Manufacture method of perovskite solar cell

Abstract

A method for manufacturing a perovskite solar cell includes providing a substrate to be coated and spraying a liquid coating agent using a spraying machine to form a functional layer on the substrate. The spraying machine includes a nozzle having a discharge port for discharging the liquid coating agent, a plurality of first control elements disposed on the nozzle for controlling the pressure parameter value of the discharging liquid, and a second control element disposed on the nozzle for controlling the dispensing amount parameter value of the discharging liquid.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a perovskite solar cell. Prior Technology

[0002] In recent years, perovskite solar cells, with their excellent photoelectric conversion efficiency, have become a target of intense research and development. However, current methods for fabricating perovskite solar cells often suffer from high manufacturing costs. Summary of the Invention

[0003] This invention provides a method for manufacturing perovskite solar cells, which can effectively reduce manufacturing costs while maintaining excellent cell conversion efficiency.

[0004] A method for manufacturing a perovskite solar cell according to the present invention includes providing a substrate to be coated and spraying a liquid coating agent using a spraying machine to form a functional layer on the substrate. The spraying machine includes a nozzle having a discharge port for discharging the liquid coating agent, a plurality of first control elements disposed on the nozzle for controlling the pressure parameter value of the discharging liquid, and a second control element disposed on the nozzle for controlling the dispensing amount parameter value of the discharging liquid.

[0005] In one embodiment of the present invention, the above-mentioned dosage parameter value is less than 8 ml / min.

[0006] In one embodiment of the present invention, the pressure parameter values ​​mentioned above include atomized air pressure parameter values ​​and graphic pressure parameter values.

[0007] In one embodiment of the present invention, the atomized air parameter value is between 0.01 MPa and 0.4 MPa.

[0008] In one embodiment of the present invention, the above-mentioned graphical pressure parameter values ​​are between 0.01 MPa and 0.4 MPa.

[0009] In one embodiment of the present invention, the distance between the nozzle and the object to be sprayed is between 10 mm and 50 mm.

[0010] In one embodiment of the present invention, the moving speed of the above-mentioned nozzle is between 300 mm / s and 700 mm / s.

[0011] In one embodiment of the present invention, the moving distance of the above-mentioned nozzle is between 0.1 mm and 30 mm.

[0012] In one embodiment of the present invention, the needle opening degree of the second control element is between 0.1 weeks and 1 week.

[0013] Based on the above, the present invention introduces a spraying machine in the manufacturing process of perovskite solar cells that can at least control the pressure and dosage parameters of the chemical solution. In this way, the amount of chemical solution used can be effectively reduced, the manufacturing cost can be lowered, and the functional layer formed by it also has good uniformity and conductivity. Therefore, perovskite solar cells including the aforementioned functional layer can also maintain excellent cell conversion efficiency.

[0014] To make the above features and advantages of the present invention more apparent and understandable, specific embodiments are described below in conjunction with the accompanying drawings for detailed explanation. Simple Explanation of the Diagram

[0015] Figure 1 is a partial flowchart of a method for manufacturing a perovskite solar cell according to an embodiment of the present invention. Figure 2 is a partial perspective view of spraying in a spraying machine according to an embodiment of the present invention. Figures 3, 4, and 5 are partial perspective views of different stages of spraying according to an embodiment of the present invention. Figures 6, 7, and 8 are partial perspective views of a nozzle according to an embodiment of the present invention from different angles. Figure 9 is a top view of a single spraying path according to an embodiment of the present invention. Figure 10 is a partial cross-sectional schematic diagram of a perovskite solar cell according to an embodiment of the present invention. Implementation

[0016] The exemplary embodiments of the present invention will be fully described below with reference to the accompanying drawings. However, the invention may be implemented in many different forms and should not be construed as limited to the embodiments described herein. In the drawings, for clarity, the size and thickness of regions, parts, and layers may not be drawn to scale. For ease of understanding, the same elements will be indicated by the same symbols in the following description.

[0017] In the following detailed description, exemplary embodiments disclosing specific details are set forth for illustrative purposes and not for limitation, to provide a thorough understanding of the various principles of the invention. However, it will be apparent to those skilled in the art that the invention can be practiced in other embodiments departing from the specific details disclosed herein, thanks to this disclosure. Furthermore, descriptions of well-known apparatus, methods, materials, and other specific details may be omitted to avoid obscuring the description of the various principles of the invention.

[0018] In this document, the range expressed as "from one value to another" is a concise way of representing a range to avoid listing all the values ​​in that range in the specification. Therefore, the description of a particular range of values ​​covers any value within that range as well as the smaller range of values ​​defined by that value, just as the arbitrary value and the smaller range of values ​​are described in the explanatory text of the specification.

[0019] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood or known to those skilled in the art to which this invention pertains.

[0020] Referring to Figures 1 to 8, a method for manufacturing a perovskite solar cell according to an embodiment of the present invention includes at least the following steps. First, a substrate 110 to be coated is provided (step S1). Then, a coating agent 10 is sprayed onto the substrate 110 using a coating machine 120 to form a functional layer (not shown) (step S2). The nozzle 12 in the coating machine 120 includes a body 121 having a discharge port 121a, and a plurality of first control elements 122 and second control elements 123 disposed on the body 121.

[0021] Furthermore, multiple first control elements 122 are used to control the pressure parameter value of the output liquid 10, while the second control element 123 is used to control the dispensing quantity parameter value of the output liquid 10. Accordingly, this embodiment incorporates a spraying machine 120 that can at least control the pressure parameter value and dispensing quantity parameter value of the liquid 10. In this way, the amount of liquid 10 used can be effectively reduced, manufacturing costs can be lowered, and the functional layer formed by it also has good uniformity and conductivity. Therefore, the perovskite solar cell including the aforementioned functional layer can also maintain excellent cell conversion efficiency. Here, the dispensing quantity is defined as the amount of liquid 10 sprayed per minute.

[0022] On the other hand, spin-coating or slit-coating methods are commonly used to fabricate the functional layer in perovskite solar cells. However, spin-coating can produce edge beads, so an additional edge bead removal (EBR) process is required after the functional layer is formed, which results in additional production costs. Slit-coating has the disadvantage of high equipment costs. In contrast, the spray coating machine 120 used in this embodiment improves the above problems and has a competitive advantage.

[0023] In some embodiments, the functional layer is such as the electron transport layer, hole transport layer, light absorption layer, etc. in a perovskite solar cell, and the object to be coated is other film layers that lie on the aforementioned film layers and are in direct contact with them. For example, when the object to be coated is a glass substrate, the functional layer is the electron transport layer.

[0024] In some embodiments, the solution used in the electron transport layer may include tin dioxide (SnO 2), titanium dioxide (TiO 2), or zinc oxide (ZnO), etc., and the solution used in the hole transport layer may include organic p-type semiconductor materials (Spiro-MeOTAD) or PEDOT / PSS, etc., but the present invention is not limited thereto, and the specific composition of the solution 10 may be determined according to the actual functional layer requirements.

[0025] In this embodiment, the pressure parameter values ​​include atomizing air (AA) and pattern air (PA) parameters. For example, firstly, as shown in Figure 3, the first state 21 is when the nozzle 12 is turned on and operating. Next, as shown in Figure 4, the second state 22 is when the nozzle 12 has introduced the atomizing air (AA) parameter value. At this time, because the liquid medicine 10 becomes smaller molecules after being atomized by air, the sprayed liquid medicine 10 will be round. Then, as shown in Figure 5, the third state 23 is when the nozzle 12 has further introduced the pattern air (PA) parameter value. At this time, because the liquid medicine 10 will be given a lateral flattening pressure through the outlet 121a, the sprayed liquid medicine 10 will be elliptical. In this way, it can have the advantages of high atomization, stable spraying of uniformly sized particles, and high compatibility with the liquid medicine 10.

[0026] For example, as shown in Figures 6 and 7, the plurality of first control elements 122 include a pressure control element 122a for controlling the atomizing air pressure parameter value and a pressure control element 122b for controlling the graphic pressure parameter value. On the other hand, as shown in Figure 8, the second control element 123 is a knob control element with a knob 123a and a scale 123b for controlling the opening size of the nozzle 121a. That is, in this embodiment, through the design of the pressure control element and the knob control element, the spraying requirements can be reliably achieved. The pressure control elements 122a and 122b can be locked onto the body 121, and the knob control element can be screwed onto the body 121, but the present invention is not limited thereto.

[0027] Here, the nozzle 12 may optionally include a third control element 124 for controlling the entry and exit of the liquid medicine 10, which is provided on the body 121. In Figures 6 and 7, the positions of the pressure control element 122a, pressure control element 122b and the third control element 124 are only schematically shown. The positions of these elements can be adjusted according to the actual design requirements. As long as there are elements on the body 121 that can achieve these functions, they are within the protection scope of this invention.

[0028] In some embodiments, the dispensing rate parameter is between 0.02 mL / min and 18 mL / min, for example, between 1 mL / min and 5 mL / min; the atomizing air parameter is between 0.01 MPa and 0.4 MPa, for example, between 0.02 MPa and 0.1 MPa; and the pattern pressure parameter is between 0.01 MPa and 0.4 MPa, for example, between 0.02 MPa and 0.1 MPa. Within these value ranges, a stable and uniform film thickness (e.g., between 10 nm and 500 nm) can be achieved in the functional layer while reducing the use of the drug solution 10 and lowering costs. In addition, the dispensing rate parameter can be achieved by adjusting the needle opening of the second control element 123 between 0.1 laps and 1 lap.

[0029] In some embodiments, the value of the atomizing air parameter is positively correlated with the particle size in the dispensed liquid 10. Therefore, by adjusting the value of this parameter, the particle size in the dispensed liquid 10 can be controlled within a better range to meet the battery performance requirements. However, the present invention is not limited thereto.

[0030] In some embodiments, the following parameter values ​​can be further designed to optimize the spraying results, as shown in FIG2: the distance D5 to 200 mm from the nozzle 12 to the object to be sprayed 110, for example, a distance between 10 mm and 50 mm; the moving speed of the nozzle 12 is between 300 mm / s and 700 mm / s, for example, a speed between 300 mm / s and 666 mm / s; and the moving distance P of the nozzle 12 is between 0.1 mm and 30 mm, for example, a moving distance between 1 mm and 10 mm, wherein the moving distance P can be defined as the distance the nozzle 12 moves each time, but the present invention is not limited thereto.

[0031] In some embodiments, when the moving distance P of the nozzle 12 remains constant, the smaller the atomizing air parameter value and the graphic pressure parameter value, the higher the battery conversion efficiency can be obtained, but the present invention is not limited thereto.

[0032] In some embodiments, the moving speed of the nozzle 12 is inversely related to the thickness of the functional layer. For example, the faster the moving speed of the nozzle 12, the thinner the thickness of the functional layer. Therefore, by adjusting the value of this parameter, the thickness of the functional layer can be controlled within a better range to meet the battery performance requirements. However, the present invention is not limited thereto.

[0033] In some embodiments, the spraying time of the nozzle 12 in a single spraying operation may vary depending on the size of the spraying area, as well as changes in the moving distance and moving speed. For example, as shown in Figures 2 and 9, a single spraying operation is the time from the starting position L1 to the ending position L2. The nozzle 12 may move back and forth in the X-axis and Y-axis directions to uniformly spray the liquid 10 onto the surface of the object to be sprayed 110. However, the present invention is not limited to this.

[0034] In some embodiments, the spraying machine 120 can spray back and forth multiple times on the same substrate area in the manner described above, wherein the number of spraying times can be between one and six, for example, between three and six, but the present invention is not limited thereto.

[0035] In some embodiments, the spraying machine 120 of this embodiment can be applied to small-area spraying (e.g., the X-axis spraying range R1 multiplied by the Y-axis spraying range R2 is 50mm x 50mm), but the present invention is not limited thereto. The spraying machine 120 of this embodiment can also be applied to large-area spraying (e.g., the X-axis spraying range R1 x the Y-axis spraying range R2 is 1800mm x 1200mm) and can be completed stably and quickly. Therefore, the spraying machine 120 of this embodiment is conducive to the realization of mass production, but the present invention is not limited thereto.

[0036] In this embodiment, the spraying machine 120 further includes a robotic arm 101 for holding the spray nozzle 12, a platform 102 for carrying the object to be sprayed 110, a housing 103 for accommodating the platform 102, the object to be sprayed 110, the spray nozzle 12, the robotic arm 101, and other components, and an operating element 104 (e.g., a touch control panel) optionally disposed on the housing 103 for operating related operating procedures. The area enclosed by the square dashed frame in Figure 2 schematically shows the situation inside the housing 103, and the temperature and humidity inside the housing 103 are similar to the atmospheric environment or can be adjusted according to the actual design requirements. This invention does not impose any limitations on this.

[0037] In some embodiments, the nozzle 12 may be made of a metal or polymer material, such as stainless steel (SUS), aluminum (Al) or polytetrafluoroethylene (PTFE), but the present invention is not limited thereto.

[0038] In some embodiments, the size Φ of the discharge port 121a is between 0.1 mm and 1 mm, for example, Φ = 0.6 mm, but the invention is not limited thereto.

[0039] In some embodiments, the plurality of first control elements 122 and third control elements 124 have the same size, Φ between 1 mm and 10 mm, for example Φ = 6 mm, but the present invention is not limited thereto.

[0040] In some embodiments, the dimensions of the housing 103 are, for example, 1800mm x 1600mm x 2155mm (length x width x height), but the present invention is not limited thereto.

[0041] In some embodiments, the method for manufacturing perovskite solar cells further includes performing an illumination step before spraying to make the surface of the object to be sprayed 110 hydrophobic. In this way, when the liquid 10 is sprayed on the surface, it can be effectively dispersed, thereby significantly improving the uniformity and conductivity of the spraying. However, the present invention is not limited thereto.

[0042] In some embodiments, the method for manufacturing perovskite solar cells further includes performing a drying process after spraying, for example, drying can be performed at 100°C for 10 minutes, but the present invention is not limited thereto.

[0043] In some embodiments, the solid content of the liquid 10 is in the range of 0.05% to 10% by weight to improve the coating quality, but the present invention is not limited thereto.

[0044] The effects of the present invention will be described in more detail below with reference to embodiments and comparative examples. Although the following embodiments are described, details and processes may be appropriately changed without departing from the scope of the present invention. Therefore, the present invention should not be interpreted as limiting based on the embodiments described below.

[0045] <Hydrophobicity Test>

[0046] An EUV lamp was used to irradiate a 15x15 mm² FTO glass substrate (irradiation distance 3 mm, illuminance 90 mW / cm²), and nitrogen gas was blown during the irradiation to test the relationship between irradiation time and contact angle. The test results are shown in Table 1. The contact angle can be reduced to 5° to 7° after irradiation, which shows that the irradiation step can indeed make the glass substrate surface hydrophobic.

[0047] Table 1 N2: 200 L / min CDA: 20 L / min time Contact angle before irradiation Contact angle after irradiation 2 minutes 43.93° 6.47° 10 minutes 43.59° 5.21° 15 minutes 42.54° 5.02° N2: 210 L / min CDA: 13.5 L / min Light accumulation: 10800 mW / cm² 2 minutes 49.6° 7.03°

[0048] Please refer to Figure 10. The fabrication steps of the perovskite solar cells in Examples 1 and 2 will be described below.

[0049] Step 1: After cleaning the FTO glass substrate 210 (the object to be coated) with acetone, isopropanol and deionized water, it is dried. Then, the light-irradiation step is performed, and the substrate is irradiated with EUV lamp for 2 minutes. During the irradiation, nitrogen gas is blown out to make the surface of the FTO glass substrate 210 hydrophobic.

[0050] Step 2: Using the above-mentioned spraying machine 120 and the operating conditions in Table 2, a tin dioxide / water solution with a solid content of 0.5% by weight is sprayed onto the FTO glass substrate 210. Then, a drying step is performed to form an electron transport layer 220 (functional layer), wherein the thickness of the electron transport layer 220 is also shown in Table 2.

[0051] Table 2 Atomizing air pressure (MPa) Graphical pressure (MPa) Needle opening Dosage (mL / min) Distance from nozzle to object to be sprayed (mm) Movement speed (mm / s) Movement distance (mm) Number of sprays X(mm) Y(mm) Drug solution usage (mL / sample) Electron transport layer thickness (nm) Example 1 0.1 0.1 Open in 0.5 weeks 4 100 333 10 1 200 200 1.28 98.6 Example 2 0.1 0.1 Open in 0.5 weeks 2 100 333 10 1 200 200 0.64 41.9

[0052] Step 3: A solution of dimethylformamide (DMF) is applied to an FTO glass substrate 210 using a spin coating method and dried at approximately 100°C to obtain a perovskite light-absorbing layer 230.

[0053] Step 4: Apply an organic P-type semiconductor material (Spiro-OMeTAD) solution onto the perovskite light-absorbing layer 230 using a spin coating method. After drying at 100~150℃, a hole transport layer 240 is obtained.

[0054] Step 5: Obtain metal electrode 250 by vacuum evaporation, wherein the material of metal electrode 250 is silver (Ag).

[0055] The perovskite solar cells of Examples 1 and 2 were manufactured through the above steps 1 to 5, and their performance was tested. The results are shown in Table 3. From the results in Table 3, it can be concluded that the perovskite solar cells manufactured by the present invention can indeed maintain a cell conversion efficiency of about 20%, where Jsc is the short-circuit current density, Voc is the open-circuit voltage, FF is the fill factor, and Eff. is the conversion efficiency.

[0056] Table 3 Jsc(mA / cm 2) Voc(V) FF Eff.(%) Example 1 22.3 1.05 0.80 18.6 Example 2 23.3 1.04 0.80 19.5

[0057] It should be noted that the specific structural design and materials of the main body are omitted above to avoid obscuring the description of the various principles of the present invention. The corresponding structural design and materials of these components may be known to those skilled in the art, and the present invention does not limit them.

[0058] In summary, this invention introduces a spraying machine into the manufacturing process of perovskite solar cells, which can at least control the pressure and dosage parameters of the chemical solution. This effectively reduces the amount of chemical solution used, lowers manufacturing costs, and the resulting functional layer also has good uniformity and coverage. Therefore, perovskite solar cells including the aforementioned functional layer can maintain excellent cell conversion efficiency.

[0059] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

[0060] 10: Medicine liquid 12: Sprayer Head 21: First State 22: Second State 23: Third State 101: Robotic Arm 102: Platform 103: Shell 104: Operating element 110: Object to be sprayed 120: Spray painting machine 121:Ontology 121a: Exhale 122: First control element 122a, 122b: Pressure control elements 123: Second control element 123a: Knob 123b: Scale 124: Third control element 210: FTO glass substrate 220: Electron transport layer 230: Perovskite light-absorbing layer 240: Hole Transport Layer 250: Metal electrode D: Distance L1: Starting position L2: Finish line P: Spacing S1, S2: Steps R1: X-axis spraying range R2: Y-axis spraying range

Claims

1. A method for manufacturing a perovskite solar cell, comprising: Provide the material to be sprayed; And using a spraying machine to spray a liquid medicine to form a functional layer on the object to be sprayed, wherein the nozzle in the spraying machine includes: a body having a discharge port for dispensing the liquid medicine; A plurality of first control elements are disposed on the main body and used to control the pressure parameter value of the output drug solution, wherein the pressure parameter value includes the atomizing air pressure parameter value and the graphic pressure parameter value; and a second control element is disposed on the main body and used to control the dispensing volume parameter value of the output drug solution.

2. The method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the dispensing rate parameter value is between 1 ml / min and 5 ml / min.

3. The method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the atomizing air parameter value is between 0.01 megapascals and 0.4 megapascals.

4. The method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the value of the pattern pressure parameter is between 0.01 megapascals and 0.4 megapascals.

5. The method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the distance between the nozzle and the object to be coated is between 10 mm and 50 mm.

6. A method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the moving speed of the nozzle is between 300 mm / s and 700 mm / s.

7. A method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the moving distance of the nozzle is between 0.1 mm and 30 mm.

8. A method for manufacturing a perovskite solar cell as claimed in claim 1, wherein the pin opening degree of the second control element is between 0.1 weeks and 1 week.

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