Photoelectric conversion element inspection device, photoelectric conversion element manufacturing device, photoelectric conversion element manufacturing method, and photoelectric conversion element

Abstract

The photoelectric conversion element inspection device (20), the photoelectric conversion element manufacturing device (30) and the photoelectric conversion element manufacturing method are provided. The photoelectric conversion element is provided with one or more light sources (21, 24), a driving device (27), cameras (22, 25) and a computer (28). The light sources (21, 24) irradiate the perovskite layer with inspection light (L1, L2) capable of transmitting the perovskite layer and / or reflecting the perovskite layer. The drive device (27) changes at least one of the distance and the angle between the substrate having the perovskite layer and the light sources (21, 24). The cameras (22, 25) detect the hue of at least one of the inspection lights (L1 ', L2') transmitted through the perovskite layer or reflected by the perovskite layer, and the computer (28) calculates the positions of points having different hues on the perovskite layer detected by the cameras (22, 25).

Description

Technical Field

[0001] Embodiments of the present invention relate to an inspection device for a photoelectric conversion element, a manufacturing device for a photoelectric conversion element, a manufacturing method for a photoelectric conversion element, and a photoelectric conversion element.

[0002] This application claims priority based on Japanese Patent Application No. 2022-120680 filed in Japan on July 28, 2022, the contents of which are cited herein. Background Art

[0003] As a multi-layer junction type photoelectric conversion element, a tandem solar cell is known. The tandem solar cell is constructed as follows. That is, the tandem solar cell has a second photoelectric conversion element including a second photoactive layer on the light-receiving side of the semiconductor substrate, and has a first photoelectric conversion element on the opposite side of the light-receiving side of the semiconductor substrate that enables the semiconductor substrate to function as a first photoactive layer. As the second photoactive layer, a photoactive layer having a photoactive layer (hereinafter referred to as a perovskite layer) composed of a material with a perovskite crystal structure is known. The photoelectric conversion element using a perovskite material has the advantage that an inexpensive coating method can be applied when forming the layer.

[0004] When manufacturing a tandem solar cell, for example, a first photoelectric conversion element is formed on the opposite side of the light-receiving surface of a semiconductor substrate so that the semiconductor substrate functions as a first photoactive layer as an intermediate. Then, a second photoelectric conversion element including a second photoactive layer is formed on the light-receiving surface side of the intermediate to complete the process.

[0005] Crystalline silicon cited as the first photoactive layer is formed by cutting out from a silicon wafer, etc. Since there are cutting marks on the surface of the silicon wafer, it is desirable to increase the thickness of the perovskite layer.

[0006] However, if the perovskite layer is thickened, pinholes are likely to be generated. In addition to pinholes caused by foreign matter, pinholes that accompany the thickening of the perovskite layer also include pinholes generated during the crystallization process of the perovskite. In the case of forming the perovskite layer by a two-step coating method (a coating method in which PBI2 is coated on a substrate and then MAI is coated), there are pinholes formed by the second liquid. Pinholes that accompany the thickening of the perovskite layer are likely to become oblique pinholes that are inclined relative to the normal direction of the perovskite layer. The oblique pinholes are difficult to detect in detection from a certain position, and the opportunity for repair may be lost.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 3935781 Summary of the invention

[0010] Technical problem to be solved by the invention

[0011] The technical problem to be solved by the present invention is to provide a photoelectric conversion element inspection device, a photoelectric conversion element manufacturing device, a photoelectric conversion element manufacturing method, and a photoelectric conversion element that can easily detect pinholes generated in a perovskite layer.

[0012] Means for solving technical problems

[0013] The inspection device of the photoelectric conversion element, the manufacturing device of the photoelectric conversion element, the manufacturing method of the photoelectric conversion element, and the photoelectric conversion element of the embodiment have one or more light sources, a driving device, a camera, and a computer. The light source irradiates the perovskite layer with an inspection light that can transmit the perovskite layer or reflect the perovskite layer. The driving device changes at least one of the distance or angle between the substrate having the perovskite layer and the light source. The camera detects the hue of at least one of the inspection lights that transmit the perovskite layer or reflect the perovskite layer. The computer calculates the position of the point with different hue on the perovskite layer detected by the camera. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 1 is a schematic cross-sectional view showing a multilayer junction type photoelectric conversion element used in a tandem solar cell according to an embodiment.

[0015] Figure 2 It is a schematic cross-sectional view showing a multilayer junction type photoelectric conversion element used in a single-unit solar cell according to an embodiment.

[0016] Figure 3 Schematic cross-sectional view showing a pinhole in a perovskite layer of a multilayer junction photoelectric conversion element according to an embodiment.

[0017] Figure 4 It is a schematic diagram showing a first embodiment of the inspection apparatus and manufacturing apparatus of the photoelectric conversion element according to the embodiment.

[0018] Figure 5 It is a schematic diagram showing a second embodiment of the inspection apparatus and manufacturing apparatus of the photoelectric conversion element according to the embodiment.

[0019] Figure 6 It is a schematic diagram showing a third embodiment of the inspection apparatus and manufacturing apparatus of the photoelectric conversion element according to the embodiment. DETAILED DESCRIPTION

[0020] Hereinafter, a photoelectric conversion element inspection apparatus, a photoelectric conversion element manufacturing apparatus, a photoelectric conversion element manufacturing method, and a photoelectric conversion element according to embodiments will be described with reference to the drawings.

[0021] In the embodiments, the photoelectric conversion element refers to both an element that converts light into electricity, such as a solar cell or a sensor, and an element that converts electricity into light, such as a light-emitting element. The two elements differ in whether the active layer functions as a power generation layer or as a light-emitting layer, but have the same basic structure.

[0022] [Photoelectric conversion element]

[0023] Figure 1 A multilayer junction type photoelectric conversion element (photoelectric conversion element) 1 used in a tandem solar cell is shown.

[0024] Figure 1 The multilayer junction photoelectric conversion element 1 shown in the figure is stacked in order from the bottom side of the figure, including a first electrode functional layer 2, a first photoactive layer 3 composed of crystalline silicon, an intermediate functional layer 4, a second photoactive layer (perovskite layer) 5 composed of a photoactive material having a perovskite crystal structure, and a second electrode functional layer 6 to form a stacked body 7. Figure 1 In the multilayer junction photoelectric conversion element 1 shown, the light-receiving surfaces of the first photoactive layer 3 and the second photoactive layer 5 are surfaces on the second electrode functional layer 6 side (upper surfaces in the figure).

[0025] The first electrode functional layer 2 is configured to include, for example, a first electrode and a first functional layer (conductive layer) disposed between the first electrode and the first photoactive layer 3 (both are not shown).

[0026] The first photoactive layer 3 is composed of a crystalline silicon layer of the first conductivity type. The crystalline silicon constituting the first photoactive layer 3 can generally adopt the same composition as the silicon used for photovoltaic cells. The composition of crystalline silicon can include single crystal silicon, polycrystalline silicon, heterojunction silicon and other crystalline silicon containing crystalline silicon. Crystalline silicon can also be a thin film cut from a silicon wafer. As a silicon wafer, an n-type silicon crystal doped with phosphorus or arsenic, etc., or a p-type silicon crystal doped with boron or gallium, etc. can also be used. Since the electrons in the p-type silicon crystal have a long diffusion length, p-type crystalline silicon is preferably used as the crystalline silicon of the first conductivity type.

[0027] The intermediate functional layer 4 has at least the following functions. That is, the intermediate functional layer 4 has the function of connecting in series the bottom unit mainly composed of the first photoactive layer 3 and the top unit mainly composed of the second photoactive layer 5. The intermediate functional layer 4 is, for example, configured to include a functional layer (second conductive layer) 4a in contact with the first photoactive layer 3, a functional layer (buffer layer) 4c in contact with the second photoactive layer 5, and a transparent electrode (substrate) 4b sandwiched between the second conductive layer 4a and the buffer layer 4c.

[0028] The second photoactive layer 5 is composed of a photoactive material having a perovskite crystal structure. The perovskite crystal structure refers to a crystal structure that is the same as perovskite. The perovskite structure is composed of ions A, B, and X. When ion B is smaller than ion A, the perovskite structure is sometimes used. The chemical composition of the crystal structure can be represented by the following general formula (1).

[0029] ABX3(1)

[0030] Ion A can utilize primary ammonium ions. Specifically, CH3NH3+ (hereinafter sometimes referred to as MA), C2H5NH3+, C3H7NH3+, C4H9NH3+, and HC(NH2)2+ (hereinafter sometimes referred to as FA) can be cited. Ion A is preferably CH3NH3+, but is not limited to this. In addition, ion A is also preferably Cs+, 1,1,1-trifluoro-ethylammonium iodide (FEAI), but is not limited to these.

[0031] Ion B is a divalent metal ion, preferably Pb2+ or Sn2+, but not limited thereto.

[0032] The ion X is preferably a halogen ion, for example, selected from F-, Cl-, Br-, I-, and At-. The ion X is preferably Cl-, Br-, and I-, but is not limited thereto.

[0033] The materials constituting the ions A, B or X may be either single or mixed. The constituent ions do not have to conform to the ratio of ABX3 to function.

[0034] The ion A constituting the perovskite of the second photoactive layer 5 is preferably composed of an atomic weight or a total of the atomic weights of the constituent ions (molecular weight) of 45 or more. More preferably, the ion A preferably contains ions of 133 or less. If the ion A under these conditions is a monomer, the stability is low, so sometimes a general MA (molecular weight 32) is mixed. When MA is mixed, the ion A is close to the band gap of silicon 1.1eV. In this way, as a series connection for wavelength division to improve efficiency, the overall characteristics are low, so it is not preferred. In the case where ion A is a combination of multiple ions and contains Cs, it is more preferred that the ratio of the number of Cs to the total number of ions A is 0.1 to 0.9.

[0035] This crystal structure has a unit lattice such as cubic, tetragonal, orthorhombic, with ions A arranged at each vertex, ions B arranged at the body center, and ions X arranged at each face center of the cubic crystal centered at the body center. In this crystal structure, the octahedron composed of one ion B and six ions X contained in the unit cell has the following characteristics. That is, the octahedron is easily strained by the interaction with ions A, and the phase transition is a symmetrical crystal. It is estimated that this phase transition causes a sharp change in the physical properties of the crystal, and electrons or holes are released outside the crystal, causing power generation.

[0036] Second electrode functional layer 6 includes, for example, functional layer (buffer layer) 6a in contact with second photoactive layer 5, second functional layer (conductive layer) 6b in contact with functional layer 6a, and second electrode 6c protruding from second functional layer 6b.

[0037] The first functional layer (not shown) included in the first electrode functional layer 2 and the second functional layer 6b included in the second electrode functional layer 6 function as follows. That is, with respect to the second photoactive layer 5, one of the first functional layer and the second functional layer 6b functions as a hole transport layer, and the other functions as an electron transport layer. In order to achieve a better conversion efficiency, the multilayer junction photoelectric conversion element 1 of the embodiment preferably includes both the first functional layer and the second functional layer 6b. The multilayer junction photoelectric conversion element 1 of the embodiment may also include at least only the second functional layer 6d.

[0038] The first conductive layer (not shown) included in the first electrode functional layer 2 and the second conductive layer 4a included in the intermediate functional layer 4 are configured as follows. That is, the first conductive layer and the second conductive layer 4a can be combined with an n-type layer, a p-type layer, a p+ type layer, a p++ type layer, etc. according to the characteristics of the first photoactive layer 3 and the purpose of improving the carrier collection efficiency. When p-type silicon is used as the first photoactive layer 3, a phosphorus-doped silicon film (n-layer) can be combined as the second conductive layer 4a, and a p+ layer can be combined as the first conductive layer.

[0039] Figure 1 The multilayer junction photoelectric conversion element 1 shown has two photoactive layers 3 and 5. The multilayer junction photoelectric conversion element 1 has a unit having the second photoactive layer 5 as a top unit and a unit having the first photoactive layer 3 as a bottom unit. The multilayer junction photoelectric conversion element 1 is a tandem solar cell having a structure in which the two photoactive layers 3 and 5 are connected in series via an intermediate functional layer 4. The first electrode functional layer 2 and the second electrode functional layer 6 serve as an anode or a cathode, and the electric energy generated by the multilayer junction photoelectric conversion element 1 is taken out to the outside from these poles.

[0040] Figure 2A multilayer junction type photoelectric conversion element (photoelectric conversion element) 11 used for a single-unit solar cell is shown.

[0041] Figure 2 The multilayer junction photoelectric conversion element 11 shown in the figure constitutes the following stacked body 17. That is, the stacked body 17 is stacked in order from the bottom side in the figure with a transparent substrate 13, a first electrode functional layer 14, a photoactive layer (perovskite layer) 15 composed of a photoactive material having a perovskite crystal structure, and a second electrode functional layer 16. Figure 2 In the multilayer junction photoelectric conversion element 11 shown, the light-receiving surface of the photoactive layer 15 is set as the surface on the second electrode functional layer 16 side (the upper surface in the figure).

[0042] The photoactive layer 15 is Figure 1 The second photoactive layer 5 of the multilayer junction photoelectric conversion element 11 is configured in the same manner.

[0043] The second electrode functional layer 16 is configured to include, for example, a functional layer (conductive layer) 16 b in contact with the photoactive layer 15 and a second electrode 16 c protruding from the functional layer 16 b .

[0044] The first electrode functional layer 14 and the second electrode functional layer 16 serve as an anode or a cathode, and the electric energy generated by the multilayer junction photoelectric conversion element 11 is extracted to the outside from these electrodes.

[0045] [Intermediate]

[0046] Next, the intermediates 8 and 18 obtained in the middle of the manufacturing process of the multilayer junction photoelectric conversion elements 1 and 11 are described. The intermediate 8 is an intermediate in the manufacturing process of the photoelectric conversion element 1, and the intermediate 18 is an intermediate in the manufacturing process of the photoelectric conversion element 11.

[0047] like Figure 1 to Figure 3 As shown, the intermediate 8, 18 has a substrate 8b, 18b having an electrode layer 8a, 18a as a film-forming object. A perovskite solution is applied to the electrode layer 8a, 18a. The applied perovskite solution is dried to form the perovskite layer 5a, 15a. The solution coating method (and coating device) can be any method (and device) as long as it can supply the solution to the film-forming object with a uniform film thickness. The solution coating is applied by a liquid coating method such as a spin coating method, a slit coating method, a screen printing method, a spray method, a meniscus coating method, etc.

[0048] For example, the intermediate body 8 in the tandem solar cell is composed of a stack of substrate 8b (first electrode functional layer 2 and first photoactive layer 3), electrode layer 8a (intermediate functional layer 4), and perovskite layer 5a.

[0049] For example, in the intermediate body 18 in the single-unit solar cell, a substrate 18 b (transparent substrate 13 ), an electrode layer 18 a (first electrode functional layer 14 ), and a perovskite layer 15 a are stacked.

[0050] For example, in the intermediate 8 of the tandem solar cell, the crystalline silicon used as the first photoactive layer 3 is formed by cutting out from a silicon wafer, etc. Considering the existence of cutting marks on the surface of the substrate such as the silicon wafer, it is desirable to thicken the perovskite layers 5a and 15a.

[0051] When the perovskite layer 5a, 15a is thickened, the following possibilities exist in the dried perovskite layer 5a, 15a. Figure 3 As shown, in addition to the usual pinholes Pa that penetrate the perovskite layers 5a and 15a in the thickness direction (normal direction) perpendicular to the front and back surfaces, pinholes (hereinafter referred to as oblique pinholes) Pb that are inclined relative to the normal direction of the perovskite layers 5a and 15a are sometimes generated. Regarding the oblique pinholes Pb, if the inspection light La is irradiated from the normal direction, the light does not pass through, making it difficult to detect. If the inspection light Lb is irradiated from an oblique direction relative to the normal direction, the light passes through the oblique pinholes Pb. However, the inclination direction and angle of the oblique pinholes Pb vary, and it is difficult to detect even if the inspection light is irradiated from a certain direction.

[0052] The solar cell is manufactured by laminating a transparent electrode film (second electrode functional layer 6 or 26) on the perovskite layer 5a, 15a. If there are pinholes or foreign matter with a certain size or more in the perovskite layer 5a, 15a, a short circuit between the front and back sides is likely to occur at the abnormal part of the perovskite layer 5a, 15a, thereby reducing the photoelectric conversion rate of the finally completed solar cell.

[0053] By repairing the abnormal part (especially the pinhole), the performance degradation can be suppressed. As a treatment, for example, by making the solution of the raw material forming the perovskite layer 5a, 15a adhere, a dried product of the perovskite structure (crystal) is formed. In addition, as another example, a solution coated with an insulating substance or with an insulating substance as a solute is adhered and dried, so that a dried product with insulating properties remains. As another example, the electrodes on the front and back sides of the perovskite layers 5a, 15a are removed by laser, or the surface in contact with the pinhole in the substrate 8b is sintered by laser irradiation to form an insulating portion. Whether the electrode is removed or sintered depends on the energy of the laser. In this way, short circuits in the pinholes of the perovskite layers 5a, 15a are prevented, and the conversion efficiency of the solar cell is well maintained.

[0054] [Inspection device and manufacturing device for photoelectric conversion film element]

[0055] Next, a photoelectric conversion element inspection apparatus and a photoelectric conversion element manufacturing apparatus according to an embodiment will be described with reference to the drawings.

[0056] (First Embodiment)

[0057] Figure 4 The manufacturing process of the photoelectric conversion element in the first embodiment is schematically shown.

[0058] like Figure 4 As shown, the inspection device 20 of the photoelectric conversion element of the first embodiment moves the intermediate 8, 18 on which the perovskite layer 5a, 15a is formed, while irradiating the intermediate 8, 18 with inspection light (for example, visible light of a wavelength with strong reflection of ITO (transparent conductive film)). The inspection device 20 detects the abnormality of the perovskite layer 5a, 15a by detecting the hue of the inspection light (at least one of the transmitted light and the reflected light) that has passed through the perovskite layer 5a, 15a.

[0059] The manufacturing device 30 of the photoelectric conversion element of the first embodiment applies (attaches) a perovskite solution to the abnormal part Pc found by the inspection device 20. The manufacturing device 30 repairs the perovskite layer 5a, 15a by covering the abnormal part Pc with a dried material with a perovskite structure. For example, the perovskite solution is not limited as long as it is a material that forms a perovskite structure at least in part.

[0060] As described above, the perovskite structure is one of the crystal structures and refers to a crystal structure that is the same as perovskite. Typically, the perovskite structure is composed of ions A, B, and X. When ion B is smaller than ion A, the perovskite structure is sometimes adopted. The chemical composition of the crystal structure can be represented by the following general formula (1).

[0061] ABX3(1)

[0062] Here, A can utilize primary ammonium ions. Specifically, CH3NH3+, C2H5NH3+, C3H7NH3+, C4H9NH3+, and HC(NH2)2+ can be cited. A is preferably CH3NH3+, but is not limited to this. In addition, A is also preferably Cs+, 1,1,1-trifluoro-ethylammonium iodide (FEAI), but is not limited to this. In addition, B is a divalent metal ion, preferably Pb2- or Sn2-, but is not limited to this. In addition, X is preferably a halogen ion. X is, for example, selected from F-, Cl-, Br-, I- and At-, preferably Cl-, Br- or I-, but is not limited to this. The materials constituting ions A, B or X can be single or mixed. The constituting ions do not have to be consistent with the ratio of ABX3 to function.

[0063] like Figure 4As shown, the inspection device 20 comprises: a first lamp 21, which irradiates the first inspection light L1 that transmits the perovskite layer 5a, 15a of the intermediate 8, 18; a first camera 22, which detects the hue of the first inspection light L1 that transmits the perovskite layer 5a, 15a; a second lamp 24, which irradiates the perovskite layer 5a, 15a with the second inspection light L2 reflected on the front side (upper surface) thereof; a second camera 25, which detects the hue of the second inspection light L2 reflected by the perovskite layer 5a, 15a; a workbench driving device 27, which appropriately displaces the workbench 27a on which the intermediate 8, 18 is placed, so as to change the distance and angle between the intermediate 8, 18 and the first lamp 21 and the second lamp 24; and a computer 28, which calculates the positions of points with different hues on the perovskite layer 5a, 15a based on the detection information of the first camera 22 and the second camera 25.

[0064] A first lamp 21 is arranged below the workbench 27a to irradiate the first inspection light L1 from the lower side to the intermediates 8 and 18 placed on the workbench 27a. The first lamp 21 includes a light source such as a fluorescent lamp or an LED, and the brightness is adjusted by a dimmer. The first lamp 21 is arranged at an angle close to the normal direction of the intermediates 8 and 18 so that the emitted first inspection light L1 passes through the intermediates 8 and 18 (substrate and perovskite layers 5a and 15a). The first inspection light L1 passes through the perovskite layers 5a and 15a to become the transmitted light L1'.

[0065] Above the workbench 27a, a first camera 22 for incident first inspection light L1 (transmitted light L1') that transmits the intermediate body 8, 18 is arranged in the irradiation direction of the first lamp 21. The first camera 22 captures the portion of the upper surface of the perovskite layer 5a, 15a through which the first inspection light L1 is transmitted. The first camera 22 converts the transmitted light L1' of the captured portion into an electrical signal and sends it to the signal processing unit of the computer 28. The signal processing unit detects a portion having a different hue from a general portion (normal portion) that occupies most of the perovskite layer 5a, 15a based on the image captured by the first camera 22. The above-mentioned "portion having a different hue" appears due to an abnormality such as a pinhole in the perovskite layer 5a, 15a. The computer 28 identifies the "portion having a different hue" as an abnormal portion Pc. The first camera 22 and the first lamp 21 constitute a transmission type inspection device.

[0066] A second lamp 24 is arranged above the workbench 27a to irradiate the second inspection light L2 from the upper side to the intermediates 8 and 18 on the workbench 27a. The second lamp 24 includes a light source such as a fluorescent lamp or an LED, and the brightness is adjusted by a dimmer. The second lamp 24 is arranged so that the emitted second inspection light L2 is incident obliquely with respect to the upper surface of the perovskite layer 5a and 15a. The second inspection light L2 is reflected on the upper surface of the perovskite layer 5a and 15a to become a reflected light L2'.

[0067] Above the workbench 27a, a second camera 25 is arranged in the reflection direction of the second inspection light L2, into which the second inspection light L2 (reflected light L2') reflected by the perovskite layer 5a, 15a is incident. The second camera 25 captures the portion of the upper surface of the perovskite layer 5a, 15a irradiated by the second inspection light L2. The second camera 25 converts the reflected light L2' of the captured portion into an electrical signal and sends it to the signal processing unit of the computer 28. The signal processing unit detects a portion having a different hue from the general portion (normal portion) of the perovskite layer 5a, 15a based on the image captured by the second camera 25. The computer 28 identifies the "portion having a different hue" as an abnormal portion Pc. The second camera 25 and the second lamp 24 constitute a regular reflection inspection device. The second camera 25 and the second lamp 24 are preferably tilted integrally according to the tilting action of the intermediate 8, 18.

[0068] The table driving device 27 drives the table 27a so that its upper surface (intermediate body loading surface) is tilted from a horizontal state to the front, back, left, and right, and can rotate the table 27a around a vertical axis. Reference numeral 27b in the figure represents a control unit of the table driving device 27. The control unit 27b detects how much the table 27a is tilted from a predetermined initial position and the amount of rotation, and outputs it to the computer 28. The computer 28 recognizes the position of each part of the upper surface of the table 27a based on the amount of movement of the table 27a output from the control unit 27b.

[0069] The computer 28 is a computer device, and includes a hardware device such as a CPU (Central Processing Unit) and a storage device that stores programs (software) executed by the CPU. The input portion of the computer 28 is connected to the output portions of the first camera 22 and the second camera 25 and the control portion 27b of the stage driving device 27. The output portion of the computer 28 is connected to the control portion 31a of the repair device (an inkjet device described later) 31 for repairing pinholes in the perovskite layers 5a and 15a.

[0070] For example, the computer 28 sets the coordinates on the perovskite layer 5a, 15a based on the movement amount of the workbench 27a obtained from the control unit 27b of the workbench driving device 27. For example, the computer 28 determines the following positions based on the relative positions and relative angles between the workbench 27a (intermediate body 8, 18) and the first lamp 21 and the second lamp 24. That is, the computer 28 determines the position of the "point (site) with different hue" on the perovskite layer 5a, 15a detected by the first camera 22 and the second camera 25. The hue itself of the above-mentioned "point with different hue" is different depending on the type of abnormality of the perovskite layer 5a, 15a. The inspection device 20 of the embodiment particularly determines the position of the "point with different hue" corresponding to the pinhole of the perovskite layer 5a, 15a. The inspection device 20 can detect whether there is an abnormality in the perovskite layer 5a, 15a and its position when there is an abnormality.

[0071] The manufacturing device 30 of the first embodiment makes the solution of the raw material for forming the perovskite layer 5a, 15a adhere to the position of the "point with different hue" determined by the computer 28 to perform repair. In the figure, reference numeral 31 represents a repair device for attaching (applying) the solution to the perovskite layer 5a, 15a. For example, the repair device 31 is an inkjet device for attaching the solution. By attaching the above-mentioned solution to the position of the "point with different hue" with the inkjet device and drying it, a perovskite structure (crystal) is formed at this position. In this way, the pinholes of the perovskite layer 5a, 15a can be removed. Alternatively, a solution with an insulating substance as a solute can be attached to the position of the above-mentioned "point with different hue" and dried, and the dried product of the solution can be left, so that short circuits in the pinholes of the perovskite layer 5a, 15a can also be prevented. In this way, the conversion efficiency of the solar cell using the intermediate 8, 18 having the perovskite layer 5a, 15a can be improved.

[0072] In the first embodiment, a laser device according to a second embodiment described later may be used for the repair device 31 instead of the inkjet device.

[0073] The pinholes in the embodiment refer to traces of foreign matter peeling off in the perovskite layer 5a, 15a, thinned portions of the perovskite layer 5a, 15a, and portions where the perovskite layer 5a, 15a does not exist. Although the pinholes are tiny, they can be visually observed by using a light and a camera to form a transmission inspection device and a regular reflection inspection device.

[0074] In particular, oblique pinholes are difficult to detect even when inspection light is irradiated from a certain direction. However, by performing inspection while changing the relative position and relative angle between the intermediate bodies 8 and 18 and the first and second lamps 21 and 24, oblique pinholes can be easily detected.

[0075] The detected abnormal part Pc can be repaired with a solution of the raw material for forming the perovskite layer 5a, 15a. An insulating dry material (film) is formed at the part repaired with the solution. Specifically, a perovskite structure (crystal) is formed at the part, and even if there are pinholes, they are buried by the insulating material. As a result, the influence of the abnormality (especially the pinhole) of the perovskite layer 5a, 15a can be eliminated as much as possible, and the conversion efficiency and durability of the solar cell can be improved.

[0076] The intermediates 8 and 18 after the repair using the solution constitute a photoelectric conversion element, which includes a perovskite layer 5a and 15a and an insulating portion formed in a pinhole extending obliquely relative to the normal direction of the perovskite layer 5a and 15a. With the lamination of the perovskite layer 5a and 15a, even if an oblique pinhole inclined relative to the normal direction of the perovskite layer 5a and 15a is easily generated, it is possible to suppress short circuits in the perovskite layer 5a and 15a by subsequent repair. As a result, it is possible to achieve improvements in conversion efficiency and durability of the solar cell.

[0077] (Second Embodiment)

[0078] Next, a photoelectric conversion element inspection apparatus and a photoelectric conversion element manufacturing apparatus according to a second embodiment will be described with reference to the drawings.

[0079] The second embodiment is particularly different from the first embodiment in the following aspects. That is, the second embodiment includes a stage driving device 127 that horizontally moves the stage 127a and the intermediate bodies 8 and 18, and includes a first lamp 121 and a second lamp 124 that irradiate diffused light, and further includes a laser device that irradiates laser light to abnormal parts of the perovskite layers 5a and 15a. The same reference numerals are given to other structures that are the same as those in the first embodiment, and detailed descriptions are omitted.

[0080] Figure 5 The manufacturing process of the photoelectric conversion element in the second embodiment is schematically shown.

[0081] like Figure 5 As shown, the inspection device 120 of the photoelectric conversion element of the second embodiment moves the intermediate body 8, 18 on which the perovskite layer 5a, 15a is formed only in the horizontal direction, while irradiating the inspection light to the intermediate body 8, 18. The inspection light is diffused light, and the incident angle to the perovskite layer 5a, 15a is different depending on the position of the intermediate body 8, 18. The inspection device 120 detects the abnormality of the perovskite layer 5a, 15a by detecting the hue of the inspection light (at least one of the transmitted light and the reflected light) that has passed through the perovskite layer 5a, 15a.

[0082] The manufacturing apparatus 130 of the photoelectric conversion element of the second embodiment irradiates the abnormal part found by the inspection apparatus 120 with laser light. The manufacturing apparatus 130 removes the electrode of the abnormal part or forms an insulating part by laser light to prevent a short circuit at the abnormal part.

[0083] like Figure 5 As shown, the inspection device 120 includes: a first lamp 121, which irradiates the first inspection light (diffused light) L3 that transmits the perovskite layer 5a, 15a of the intermediate 8, 18; a first camera 122, which detects the hue of the first inspection light L3 that transmits the perovskite layer 5a, 15a; a second lamp 124, which irradiates the second inspection light (diffused light) L4 reflected on the surface (upper surface) of the perovskite layer 5a, 15a; a second camera 125, which detects the hue of the second inspection light L4 reflected by the perovskite layer 5a, 15a; a workbench driving device 127, which moves the workbench 127a on which the intermediate 8, 18 is placed horizontally; and a computer 128, which calculates the positions of points with different hues on the perovskite layer 5a, 15a based on the detection information of the first camera 122 and the second camera 125.

[0084] A first lamp 121 is disposed below the stage 127a to irradiate the first inspection light L3 from below to the intermediate products 8 and 18 placed on the stage 127a. The first lamp 121 has the same configuration as the first lamp 21 of the first embodiment except that it irradiates diffuse light.

[0085] Above the workbench 127a, a first camera 122 is arranged in the irradiation direction of the first lamp 121, into which the first inspection light L3 (transmitted light L3') that has transmitted through the intermediates 8 and 18 is incident. The first camera 122 has the same structure as the first camera 22 of the first embodiment except that it detects diffused light. The first camera 122 and the first lamp 121 constitute a transmission type inspection device.

[0086] A second lamp 124 is disposed above the stage 127a to irradiate the second inspection light L4 from above the intermediate products 8 and 18 on the stage 127a. The second lamp 124 has the same configuration as the second lamp 24 of the first embodiment except that it irradiates diffuse light.

[0087] Above the workbench 127a, a second camera 125 is arranged in the reflection direction of the second inspection light L4, into which the second inspection light L4 (reflected light L4') reflected by the perovskite layers 5a and 15a enters. The second camera 125 has the same structure as the second camera 25 of the first embodiment except that it detects diffuse light. The second camera 125 and the second lamp 124 constitute a regular reflection type inspection device.

[0088] The workbench driving device 127 drives the workbench 127a in the horizontal direction of front, back, left, and right while keeping its upper surface (intermediate body loading surface) horizontal. Reference numeral 127b in the figure indicates the control unit of the workbench driving device 127. The control unit 127b detects the movement amount of the workbench 127a from the predetermined initial position and outputs it to the computer 128. The computer 128 recognizes the position of each part of the upper surface of the workbench 127a based on the movement amount of the workbench 127a output from the control unit 127b. For example, the movement amount (horizontal movement amount) of the workbench 127a is about the horizontal width of one sheet of the intermediate bodies 8 and 18 that can be loaded on the workbench 127a.

[0089] The workbench 127a and the intermediate bodies 8 and 18 move in the horizontal direction relative to the first lamp 121 and the second lamp 124. The first lamp 121 and the second lamp 124 have light-emitting elements inside in order to irradiate diffuse light, and have scattering materials that scatter the light from the light-emitting elements. The scattering materials are made of plate-shaped, granular, or other materials with different refractive indices, and are not restricted as long as they are materials that change the optical path.

[0090] The inspection device 120 is independent of the production line of the photoelectric conversion element, but may be incorporated in the middle of the production line. In this case, the conveyor of the production line may be used as the stage driving device 127.

[0091] The computer 128 has the same configuration as the computer 28 of the first embodiment, except for the details of the program for determining the positions of the “points (locations) having different hues” on the perovskite layers 5 a and 15 a .

[0092] The manufacturing device 130 of the second embodiment irradiates the position of the "point with different hue" determined by the computer 128 with a laser for repair. In the figure, reference numeral 131 indicates a repair device for irradiating the above-mentioned laser to the perovskite layer 5a, 15a, and reference numeral 131a indicates a control unit of the repair device 131. For example, the repair device 131 is a laser device with wavelengths of 1064nm, 532nm, 355nm, and 266nm. By irradiating the position of the "point with different hue" with a laser device, the electrode at the abnormal part can be removed or insulated by the laser, thereby preventing a short circuit in the pinhole of the perovskite layer 5a, 15a. As a result, the conversion efficiency of the solar cell using the intermediate 8, 18 having the perovskite layer 5a, 15a can be improved.

[0093] In the second embodiment, the inkjet device of the first embodiment may be used as the repair device 131 instead of the laser device.

[0094] (Third Embodiment)

[0095] Next, a photoelectric conversion element inspection apparatus and a photoelectric conversion element manufacturing apparatus according to a third embodiment will be described with reference to the drawings.

[0096] The third embodiment is different from the first embodiment in that a spin coating device for coating a perovskite solution on a substrate is used as a stage driving device. The same reference numerals are used for the same structures as those in the first embodiment, and detailed description thereof is omitted.

[0097] Figure 6 The manufacturing process of the photoelectric conversion element in the third embodiment is schematically shown.

[0098] like Figure 6 As shown, the inspection device 220 of the photoelectric conversion element of the third embodiment rotates the intermediate body 8, 18 formed with the perovskite layer 5a, 15a around the vertical axis while irradiating the inspection light to the intermediate body 8, 18. The inspection light is diffused light, and the incident angle to the perovskite layer 5a, 15a is different depending on the position of the intermediate body 8, 18. The inspection device 220 detects the abnormality of the perovskite layer 5a, 15a by detecting the hue of the inspection light (at least one of the transmitted light and the reflected light) that has passed through the perovskite layer 5a, 15a.

[0099] The photoelectric conversion element manufacturing apparatus 230 of the third embodiment applies a perovskite solution or a solution having insulating solute to the abnormal portion found by the inspection apparatus 220 as in the first embodiment, or irradiates laser light as in the second embodiment.

[0100] like Figure 6 As shown, the inspection device 220 comprises: a first lamp 221, which irradiates the first inspection light L5 (diffused light) that transmits the perovskite layer 5a, 15a of the intermediate 8, 18; a first camera 222, which detects the hue of the first inspection light L5 that transmits the perovskite layer 5a, 15a; a second lamp 224, which irradiates the second inspection light L6 (diffused light) reflected on the surface (upper surface) of the perovskite layer 5a, 15a; a second camera 225, which detects the hue of the second inspection light L6 reflected by the perovskite layer 5a, 15a; a spin coating device (driving device) 227, which horizontally rotates the workbench 227a on which the intermediate 8, 18 is placed; and a computer 228, which calculates the positions of points with different hues on the perovskite layer 5a, 15a based on the detection information of the first camera 222 and the second camera 225.

[0101] A first lamp 221 is disposed below the table 227a to irradiate the first inspection light L5 from below to the intermediate products 8 and 18 placed on the table 227a. The first lamp 221 has the same configuration as the first lamp 221 of the first embodiment except that it irradiates diffuse light.

[0102] Above the workbench 227a, a first camera 222 is arranged in the irradiation direction of the first lamp 221, into which the first inspection light L5 (transmitted light L5') that transmits the intermediate bodies 8 and 18 is incident. The first camera 222 has the same structure as the first camera 22 of the first embodiment except that it detects diffused light. The first camera 222 and the first lamp 221 constitute a transmission type inspection device.

[0103] A second lamp 224 is disposed above the stage 227a to irradiate the second inspection light L6 from above to the intermediate products 8 and 18 on the stage 227a. The second lamp 224 has the same configuration as the second lamp 224 of the first embodiment except that it irradiates diffuse light.

[0104] Above the workbench 227a, a second camera 225 is arranged in the reflection direction of the second inspection light L6, into which the second inspection light L6 (reflected light L6') reflected by the perovskite layers 5a and 15a enters. The second camera 225 has the same structure as the second camera 25 of the first embodiment except that it detects diffuse light. The second camera 225 and the second lamp 224 constitute a regular reflection type inspection device.

[0105] The spin coating device 227 has an inspection mode that can rotate the workbench 227a at a low rotation speed relative to the known spin coating device. Reference numeral 227b in the figure represents the control unit of the spin coating device 227. The control unit 227b detects the amount of movement of the workbench 227a from a predetermined initial position and outputs it to the computer 228. The computer 228 recognizes the position of each part on the upper surface of the workbench 227a based on the amount of movement of the workbench 227a output from the control unit 227b.

[0106] The computer 228 has the same configuration as the computer 28 of the first embodiment, except for the details of the program for specifying the positions of the “points (locations) having different hues” on the perovskite layers 5 a and 15 a .

[0107] The manufacturing device 230 of the third embodiment repairs the position of the "point with different hue" determined by the computer 228. Reference numeral 231 in the figure represents a repair device, and reference numeral 231a represents a control unit of the repair device 231. By making the solution adhere to the position of the "point with different hue" and drying it, the pinholes of the perovskite layer 5a, 15a are removed or an insulator is formed, thereby preventing a short circuit. Alternatively, by removing the electrode of the "point with different hue" or forming an insulating portion with a laser, a short circuit in the pinhole of the perovskite layer 5a, 15a is prevented. As a result, the conversion efficiency of the solar cell using the intermediate 8, 18 having the perovskite layer 5a, 15a can be improved.

[0108] By using a spin coating device, the intermediate 8, 18 formed with the perovskite layer 5a, 15a can be rotated while the abnormality of the perovskite layer 5a, 15a can be inspected over the entire area of ​​the intermediate 8, 18. By irradiating the inspection light obliquely relative to the normal direction of the perovskite layer 5a, 15a, it is easy to detect the oblique pinholes of the perovskite layer 5a, 15a. If the inspection light is diffuse light or the relative angle between the intermediate 8, 18 and the first lamp 221 and the second lamp 224 can be changed, it is easy to detect various oblique pinholes. As a result, the abnormality of the perovskite layer 5a, 15a (especially the pinhole) can be eliminated as much as possible, and the conversion efficiency and durability of the solar cell can be improved. By using a spin coating device used in the manufacturing process of the photoelectric conversion element, it is possible to reduce the equipment cost compared to the case where a workbench driving device is separately provided.

[0109] (Other embodiments)

[0110] In the above-mentioned embodiments, the inspection device and the repair device are mainly described, but a device for confirming whether the repair is successful when the repair is performed may also be provided. Specifically, a device equivalent to the inspection device may be provided in the post-process of the repair device for inspection, or when the repair is performed using the repair device, the inspection device of the previous process may be returned to and inspected again. In addition, when inspecting after the repair, the repaired part (the part determined to be abnormal before the repair) may also be inspected with emphasis. Moreover, depending on the content of the repair, the hue of the repaired part when the abnormality is determined is different from that of the surrounding normal parts. Therefore, in this case, the hue when the abnormality is determined before the repair can also be compared with the hue after the repair to determine whether the repair is successful.

[0111] According to at least one embodiment described above, by having one or more light sources, a driving device, a camera and a computer, it is possible to appropriately change the relative distance and relative angle between the substrate having the perovskite layer and the light source while detecting at least one of the transmitted light and the reflected light of the inspection light. Thus, it is possible to easily detect abnormalities in the perovskite layer. In particular, by performing an inspection while changing the relative angle between the substrate and the light source, it is possible to easily detect oblique pinholes that are tilted relative to the normal direction of the perovskite layer. As a result, it is possible to eliminate abnormalities (especially pinholes) in the perovskite layer as much as possible, thereby achieving improved conversion efficiency and durability of solar cells.

[0112] Several embodiments of the present invention have been described, but these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other ways, and various omissions, substitutions, and changes can be made without departing from the scope of the subject matter of the invention. These embodiments and their variations are included in the scope and subject matter of the invention, and are also included in the invention described in the claims and their equivalents.

[0113] (Note 1)

[0114] A device for inspecting a photoelectric conversion element, comprising:

[0115] One or more light sources for irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer;

[0116] A driving device that changes at least one of a distance or an angle between the substrate having the perovskite layer and the light source;

[0117] a camera that detects the hue of at least one of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer while changing at least one of the distance or angle between the substrate and the light source; and

[0118] The computer calculates the positions of the points with different hues on the perovskite layer based on the detection information of the camera.

[0119] (Note 2)

[0120] A device for manufacturing a photoelectric conversion element, comprising:

[0121] One or more light sources, irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer;

[0122] A driving device that changes at least one of a distance or an angle between the substrate having the perovskite layer and the light source;

[0123] a camera that detects the hue of at least one of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer while changing at least one of the distance or the angle between the substrate and the light source;

[0124] a computer, calculating the positions of the points with different hues on the perovskite layer detected by the camera; and

[0125] A repair device makes a solution of a raw material for forming the perovskite layer or a solution containing an insulating substance as a solute adhere to the position of the point with different hue on the perovskite layer calculated by the computer.

[0126] (Note 3)

[0127] According to the photoelectric conversion element manufacturing apparatus described in Supplementary Note 2, the solution is formed into a dry product having insulating properties.

[0128] (Note 4)

[0129] According to the photoelectric conversion element manufacturing apparatus described in Supplementary Note 2, the solution forms a dried product having a perovskite structure.

[0130] (Note 5)

[0131] A device for manufacturing a photoelectric conversion element, comprising:

[0132] One or more light sources, irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer;

[0133] A driving device that changes at least one of a distance or an angle between the substrate having the perovskite layer and the light source;

[0134] a camera that detects the hue of at least one of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer while changing at least one of the distance or the angle between the substrate and the light source;

[0135] a computer, calculating the positions of the points with different hues on the perovskite layer detected by the camera; and

[0136] A laser device irradiates the position of the point with different hue on the perovskite layer calculated by the computer with a laser for removing the electrodes on the front and back sides of the perovskite layer, or with a laser for sintering the surface of the substrate in contact with the pinhole to form an insulating portion.

[0137] (Note 6)

[0138] A device for manufacturing a photoelectric conversion element, comprising:

[0139] A spin coating device capable of coating a solution of a raw material for forming a perovskite structure onto a surface of a substrate, and capable of inspecting a perovskite layer formed on the surface of the substrate while rotating the substrate;

[0140] One or more light sources, irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer;

[0141] a camera that detects the hue of at least one of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer while changing at least one of the distance or the angle between the substrate and the light source; and

[0142] The computer calculates the positions of the points with different hues on the perovskite layer detected by the camera.

[0143] (Note 7)

[0144] A photoelectric conversion element manufactured by the photoelectric conversion element manufacturing device according to Supplementary Note 2, comprising:

[0145] the perovskite layer; and

[0146] The insulating portion is formed by allowing the solution to adhere to pinholes extending obliquely with respect to a normal direction of the perovskite layer and drying the solution.

[0147] (Note 8)

[0148] A method for manufacturing a photoelectric conversion element,

[0149] irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer from a light source;

[0150] While changing at least one of the distance or angle between the substrate having the perovskite layer and the light source by using a driving device, detecting at least one of the hue of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer by using a camera;

[0151] calculating, by a computer, the positions of the points with different hues on the perovskite layer detected by the camera;

[0152] The positions of the points with different hues on the perovskite layer calculated by the computer are irradiated with a laser that removes electrodes on the front and back surfaces of the perovskite layer or a laser that sinters the surface of the substrate in contact with the pinhole to form an insulating portion.

[0153] (Note 9)

[0154] A method for inspecting a photoelectric conversion element,

[0155] irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer from a light source;

[0156] While changing at least one of the distance or angle between the substrate having the perovskite layer and the light source by using a driving device, detecting the hue of at least one of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer by using a camera;

[0157] The positions of the points with different hues on the perovskite layer detected by the camera are calculated using a computer.

[0158] [Explanation of Reference Numerals]

[0159] 1, 11…photoelectric conversion element, 5a, 15a…perovskite layer, 8b, 18b…substrate, 20, 120, 220…inspection device, 21, 121, 221…first lamp (light source), 22, 122, 222…first camera (camera), 24, 124, 224…second lamp (light source), 25, 125, 225…second camera (camera), 27, 127…workbench driving device (driving device), 28, 128, 228…computer, 30, 130, 230…manufacturing device, 31, 131, 231…repairing device, 227…spin coating device (driving device), L1, L3, L5…first inspection light (inspection light), L2, L4, L6…second inspection light (inspection light), Pa, Pb…pinhole.

Claims

1. A photoelectric conversion element inspection device, comprising: One or more light sources for irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer; A driving device that changes at least one of a distance or an angle between the substrate having the perovskite layer and the light source; a camera that detects the hue of at least one of the inspection light that has passed through the perovskite layer or has been reflected by the perovskite layer while changing at least one of the distance or angle between the substrate and the light source; as well as The computer calculates the positions of the points with different hues on the perovskite layer based on the detection information of the camera.

2. A device for manufacturing a photoelectric conversion element, comprising: A repair device performs repair processing on the positions of the points with different hues on the perovskite layer calculated by the computer of the inspection device according to claim 1.

3. The photoelectric conversion element manufacturing device according to claim 2, The repair device is a repair device that allows a solution of a raw material for forming the perovskite layer or a solution having an insulating substance as a solute to adhere.

4. The photoelectric conversion element manufacturing device according to claim 3, The solution forms a dry product having insulating properties.

5. The photoelectric conversion element manufacturing device according to claim 3, The solution forms a dried product having a perovskite structure.

6. The photoelectric conversion element manufacturing device according to claim 2, The repair device is a laser device that irradiates the position of the point with different hue on the perovskite layer calculated by the computer with a laser to remove the electrodes on the front and back sides of the perovskite layer, or with a laser to sinter the surface of the substrate in contact with the pinhole to form an insulating portion.

7. A device for manufacturing a photoelectric conversion element, comprising: A spin coating device capable of coating a solution of a raw material for forming a perovskite structure onto a surface of a substrate, and capable of inspecting a perovskite layer formed on the surface of the substrate while rotating the substrate; and The inspection device according to claim 1, inspects the perovskite layer.

8. A method for manufacturing a photoelectric conversion element, irradiating the perovskite layer with inspection light capable of at least one of transmitting through the perovskite layer or being reflected by the perovskite layer from a light source; While changing at least one of the distance or angle between the substrate having the perovskite layer and the light source by using a driving device, detecting at least one of the hue of the inspection light transmitted through the perovskite layer or reflected by the perovskite layer by using a camera; Calculating the positions of the points with different hues on the perovskite layer detected by the camera using a computer; The positions of the points with different hues on the perovskite layer calculated by the computer are repaired.

9. A photoelectric conversion element manufactured by the manufacturing method according to claim 8, comprising: a perovskite layer; and The insulating portion is formed in a pinhole extending obliquely with respect to a normal direction of the perovskite layer.

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