Slot die, method for manufacturing the slot die, coating apparatus equipped with the slot die, and perovskite solar cell manufactured by the coating apparatus.

Abstract

The objective is to develop a slot die that prevents cracks from occurring during the processing of the HIP layer formed in the die channel during the manufacturing of the slot die, and prevents contamination of the die channel by halides during the manufacturing of perovskite solar cells. [Solution] The Rockwell hardness of the first HIP layer formed in the manifold section and discharge-side flow path section of the upper body, and the Rockwell hardness of the second HIP layer formed in the discharge-side flow path section of the lower body, are formed to be greater than the Rockwell hardness of the HIP layer formed in the manifold section of the lower body, and a pre-HIP-treated HIP rod-shaped body is provided between the second HIP layer formed in the discharge-side flow path section of the lower body and the third HIP layer formed in the manifold section of the lower body.

Description

Technical Field

[0001] The present invention relates to a slot die in which a HIP layer is formed by HIP treatment from at least the manifold part to the discharge port of a slot die flow path. More specifically, the present invention relates to a slot die in which a coating liquid or molten resin containing a halide is supplied to a die flow path, and a HIP layer for protecting the die flow path from the corrosiveness of the halide is provided.

Background Art

[0002] Among solar cells, a perovskite solar cell, which is a technology developed in Japan, has recently attracted particular attention. This perovskite solar cell can be manufactured as thin as a film, is lightweight and can be bent, and can be installed in various places such as roofs with low load-bearing capacity, building walls and windows, carports, storage sheds, and even handy fans and the outer surfaces of automobiles. Moreover, perovskite solar cells can be manufactured by a coating method, and are also characterized by being able to be manufactured with high efficiency and low cost, and are a technology that is highly anticipated.

[0003] FIG. 4 illustrates, for example, a process of manufacturing a cell member of a solar cell called a cell process. In FIG. 4, a substrate 104 on which an electrode and a barrier film are laminated is being conveyed by a back roll 102 and an adjustment roll 103, and a coating liquid composed of a perovskite compound containing a halide is supplied from a supply flow path 106 to a manifold part 107 using a slot die 104, and is discharged from a discharge port 108 to form a photoelectric conversion element layer 105.

[0004] Generally, as a suitable perovskite compound contained in the photoelectric conversion element layer 105, the following compositional formula (1) RNH3PbX3 ··· (1) Examples include alkylamino lead halides represented by the formula (1). In the formula (1), R represents an alkyl group, and X represents a halogen anion. Examples of halogens constituting the halogen anion include F, Cl, Br, and I. Perovskite compounds having this formula (1) have a wide absorption wavelength range and can absorb a wide range of wavelengths in sunlight, so it is said that they can obtain excellent photoelectric conversion efficiency.

[0005] Although it is a very promising technology, there is a major problem in the manufacturing of perovskite solar cells. This is the use of halides in the manufacturing of perovskite solar cells. For example, Patent Document 1 states, "When a perovskite layer is formed by coating, surfaces other than the coated surface, such as the surface of the second electrode, may be contaminated. Since perovskites contain corrosive halogen elements, it is preferable to remove the contamination." (0038) Patent Document 1 proposes devising the layer structure of the photoelectric conversion element as a countermeasure against corrosive halides, but there are also applications that propose devising the coating solution as a countermeasure against corrosive halides.

[0006] While various measures have been proposed to address corrosive halogen elements, the current situation is far from satisfactory. This is likely because the contamination of slot dies by halides has not been adequately considered. In fact, when observing slot dies used in the manufacturing process, black contaminants are often found adhering to the manifold section of the slot die flow path, around the discharge port, and in the flow path between the manifold and the discharge port. These are clearly contaminants caused by halides. However, there are currently very few patent applications related to countermeasures against contamination of slot dies by halides.

[0007] In a previous application (Patent Document 2), the applicant explained that, "To describe the HIP layer that prevents the die from being corroded, scratched, or worn by the binder liquid, negative electrode paste, and positive electrode paste (hereinafter referred to as coating liquid), the alloy powder used to form the HIP layer in the present invention is an alloy powder made of a Ni-Cr-Si-B nickel-based alloy or an alloy powder made of a Co-Cr-Si-B cobalt-based alloy. The HIP layer is formed by directly diffusion bonding such alloy powders by HIP treatment. The HIP layer made of such alloy powder has an HRC of 57-62, and a die with excellent corrosion resistance to highly corrosive halogen gases (fluorine-based gases and chlorine-based gases) can be created." Figure 4 of Patent Document 2 illustrates an HIP layer formed by directly diffusion bonding an alloy powder with good corrosion resistance to the base material of the die body by HIP treatment to the manifold section of the slot die flow path and the discharge port side flow path section formed from the manifold section to the discharge port. The coating solution containing halogen compounds is supplied from the tank to the slot die's supply port via piping using a pump. While contamination of the piping can be easily addressed through maintenance, contamination or damage inside the slot die will immediately shut down the production line. Therefore, measures to prevent contamination and damage to the slot die are extremely important. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] WO2022 / 102128 publication [Patent Document 2] Patent No. 6654769 [Overview of the project] [Problems that the invention aims to solve]

[0009] As proposed in Patent Document 2, forming a HIP layer with a Rockwell hardness of HRC57-62 on the manifold portion of the die channel and the discharge port side channel formed from the manifold portion to the discharge port by HIP treatment poses no manufacturing problems. However, it has become clear that there are problems when using a slot die in which the curved surface (R surface) of the manifold portion has been polished after HIP treatment. Specifically, when the curved surface (R surface) of the manifold portion is polished by machining with a diamond cutting tool or a borazon cutting tool after HIP treatment, it has become clear that when a slot die is used in the manufacturing process of the photoelectric conversion element layer, although the problem of contamination by halides is solved by the HIP layer, there is a high probability that cracks will occur on the machined surface of the curved surface (R surface).

[0010] The present invention aims to develop a slot die that prevents contamination of the slot die by halides by forming a HIP layer in the die channel of the slot die, and prevents cracks from occurring in the HIP layer during the manufacturing of the slot die. [Means for solving the problem]

[0011] The slot die of the present invention, made to solve the above problems, comprises an upper body and a lower body, a die channel formed by the upper body and the lower body, and a discharge port for discharging coating liquid or molten resin supplied to the die channel provided on the tip side of the die body, wherein a HIP layer is formed in at least the manifold portion of the die channel and the discharge port side channel portion formed from the manifold portion to the discharge port, by directly diffusing an alloy powder or gel with good corrosion resistance by HIP treatment onto the base material of the die body, wherein the Rockwell hardness of the first HIP layer formed in the manifold portion and the discharge port side channel portion of the upper body, and the Rockwell hardness of the second HIP layer formed in the discharge port side channel portion of the lower body are greater than the Rockwell hardness of the third HIP layer formed in the manifold portion of the lower body, and a HIP-treated HIP rod-shaped body is provided between the second HIP layer formed in the discharge port side channel portion of the lower body and the third HIP layer formed in the manifold portion of the lower body.

[0012] Furthermore, the present invention, which was developed to solve the above problems, is a method for manufacturing a slot die in which the slot die body consists of an upper body and a lower body, a die channel is formed between the upper body and the lower body, and a discharge port is provided on the tip side of the die body for discharging the coating liquid or molten resin supplied to the die channel, wherein when forming a HIP layer by direct diffusion bonding of an alloy powder or gel with good corrosion resistance to the base material of the die body by HIP treatment in at least the manifold portion of the die channel and the discharge port side channel portion formed from the manifold portion to the discharge port, a second HIP layer formed in the discharge port side channel portion of the lower body and the manifold portion of the lower body This method for manufacturing a slot die is characterized by first placing a pre-HIP-treated HI rod-shaped body between the die and the third HIP layer formed in the die section, then filling the die with alloy powder or gel suitable for forming each HIP layer so that the Rockwell hardness of the first HIP layer formed in the manifold section and discharge-side flow path section of the upper body, and the Rockwell hardness of the second HIP layer formed in the discharge-side flow path section of the lower body are greater than the Rockwell hardness of the third HIP layer formed in the manifold section of the lower body, and then forming the first HIP layer, second HIP layer, and third HIP layer on the base material of the die body by HIP treatment.

[0013] Furthermore, the coating apparatus of the present invention, which was made to solve the above problems, is a slot die in which the slot die body consists of an upper body and a lower body, a die channel is formed by the upper body and the lower body, and a discharge port is provided on the tip side of the die body for discharging the coating liquid or molten resin supplied to the die channel, wherein at least the manifold portion of the die channel and the discharge port side channel portion formed from the manifold portion to the discharge port have a HIP layer formed by directly diffusing an alloy powder or gel with good corrosion resistance by HIP treatment onto the base material of the die body, and the coating apparatus is provided with a slot die in which the manifold portion of the upper body and the discharge port side channel portion are formed from the manifold portion to the discharge port A coating apparatus is characterized in that a slot die is installed in which a first HIP layer formed in the flow channel section has a Rockwell hardness greater than the Rockwell hardness of a third HIP layer formed in the manifold section of the lower body, and a HIP-treated HIP rod is provided between the second HIP layer formed in the flow channel section on the discharge port side of the lower body and the third HIP layer formed in the manifold section of the lower body, and a coating liquid or molten resin containing a halogen is supplied to the die flow channel. [Effects of the Invention]

[0014] By preventing crack formation during the processing of the HIP layer, it is possible to prevent the accumulation of black halogen contaminants in the manifold section of the slot die flow path and in the discharge-side flow path formed from the manifold section to the discharge port over the long term. This enables the formation of the photoelectric conversion element layer over a long period, allowing for continuous manufacturing of perovskite solar cells without compromising quality. [Brief explanation of the drawing]

[0015] [Figure 1] Cross-sectional view of the slot die of the present invention [Figure 2] Plan view, right side view, and BB cross-section view of the slot die of this invention. [Figure 3] A diagram illustrating the manufacturing process of the slot die of the present invention. [Figure 4] Diagram illustrating the slot die during the formation of the photoelectric conversion element layer. [Modes for carrying out the invention]

[0016] Embodiments of the present invention will be described below with reference to Figures 1 and 2. Figure 1 is a clear illustration of the AA cross-section in the overall view of Figure 2(a) for the purpose of explaining the configuration of the present invention. As shown in Figure 1, the slot die 1 of the present invention is composed of an upper body 2 and a lower body 3. The die flow path in the slot die is formed by a supply path (not shown) provided in the upper body 2 or the lower body 3, a manifold section 4 provided in the lower body, and a discharge port side flow path section 5 from the manifold section 4 to the discharge port 6. A shim member, as shown in Figure 2(b), is fitted between the upper body 2 and the lower body 3 to adjust the vertical width of the flow path corresponding to the thickness of the photoelectric conversion element layer.

[0017] In the die channel of slot die 1, to prevent corrosion by halides in the die channel, a first HIP layer 11 is formed on the lower surface of the upper body 2 along the discharge channel section 5 from the manifold section 4, a second HIP layer 12 is formed on the upper surface of the lower body 3 along the discharge channel section 5, and a third HIP layer 13 is formed on the manifold section of the lower body 2. These first HIP layer 11, second HIP layer 12, and third HIP layer 13 are all HIP layers formed by directly diffusion bonding alloy powder or gel made of a Ni-Cr-Si-B nickel-based alloy or a Ni-Cr-Si-B cobalt-based alloy to the die body by HIP treatment.

[0018] One of the features of the present invention is that the Rockwell hardness of the first HIP layer 11 and the Rockwell hardness of the second HIP layer 12 are formed with a hardness greater than the Rockwell hardness of the third HIP layer 13. By adopting such a configuration, it is possible to prevent the occurrence of cracks on the curved surface of the lower body 3 in the manifold portion 4. As a result of examination, when the Rockwell hardness of the first HIP layer and the Rockwell hardness of the second HIP layer are set to 55 to 68, and the Rockwell hardness of the third HIP layer is set to 30 to 50, it was found that the occurrence of cracks on the curved surface of the lower body 3 in the manifold portion 4 can be suppressed as much as possible. In addition, if the Rockwell hardness of the first HIP layer 11 and the Rockwell hardness of the second HIP layer 12 are set to be the same, it is efficient in the production of the slot die.

[0019] Another feature of the present invention is that a HIP-processed HIP rod 14 is provided between the second HIP layer 12 formed in the discharge port side flow path portion 5 of the lower body 3 and the third HIP layer 13 formed in the manifold 4 portion of the lower body 3. By adopting such a configuration, it is possible to prevent the occurrence of cracks between the second HIP layer 12 and the third HIP layer 13 due to different Rockwell hardnesses. As a result of examination, it was also found that when the Rockwell hardness of the HIP rod 14 to be installed is the same as the Rockwell hardness of the second HIP layer 12 or the same as the Rockwell hardness of the third HIP layer 13, the occurrence of cracks between the second HIP layer 12 and the third HIP layer 13 can be suppressed over a long period.

[0020] Next, the manufacturing method of the slot die 1 of the present invention will be described using FIG. 3. In Fig. 3(a), it shows the first stage for manufacturing the slot die. A member to be the upper body 2 and a member to be the lower body 3 are assembled. On the side of the member to be the upper body 2, the core 21-1 is set and assembled so that the first HIP layer 11 along the manifold part 4 and the discharge port side flow path part 5 can be formed. On the side of the member to be the lower body 3, the cores 21-2 and 21-3 are set, and it shows the state that they are assembled so that the second HIP layer 12 can be formed in the discharge port side flow path part 5 and the third HIP layer 13 can be formed in the manifold part. Also, between the second HIP layer 12 planned to be formed in the discharge port side flow path part 5 of the member to be the lower body 3 and the third HIP layer 13 planned to be formed in the manifold part, a HIP rod-shaped body 14 that has been HIP-treated and manufactured in advance is set.

[0021] In Fig. 3(b), it shows the next stage. From the powder supply ports provided in the HIP processing apparatus, the parts where the first HIP layer 11, the second HIP layer 12, and the third HIP layer 13 are to be formed are all in a state filled with alloy powder or gel made of Ni-Cr-Si-B-based nickel-based alloy or gel, or Ni-Cr-Si-B-based cobalt-based alloy. It is efficient to fill the same alloy powder or gel for forming the first HIP layer 11 and the second HIP layer 12 from the first powder supply port 22 provided in the HIP processing apparatus, and fill the alloy powder or gel for forming the third HIP layer 13 from the second powder supply port 23 provided in the HIP processing apparatus. Also, it is preferable that the HIP rod-shaped body 14 that has been HIP-treated in advance is manufactured with the same alloy powder or gel as the second HIP layer or the third HIP layer to be formed.

[0022] It is efficient to fill the first HIP layer 11 and the second HIP layer 12 with alloy powder or gel adapted to achieve a Rockwell hardness of 55-68, and the third HIP layer 13 with alloy powder or gel adapted to achieve a Rockwell hardness of 30-50. In Figure 3(b), the same alloy powder or gel is supplied from the first powder supply port 22 to make the Rockwell hardness of the first HIP layer 11 and the second HIP layer 12 the same. However, separate powder supply ports can be provided to make the Rockwell hardness of the first HIP layer 11 and the second HIP layer 12 different. Even in that case, however, it is necessary to select alloy powder or gel so that the Rockwell hardness of the first HIP layer 11 and the second HIP layer 12 is greater than the Rockwell hardness of the third HIP layer 13. Furthermore, it is preferable that the hardness of the pre-treated HIP rod-shaped body 14 be the same as the hardness of the alloy powder or gel that forms the second or third HIP layer.

[0023] After filling with alloy powder or gel, the next step is HIP treatment, in which alloy powder or gel consisting of a Ni-Cr-Si-B nickel-based alloy or a Ni-Cr-Si-B cobalt-based alloy is directly diffusion-bonded to the upper body 2 and the lower body 3 by HIP treatment, forming HIP layers. Figure 3(c) shows the combination of the upper body 2 and the lower body 3 in an unfolded state after HIP treatment. In this state with the core removed, with core 21-1 removed from the upper body 2, the first HIP layer 11 is integrally formed on the upper body 2 by direct diffusion bonding to the upper body 2; with core 21-2 removed from the lower body 3, the second HIP layer 12 is integrally formed on the lower body 3 by direct diffusion bonding to the lower body 3; and with core 21-3 removed from the lower body 3, the third HIP layer 13 is integrally formed on the lower body 3 by direct diffusion bonding to the lower body 3. Furthermore, the HIP-treated HIP rod-shaped body 14, which was placed between the second HIP layer 12 and the third HIP layer 13 at the stage shown in Figure 3(a), is directly diffusion-bonded to the lower body 3, the second HIP layer, and the third HIP layer.

[0024] Next, the upper body 2 and the lower body 3 are shaped into slot dies as shown in Figure 1 by grinding. The first HIP layer 11 and the second HIP layer are polished with a diamond grinding wheel or a borazon grinding wheel, and the third HIP layer 13 is machined with a diamond cutting tool or a borazon cutting tool because it is necessary to polish the curved surface (R surface) of the manifold section. After that, the slot die 1 is completed by inserting a shim member between the finished upper body 2 and lower body 3 and assembling them.

[0025] Next, embodiments of the present invention will be described. The slot die is manufactured by the manufacturing method described in the Embodiments section. The size of the slot die can be explained using the overall view in Figure 2(a). In the left side of Figure 2(a), the vertical width is generally 100 mm to 150 mm, and the horizontal width is generally 500 mm or more. In the right side of Figure 2(a), the horizontal width is generally 80 mm to 100 mm. In the left side of Figure 2(a), the configuration with a horizontal width of 500 mm or more corresponds to handling a single sheet with a horizontal width of 500 mm. When handling multiple sheets, the horizontal width will be adjusted.

[0026] The thickness of the first HIP layer formed on the upper body and the second HIP layer formed on the lower body is generally 3 mm or more. The depth of the manifold section in the lower body is generally around 200 mm, and the thickness of the HIP layer formed there is also generally 3 mm or more. The HIP rod-shaped body is a long rod-shaped body with a width of 3 mm to 4 mm from left to right and a width of 4 mm to 5 mm from top to bottom, and the length of the rod-shaped body is adjusted to correspond to the length of the manifold section. It should be noted that the sizes related to the slot die described above are merely commonly used sizes, and the slot die of the present invention is not limited to these sizes.

[0027] The applicant uses an upper body 2 and a lower body 3 made of SUS329J series stainless steel (HRC25~35) as the base material for the throttle die, and in order to create a slot die corresponding to a single sheet of 80 × 100 × 500 mm, in the manufacturing process of the slot die of the present invention, as described with reference to Figure 3 in the embodiment, an HIP rod 14, which has been prepared in advance by HIP treatment of alloy powder made of Ni-Cr-Si-B nickel-based alloy having a Rockwell hardness of 40, is attached to the lower body 3, alloy powder made of Ni-Cr-Si-B nickel-based alloy having a Rockwell hardness of 60 is filled to form the first HIP layer 11 and the second HIP layer 12, and alloy powder made of Ni-Cr-Si-B nickel-based alloy having a Rockwell hardness of 40 is filled to form the third HIP layer 13, and then HIP treatment is performed.

[0028] Then, the upper body 2 and lower body 3, after HIP treatment, were ground to the shape shown in Figure 1. The first HIP layer 11 and the second HIP layer 12 after HIP treatment were ground with a diamond grinding wheel or a borazon grinding wheel to shape the HIP layer to 3 mm, and the third HIP layer 13 after HIP treatment was machined using a diamond cutting tool or a borazon cutting tool to grind a curved surface (R surface) to shape the HIP layer to 3 mm. After that, a shim member 7 of an appropriate thickness corresponding to the film thickness of the photoelectric conversion element layer was installed between the upper body 2 and the lower body 3 to complete the slot die of the present invention. No cracks occurred in any of the HIP layers during processing of the HJP layer.

[0029] In a perovskite solar cell manufacturing line that supplies a coating solution containing halogen compounds as a coating solution for the photoelectric conversion element layer, the process was observed using the finished slot dies. As a result, even after one year, no black contaminants due to halogens were found to adhere to the manifold portion of the slot die's flow path or the discharge side flow path.

[0030] In order to prevent black contaminants caused by halogens from adhering to the slot die's flow path, a HIP layer is formed in at least the manifold portion of the die flow path and in the discharge port side flow path formed from the manifold portion to the discharge port, (1) The Rockwell hardness of the third HIP layer in the manifold section of the lower body is made smaller than the Rockwell hardness of the first and second HIP layers. (2) During the HIP treatment, before filling with the alloy powder or gel that will form the HIP layer, a pre-HIP-treated HIP rod is placed between the second HIP layer and the third HIP layer to be formed. These conditions constitute the essence of the present invention and are not limited to the configuration described in the embodiments. [Explanation of symbols]

[0031] 1...Slot die 2. Upper body 3. Lower body 4. Manifold section 5...Discharge port side flow path section 6...Discharge port 7. Shim component 11. The first HIP layer 12. The second HIP layer 13. The third HIP layer 14...HIP rod 21...Nakako 22...1st powder supply port 23...Second powder supply port 101...Base material 102...back roll 103... Adjustment Roll 104... Slot Die 105...Photoelectric conversion element layer 106...supply route 107...Manifold section 108...Discharge port

Claims

1. The slot die body consists of an upper body and a lower body, a die channel is formed by the upper body and the lower body, and a discharge port is provided on the tip side of the die body for discharging the coating liquid or molten resin supplied to the die channel, In a slot die in which an HIP layer is formed in at least the manifold portion of the die flow path and the discharge port side flow path portion formed from the manifold portion to the discharge port, by directly diffusing and bonding an alloy powder or gel with good corrosion resistance to the base material of the die body through HIP treatment, The HIP layer is formed such that the Rockwell hardness of the first HIP layer formed in the manifold section and discharge-side flow path section of the upper body, and the Rockwell hardness of the second HIP layer formed in the discharge-side flow path section of the lower body, are greater than the Rockwell hardness of the third HIP layer formed in the manifold section of the lower body. Furthermore, a HIP-treated HIP rod-shaped body is provided between the second HIP layer formed in the discharge-side flow path of the lower body and the third HIP layer formed in the manifold portion of the lower body. A slot die characterized by the following features.

2. The slot die according to claim 1, characterized in that the HIP layer is an alloy powder or gel made of a Ni-Cr-Mo-Si-B nickel-based alloy or a Co-Cr-Mo-Si-B cobalt-based alloy that is directly diffusion-bonded by HIP treatment.

3. The slot die according to claim 1, characterized in that the HIP layer is an alloy powder or gel obtained by directly diffusion bonding a Ni-Cr-Si-B nickel-based alloy or a Co-Cr-Si-B cobalt-based alloy with ceramics added to it, by HIP treatment.

4. The slot die according to claim 1, characterized in that the Rockwell hardness of the first HIP layer and the Rockwell hardness of the second HIP layer are preferably 55 to 68, and the Rockwell hardness of the third HIP layer is preferably 30 to 50.

5. The slot die according to claim 1, characterized in that the Rockwell hardness of the first HIP layer and the Rockwell hardness of the second HIP layer are the same.

6. The slot die according to claim 1, characterized in that the Rockwell hardness of the HIP rod is the same as the Rockwell hardness of the second HIP layer or the Rockwell hardness of the third HIP layer.

7. A method for manufacturing a slot die, wherein the slot die body consists of an upper body and a lower body, a die channel is formed by the upper body and the lower body, and a discharge port is provided on the tip side of the die body for discharging the coating liquid or molten resin supplied to the die channel, When forming an HIP layer in at least the manifold portion of the die flow path and the discharge port side flow path portion formed from the manifold portion to the discharge port, by directly diffusing and bonding an alloy powder or gel with good corrosion resistance to the base material of the die body through HIP treatment, A method for manufacturing a slot die, characterized by: first, placing a pre-HIP-treated HI rod-shaped body between a second HIP layer formed in the discharge-side flow path of the lower body and a third HIP layer formed in the manifold portion of the lower body; then filling the space with alloy powder or gel suitable for forming each HIP layer so that the Rockwell hardness of the first HIP layer formed in the manifold portion and discharge-side flow path of the upper body, and the Rockwell hardness of the second HIP layer formed in the discharge-side flow path of the lower body, are greater than the Rockwell hardness of the third HIP layer formed in the manifold portion of the lower body; and then forming the first HIP layer, the second HIP layer, and the third HIP layer in the base material of the die body by HIP treatment.

8. The slot die body consists of an upper body and a lower body, a die channel is formed by the upper body and the lower body, and a discharge port is provided on the tip side of the die body for discharging the coating liquid or molten resin supplied to the die channel, In a coating apparatus equipped with a slot die in which a HIP layer is formed in at least the manifold portion of the die flow path and the discharge port side flow path portion formed from the manifold portion to the discharge port, the HIP layer is formed by directly diffusing and bonding an alloy powder or gel with good corrosion resistance to the base material of the die body by HIP treatment, The coating apparatus is equipped with a slot die in which a HIP layer is formed with a Rockwell hardness greater than that of the Rockwell hardness of the third HIP layer formed in the manifold portion of the lower body, and the Rockwell hardness of the first HIP layer formed in the discharge port side flow path portion of the upper body, and the Rockwell hardness of the second HIP layer formed in the discharge port side flow path portion of the lower body, and a HIP-treated HIP rod is provided between the second HIP layer formed in the discharge port side flow path portion of the lower body and the third HIP layer formed in the manifold portion of the lower body. A coating liquid or molten resin containing a halide is supplied to the die channel. A coating apparatus characterized by the following features.

9. A perovskite solar cell characterized by being manufactured by the coating apparatus of claim 8.

10. An electronic device comprising a perovskite solar cell manufactured by the coating apparatus of claim 8, and an electronic device electrically connected to the perovskite solar cell.

11. An electronic device comprising a perovskite solar cell manufactured by the coating apparatus of claim 8, a storage battery electrically connected to the perovskite solar cell, and an electronic device electrically connected to the perovskite solar cell and the storage battery.

12. A power supply module comprising a perovskite solar cell manufactured by the coating apparatus of claim 8, and a power supply IC electrically connected to the perovskite solar cell.

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