and the detection signal Vdet without illumination is calculated and used as the sensor output voltage Vo. Furthermore, the detection signal amplification circuit 42 includes a capacitor element Cb and a reset switch RSW. During reset, the reset switch RSW is turned on, and the charge on the capacitor element Cb is reset.

[0101] Next, the configuration of photodiode 30 and filter 7 will be explained. Figure 6 This is a cross-sectional view showing the approximate cross-sectional structure of the sensor section. (See attached image.) Figure 6 As shown, the sensor unit 10 includes a photodiode (photoelectric conversion element) 30 and a sealing layer 25. Furthermore, a filter 7 is provided on the sealing layer 25.

[0102] The photodiode 30 has a detection electrode 31, an electron transport layer 32, an active layer 33, a hole transport layer 34, and a counter electrode 35. The detection electrode 31, the electron transport layer 32, the active layer 33, the hole transport layer 34, and the counter electrode 35 are sequentially stacked on the sensor substrate 2.

[0103] The detection electrode 31 is connected to the first switching element Tr (reference) of the sensor substrate 2 via a contact hole (not shown). Figure 5 Electrical connection. The detection electrode 31 is the cathode of the photodiode 30 and is used to read the detection signal Vdet. The detection electrode 31 is made of, for example, silver (Ag) or titanium (Ti). Alternatively, the detection electrode 31 may also be made of a transparent conductive material such as ITO (indium tin oxide).

[0104] The electron transport layer 32 and the hole transport layer 34 are provided to facilitate the arrival of holes and electrons generated in the active layer 33 at the counter electrode 35 or the detection electrode 31. The electron transport layer 32 and the hole transport layer 34 are, for example, made of zinc oxide (ZnO) and polythiophene-based conductive polymer (PEDOT:PSS).

[0105] The active layer 33 is a thin film made of polyimide having repeating units represented by the following chemical formula 6. Furthermore, the polyimide in the active layer 33 has a crystalline structure and possesses photoelectric conversion functionality. Therefore, when light is irradiated onto the active layer 33, holes and electrons are generated within it. The holes and electrons generated in the active layer 33 move through the electron transport layer 32 and the hole transport layer 34, respectively, and move towards the detection electrode 31 or the counter electrode 35.

[0106] [Chemical Formula 6]

[0107]

[0108] The counter electrode 35 is the anode of the photodiode 30 and is used to supply a power signal VDDSNS to the active layer 33. The counter electrode 35 and the detection electrode 31 are positioned opposite each other by clamping the active layer 33. The counter electrode 35 is made of ITO, for example.

[0109] The sealing layer 25 covers the photodiodes 30 and serves as a layer for planarizing the sensor section 10. More specifically, the sealing layer 25 fills the spaces between the photodiodes 30 and simultaneously covers the counter electrode 35 of each photodiode 30. The material of the sealing layer 25 is aluminum oxide (Al2O3).

[0110] The filter 7 is an optical component that transmits light along a third direction Dz and suppresses stray light outside the third direction Dz. The filter 7 includes a base 70 and multiple apertures 71. The base 70 functions as a light-blocking component that does not transmit light. Each aperture 71 is a cylindrical through-hole formed in the base 70. Furthermore, the base 70 is formed directly on the sealing layer 25. The multiple apertures 71 are arranged along the plane of the first direction Dx-second direction Dy of the base 70. It should be noted that the filter disclosed herein is not limited to this. It can be a multilayer pinhole type formed by alternately overlapping layers with a transparent resin layer containing multiple holes (pinholes). Alternatively, it can be a microlens type formed by alternately overlapping layers with pinholes and a transparent resin layer, with microlenses superimposed on the pinholes on the light-incident surface.

[0111] Next, the manufacturing method of photodiode 30 will be explained. Figure 7 A diagram illustrating the manufacturing process of the photodiode according to Embodiment 1. Figure 8 The diagram illustrates the manufacturing process of the active layer according to Embodiment 1. The manufacturing method of the photodiode 30 includes: a step S1 of generating a detection electrode 31; a step S2 of generating an electron transport layer 32; a step S3 of generating an active layer 33; a step S4 of generating a hole transport layer 34; and a step S5 of generating a counter electrode 35.

[0112] In process S1, conductive materials such as ITO are deposited on the sensor substrate 2 by means of vacuum evaporation, sputtering, ion plating, and deposition, thereby generating the detection electrode 31.

[0113] In step S2, a zinc acetate ethanol solution is coated onto the detection electrode 31 to form a zinc acetate sol-gel film. Next, the film is heated to generate an electron transport layer 32 comprising ZnO.

[0114] like Figure 8 As shown, the process S3 for generating the active layer includes a first layer forming process S11, a first heating process S12, and a second heating process S13. The process S3 for generating the active layer is sometimes referred to as the active layer generating process.

[0115] The first layer forming process S11 is a process of forming the first layer 51 by coating a solution of polyamic acid, which is a precursor of polyimide, onto the electron transport layer 32.

[0116] The first heating step S12 is a step of heating the first layer 51 at 120°C for 60 minutes. As a heating method, for example, ... Figure 8 As shown, one method is to place the sensor substrate 2 together with the sensor substrate 2 into an oven 50 for heating. It should be noted that the polyamic acid undergoes an imidization reaction through heating to above 200°C. Therefore, in the first heating step S12, the first layer 51 does not undergo an imidization reaction, resulting in reduced solvent residue and increased viscosity.

[0117] The second heating step S13 is, for example, heating the first layer 51 at 230°C to 280°C for 10 minutes using an oven 50. Through this second heating step S13, the first layer 51 undergoes an imidization reaction to become the active layer 33. It should be noted that the first heating step S12 and the second heating step S13 of this disclosure can also use heating methods other than an oven 50.

[0118] Next, as Figure 7 As shown, in step S4, PEDOT:PSS is coated onto the active layer 33 and then further heated. This forms a hole transport layer 34.

[0119] In step S5, conductive materials such as ITO and IZO are deposited on the hole transport layer 34 by, for example, vacuum evaporation, sputtering, ion plating, or deposition. Thus, step S5 is the step for generating the counter electrode 35.

[0120] The photodiode (photoelectric conversion element) 30 manufactured by the method of Embodiment 1 exhibits higher crystallinity and superior photoelectric conversion sensitivity compared to conventional photodiodes. Furthermore, the active layer 33, formed of polyimide, does not degrade thermally at temperatures up to 320°C. It should be noted that in the case of a bulk heterostructure active layer composed of PCBM (phenyl C61-butyric acid methyl ester), P3HT (poly(3-hexylthiophene)), and F8BT (F8-alt-benzothiadiazole), the heat resistance temperature is 100°C. Therefore, the photodiode (photoelectric conversion element) 30 manufactured by the method of Embodiment 1 has a higher heat resistance temperature than conventional photodiodes. Therefore, conventionally, when the filter 7 is formed on the sealing layer 25 covering the photodiode 30, it may cause thermal effects on the active layer 33. Furthermore, the filter 7 is manufactured separately and bonded to the sensor portion 10 with adhesive tape. However, according to Embodiment 1, even if the filter 7 is formed directly on the sealing layer 25 by photolithography, the impact on the active layer 33 is relatively low. That is, there is no need for adhesive tape to bond the filter 7, and the detection device 1 can be made thinner.

[0121] The photoelectric conversion element according to Embodiment 1 has been described above, but the photoelectric conversion element disclosed herein is not limited to the above-described situation. Other embodiments will be described below, but only the differences in the photoelectric conversion element according to Embodiment 1 will be explained.

[0122] (Implementation Method 2)

[0123] Figure 9 This is a cross-sectional view showing a schematic cross-sectional configuration of the sensor section according to Embodiment 2. The photodiode 30A according to Embodiment 2 differs from the photodiode 30 according to Embodiment 1 in that it has an active layer 33A instead of an active layer 33.

[0124] The active layer 33A in Embodiment 2 is a thin film formed of polyimide having repeating units represented by the following chemical formula 7. Furthermore, the active layer 33A has a crystalline structure and photoelectric conversion functionality.

[0125] [Chemical Formula 7]

[0126]

[0127] Figure 10A diagram illustrating the manufacturing process of the active layer according to Embodiment 2 is provided. The manufacturing method of the photodiode 30A is the same as that of Embodiment 1, including: a step S1 of generating a detection electrode 31; a step S2 of generating an electron transport layer 32; a step S3 of generating an active layer 33A; a step S4 of generating a hole transport layer 34; and a step S5 of generating a counter electrode 35 (see reference). Figure 7 In addition, such as Figure 10 As shown, the process of generating the active layer 33A includes: a first layer forming process S21; a first heating process S22; and a second heating process S23.

[0128] In the first layer formation process S21, a polyamic acid solution, serving as a precursor, is coated onto the electron transport layer 32 to form the first layer 52.

[0129] The first heating step S22 involves placing the sensor substrate 2 and the first layer 52 together in an oven 50 and heating it at 120°C for 20 to 60 minutes. It should be noted that the polyamic acid (precursor) undergoes an imidization reaction through heating to above 200°C. Therefore, in the first heating step S22, the first layer 52 does not undergo an imidization reaction, resulting in a reduced amount of residual solvent.

[0130] The second heating step S23 is a process in which the first layer 52 is heated in an oven 50 at 180°C to 260°C for 10 minutes. As a result, the polyamic acid (precursor) of the first layer 52 undergoes an imidization reaction to form an active layer 33A.

[0131] According to the manufacturing method of Embodiment 2, a photodiode 30 with high crystallinity of active layer 33A and excellent photoelectric conversion sensitivity can also be manufactured. In addition, the active layer 33A has a high heat resistance temperature of 300°C or higher, which allows the filter 7 to be formed directly on the sealing layer 25, and enables the detection device 1 to be thinner.

[0132] (Implementation Method 3)

[0133] Figure 11 This is a cross-sectional view showing a schematic cross-sectional configuration of the sensor unit according to Embodiment 3. The photodiode 30B according to Embodiment 3 differs from the photodiode 30 according to Embodiment 1 in that it has an active layer 33B instead of an active layer 33.

[0134] The active layer 33B involved in Embodiment 3 is a thin film formed of polyimide having repeating units represented by the following chemical formula 8. Furthermore, the active layer 33B has a crystalline structure and photoelectric conversion functionality.

[0135] [Chemical Formula 8]

[0136]

[0137] X: -O-, -S-, >CO, >C-R2, >SO2, -C(=O)-O-, -C(=O)-O-Φ-OC(=O)-

[0138] Here, R is -H, -CH3, or -CF3.

[0139] Y: S, Se, Te

[0140] m: 2, 4, 6, 8, 10

[0141] n: 3 or more oligomers or polymers

[0142] Figure 12 A diagram illustrating the manufacturing process of the active layer according to Embodiment 3 is provided. The manufacturing method of the photodiode 30B is the same as that of Embodiment 1, including: a process S1 for generating a detection electrode 31; a process S2 for generating an electron transport layer 32; a process S3 for generating an active layer 33B; a process S4 for generating a hole transport layer 34; and a process S5 for generating a counter electrode 35 (see reference). Figure 7 In addition, such as Figure 12 As shown, the process of generating the active layer 33B includes: a first layer forming process S31; a first heating process S32; and a second heating process S33.

[0143] The first layer forming step S31 is a step in which a polyamide carboxylic acid, as a precursor, is coated onto the electron transport layer 32 to form the first layer 53. Furthermore, the polyamide carboxylic acid has repeating units represented by the following chemical formula 9. It should be noted that the polyamide carboxylic acid of the following formula is obtained by a dehydration condensation reaction of an acid anhydride with a diamine compound.

[0144] [Chemical Formula 9]

[0145]

[0146] X: -O-, -S-, >CO, >C-R2, >SO2, -C(=O)-O-, -C(=O)-O-Φ-OC(=O)-

[0147] Here, R is -H, -CH3, or -CF3.

[0148] Y: S, Se, Te

[0149] m: 2, 4, 6, 8, 10

[0150] n: 3 or more oligomers or polymers

[0151] The first heating step S32 involves placing the first layer 53 in an oven 50 and heating it at 120°C for 20 minutes. Furthermore, the polyamide carboxylic acid in the above formula undergoes an imidization reaction through heating to above 200°C. Therefore, in the first heating step S32, the first layer 53 does not undergo an imidization reaction.

[0152] The second heating step S33 is a process in which the first layer 53 is heated in an oven 50 at 200°C to 240°C for 10 minutes. As a result, the polyamide carboxylic acid of the first layer 53 undergoes an imidization reaction to form a film as the active layer 33B.

[0153] Even with the manufacturing method described in Embodiment 3, a photodiode 30B with high crystallinity of the active layer 33B and excellent photoelectric conversion sensitivity can be manufactured. The active layer 33B has a high heat resistance temperature of 300°C, allowing the filter 7 to be formed directly on the sealing layer 25 (sensor section 10). Therefore, the detection device 1 can be made thinner.

[0154] (Implementation Method 4)

[0155] Figure 13 This is a cross-sectional view showing the schematic cross-sectional configuration of the sensor section according to Embodiment 4. The photodiode 30C according to Embodiment 4 differs from the photodiode 30 according to Embodiment 1 in that it has an active layer 33C instead of an active layer 33.

[0156] In Embodiment 4, the active layer 33C is formed by heterojunction of an n-type semiconductor 38 and a p-type semiconductor 37. The p-type semiconductor 37 is one of the polyimides represented by chemical formulas 5, 6, and 7 described in Embodiments 1 to 3, and has a crystal structure. Therefore, the p-type semiconductor 37 alone has photoelectric conversion function.

[0157] Furthermore, the n-type semiconductor 38 is obtained by heating and crystallizing a soluble porphyrin or phthalocyanine compound. The n-type semiconductor 38 has multiple columnar pillars 38a extending into the hole transport layer 34, and the n-type semiconductor 38 and the p-type semiconductor 37 form a three-dimensional pn junction. Therefore, more current can be extracted from the interface between the n-type semiconductor 38 and the p-type semiconductor 37. Therefore, compared to a single layer of p-type semiconductor 37, in other words, compared to the active layers 33, 33A, and 33B of Embodiments 1 to 3, the photoelectric sensitivity of the active layer 33C is improved. Next, the manufacturing method of the active layer 33C in Embodiment 4 will be described.

[0158] Figure 14 A diagram illustrating the manufacturing process of the active layer according to Embodiment 4. (See diagram below.) Figure 14As shown, the process of generating the active layer 33C includes: a substrate layer forming process S41; a substrate layer heating process S42; a first layer forming process S43; a first heating process S44; and a second heating process S45.

[0159] The substrate layer formation process S41 is a process of forming the substrate layer 54 by coating a soluble porphyrin or phthalocyanine compound on the electron transport layer 32.

[0160] The substrate heating process S42 is a process in which the substrate 54 is heated at 150°C for 30 minutes in an oven 50. As a result, the substrate 54 is cured and becomes part of the n-type semiconductor 38.

[0161] The first layer formation process S43 is a process of coating a substance made by mixing one of the polyimides shown in chemical formulas 5, 6, and 7 with a soluble porphyrin or phthalocyanine compound used in the base layer 54 onto a portion of the n-type semiconductor 38 to form the first layer 55.

[0162] In the first heating process S44, the sensor substrate 2 is placed in the oven 50, and the first layer 55 is heated at 120°C for 60 minutes.

[0163] Next, in the second heating process S45, the first layer 55 is heated at 120°C to 180°C for 10 minutes. Thus, as... Figure 14 As shown, starting from the soluble porphyrin or phthalocyanine compound contained in the first layer 55, a pillar 38a is formed on the substrate of the n-type semiconductor 38, extending toward the hole transport layer 34 (see reference). Figure 13 In addition, the polyimide also undergoes an imidization reaction to generate a crystallized p-type semiconductor 37.

[0164] Figure 15 A cross-sectional view showing a modified example of the active layer in Embodiment 4 is provided. It should be noted that, in this disclosure, for the heterogeneously bonded active layer 33C, the soluble porphyrin or phthalocyanine compound of the first layer 55 may not be columnar in shape during the second heating step S45. For example, as... Figure 15 As shown, it can be a state in which n-type semiconductor 38 and p-type semiconductor 37 coexist.

[0165] According to the manufacturing method of Embodiment 4, a photodiode 30D (photoelectric conversion element) with further improved sensitivity of photoelectric effect can be manufactured.

[0166] Figure 16 This is a cross-sectional view showing a modified example of the photoelectric conversion element. The embodiments have been described above, but as... Figure 16As shown, the photodiode (photoelectric conversion element) of this disclosure may also be a photodiode 30D in which the stacking order of the detection electrode 31, electron transport layer 32, active layer 33, hole transport layer 34, and counter electrode 35 is reversed from the order described in Embodiments 1 to 4.

[0167] (Example)

[0168] Next, the embodiments will be described. In Embodiment 1, a photodiode (photoelectric conversion element) was manufactured using the manufacturing method of Embodiment 1, and its crystallinity was confirmed. In Embodiment 2, a photodiode (photoelectric conversion element) was manufactured using the manufacturing method of Embodiment 2, and its crystallinity was confirmed. Hereinafter, Embodiment 1 and Embodiment 2 will be described.

[0169] (Example 1)

[0170] Figure 17 A graph showing the X-ray diffraction analysis results of samples 1 to 8. Figure 18 A graph showing the relationship between the half-width at half-maximum (WHM) of the X-ray spectra of samples 2, 3, 4, 5, 6, 7, and 8 and the substrate temperature during film formation is provided. In Example 1, a total of eight photodiodes were manufactured (hereinafter referred to as Sample 1, Sample 2, ..., Sample 8). Part of the samples were based on the manufacturing method of Embodiment 1, and the remainder were based on manufacturing methods other than those of Embodiment 1 (comparative examples).

[0171] In detail, samples 1 to 8 formed a first layer 51 using a first liquid containing polyamic acid in the first layer forming step S11. For samples 1 to 6, the first layer 51 was heated at 120°C for 60 minutes in the first heating step S12. On the other hand, samples 7 and 8 did not undergo the first heating step S12. Therefore, samples 7 and 8 are comparative examples.

[0172] Furthermore, for samples 1 to 8, the heating temperature and time in the second heating step S13 were changed respectively. Specifically, sample 1 was heated at 120°C for 20 to 60 minutes. Sample 2 was heated at 200°C for 10 minutes. Sample 3 was heated at 220°C for 10 minutes. Sample 4 was heated at 240°C for 10 minutes. Sample 5 was heated at 260°C for 10 minutes. Sample 6 was heated at 280°C for 10 minutes. Sample 7 was heated at 280°C for 60 minutes. Sample 8 was heated at 290°C for 60 minutes. As can be seen from the above, samples 1, 2, 3, 7, and 8 are comparative examples that do not meet the conditions of heating at 230°C to 280°C for 10 minutes as shown in the embodiment.

[0173] Next, X-ray diffraction was used to analyze the crystallinity of samples 1 to 8. The analytical results are shown below. Figure 17 .

[0174] like Figure 17 As shown, no obvious peaks were found in samples 1 to 3 and sample 7. That is, the polyimide (active layer 33) in samples 1 to 3 and sample 7 did not crystallize during the second heating process S13 and was mainly in an amorphous state. Samples 4 to 6 showed obvious diffraction peaks at 2θ = 18.5° and 2θ = 22.3°. In addition, the diffraction peak values ​​were also high. Therefore, it can be concluded that the polyimide (active layer 33) was sufficiently crystallized. Furthermore, although sample 8 showed a diffraction peak at 2θ = 22.3°, the peak value was small, indicating that the crystallinity was not sufficient.

[0175] Next, for samples 2, 3, 4, 5, 6, 7, and 8, the half-width at half-maximum (WWHM) of the X-ray spectra during X-ray diffraction was calculated (2θ = 18.5° for samples 2, 3, 4, 5, and 6; 2θ = 22.3° for samples 7 and 8), and the size of the microcrystals was determined. It should be noted that sample 8, like sample 7, is a photodiode generated without the first heating step S12; the heating temperatures of the second heating step S13 are 280°C and 290°C, respectively. The WWHM of the X-ray spectra is shown below. Figure 18 .

[0176] like Figure 18 As shown, the half-width decreases sequentially for samples 2, 3, 4, 5, and 6. Therefore, it can be concluded that within the heating temperature range of 200°C to 260°C in the second heating process, the crystallite size increases and crystallinity improves as the heating temperature rises. On the other hand, for samples 7 and 8, the half-width value is 0.7 or higher, indicating high polymorphism. Therefore, compared to samples 7 and 8, samples 4, 5, and 6, with heating temperatures of 230°C to 280°C in the second heating process S13, exhibit higher crystallinity, resulting in excellent photoelectric conversion sensitivity.

[0177] (Example 2)

[0178] Figure 19 A graph showing the X-ray diffraction analysis results of samples 11 to 16. Figure 20 A graph showing the relationship between the half-width at half-maximum (WHM) of the X-ray spectra of samples 11 to 16 involved in Example 2 and the substrate temperature during film formation is provided. Next, Example 2 will be described. In Example 2, a total of six photodiodes were manufactured (hereinafter referred to as Sample 11, Sample 12, ..., Sample 16). A portion of the samples were based on the manufacturing method of Example 2, and the remainder were based on manufacturing methods other than those of Example 2 (comparative examples).

[0179] In detail, for samples 11 to 16, a first layer 52 is formed by coating an amic acid solution, which is a precursor of chemical formula 2, in the first layer forming step S21. For samples 11 to 16, the first layer 52 is heated at 120°C for 20 to 60 minutes in the first heating step S12.

[0180] Furthermore, for samples 11 to 16, the heating temperature in the second heating step S13 was changed respectively. Specifically, sample 11 was heated at 180°C. Sample 12 was heated at 200°C. Sample 13 was heated at 220°C. Sample 14 was heated at 240°C. Sample 15 was heated at 260°C. Sample 16 was heated at 280°C. As can be seen from the above, samples 11 to 15 meet the condition of heating at 180°C to 260°C for 10 minutes as shown in Embodiment 2, while sample 16 is a comparative example that does not meet the condition of the embodiment. It should be noted that the heating time for samples 11 to 16 is 10 minutes.

[0181] Next, X-ray diffraction was used to analyze the crystallinity of samples 11 to 16. The analytical results are shown below. Figure 19 Furthermore, the half-width at half-maximum (WHM) of the X-ray spectrum was determined for X-ray diffraction (2θ = 18.6° and 2θ = 22.0°), and the size of the microcrystal was calculated. The WHM of the X-ray spectrum is shown below. Figure 20 .

[0182] like Figure 19 As shown, samples 11 to 16 exhibit diffraction peaks at 2θ = 18.6° and 2θ = 22.0°. Furthermore, samples 11 to 15 also show high diffraction peaks, indicating sufficient crystallization of the polyimide film. Sample 16 shows a small peak, indicating insufficient crystallinity. Therefore, it can be concluded that sufficient crystallization can be achieved when the condition of heating at 180°C to 260°C for 10 minutes in the second heating step S23 is met.

[0183] In addition, such as Figure 20 As shown, among samples 11 to 15, sample 13 (heating temperature 220℃) has a half-width value below 0.4, indicating the strongest crystallinity. Therefore, it can be concluded that sample 13 has the highest crystallinity and excellent photoelectric conversion sensitivity among samples 11 to 15.

[0184] Explanation of reference numerals in the attached figures

[0185] 120 Optical Sensor

[0186] 121 lighting fixtures

[0187] 1. Detection device

[0188] 2. Sensor substrate

[0189] 3. Detection element

[0190] 7. Filters

[0191] 10. Sensor Department

[0192] 15. Scan line drive circuit

[0193] 16 Signal line selection circuit

[0194] 21 substrate

[0195] 25 Sealing layer

[0196] 30. Photodiode (photoelectric conversion element)

[0197] 31 Detection Electrode

[0198] 32 Electron Transport Layer

[0199] 33 Active layer

[0200] 34 Hole transport layer

[0201] 35 Opposite Electrode

[0202] 51, 52, 53, 55 First Floor

[0203] 70 base

[0204] 71 aperture

[0205] 102 Control Circuit

[0206] 103 Power Supply Circuit

[0207] S11, S21, S31, S43 First layer forming process

[0208] S12, S22, S32, S44 First heating process

[0209] S13, S23, S33, S45 Second heating process

[0210] S41 Base Layer Formation Process

[0211] S42 Base Layer Heating Process

Claims

1. A method for manufacturing a photoelectric conversion element, comprising an active layer forming step of forming an active layer having a repeating unit represented by the following Chemical Formula 1, the active layer forming step comprising: a base layer forming step, wherein applying a soluble porphyrin or phthalocyanine compound to form a base layer of the active layer; a base layer heating step of performing heat treatment on the base layer at 150°C; a first layer forming step of applying a polyamic acid as a precursor to form a first layer; a first heating step of heating the first layer at 120°C for 20 minutes to 60 minutes; and a second heating step of heating the first layer at 230°C to 280°C for 10 minutes, wherein, in the first layer forming step, after the base layer heating step, a substance obtained by adding and mixing the soluble porphyrin or phthalocyanine compound used in the base layer to the precursor is applied to form the first layer, [Chemical Formula 1] 。 2. A method for manufacturing a photoelectric conversion element, comprising an active layer forming step of forming an active layer having a repeating unit represented by the following Chemical Formula 2, the active layer forming step comprising: a base layer forming step, wherein applying a soluble porphyrin or phthalocyanine compound to form a base layer of the active layer; a base layer heating step of performing heat treatment on the base layer at 150°C; a first layer forming step of applying a polyamic acid solution as a precursor of the following Chemical Formula 2 to form a first layer; a first heating step of heating the first layer at 120°C for 20 minutes to 60 minutes; and a second heating step of heating the first layer at 180°C to 280°C for 10 minutes, wherein, in the first layer forming step, after the base layer heating step, a substance obtained by adding and mixing the soluble porphyrin or phthalocyanine compound used in the base layer to the precursor is applied to form the first layer, [Chemical Formula 2] 。 3. A method for manufacturing a photoelectric conversion element, comprising an active layer forming step of forming an active layer having a repeating unit represented by the following Chemical Formula 3, the active layer forming step comprising: a base layer forming step, wherein applying a soluble porphyrin or phthalocyanine compound to form a base layer of the active layer; a base layer heating step of performing heat treatment on the base layer at 150°C; a first layer forming step of applying a polyamic carboxylic acid as a precursor and having a repeating unit represented by the following Chemical Formula 4 to form a first layer; a first heating step of heating the first layer at 120°C for 20 minutes to 60 minutes; and a second heating step of heating the first layer at 180°C to 280°C for 10 minutes, wherein, in the first layer forming step, after the base layer heating step, a substance obtained by adding and mixing the soluble porphyrin or phthalocyanine compound used in the base layer to the precursor is applied to form the first layer, [Chemical Formula 3] X: -O-, -S-, >CO, >C-R2, >SO2, -C(=O)-O-, -C(=O)-O-Φ-O-C(=O)-, where, R is -H, -CH3, -CF3, Y: S, Se, Te, m：2、4、6、8、10， n: 3 or more [Chemical Formula 4] X: -O-, -S-, >CO, >C-R2, >SO2, -C(=O)-O-, -C(=O)-O-Φ-O-C(=O)-, Here, R is -H, -CH3, -CF3, Y: S, Se, Te, m：2、4、6、8、10， n: 3 or more.

4. An optical sensor comprising: a substrate; and a sensor portion laminated to the substrate, the sensor portion having a detection electrode, an electron transport layer, an active layer, a hole transport layer, and a counter electrode, and having a photoelectric conversion element laminated to the substrate, the active layer having: an n-type semiconductor laminated to the electron transport layer, the n-type semiconductor being obtained by crystallizing a soluble porphyrin or a phthalocyanine compound by a heat treatment at 150°C for 30 minutes; and a p-type semiconductor laminated to the n-type semiconductor, the p-type semiconductor being formed of a polyimide-based material having a repeating unit represented by Chemical Formula 5 below, and being obtained by crystallizing the soluble porphyrin or the phthalocyanine compound used in the n-type semiconductor by a heat treatment at 120°C for 60 minutes, followed by a heat treatment at 120°C to 180°C for 10 minutes, the n-type semiconductor and the p-type semiconductor being heterojunction, and being in a state where a column portion extending toward the hole transport layer is formed with the n-type semiconductor as a base material, or being in a state where the n-type semiconductor and the p-type semiconductor are mixedly present, [Chemical Formula 5] 。 5. The optical sensor according to claim 4, comprising a filter laminated to the sensor portion. the filter being directly formed on the sensor portion.

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