Roll-to-roll slot-die perovskite thin film deposition apparatus

Abstract

The present application belongs to the technical field of solar photovoltaic, and specifically relates to a roll-to-roll slot coating perovskite thin film deposition equipment. The present application comprises an unwinding device, an ultraviolet ozone machine, a slot coating device, a drying annealing device and a winding device. The unwinding device is an unwinding driven wheel; the slot coating device comprises a tensioning wheel and a slot coater; the drying annealing device comprises a reverse solvent gas air knife, a nitrogen gas air knife and an infrared annealing machine; and the winding device comprises a winding driving wheel. Guide rollers are arranged between the unwinding device and the ultraviolet ozone machine and between the drying annealing device and the winding device respectively, for tensioning and guiding the flexible film to run. The roll-to-roll slot coating perovskite thin film deposition equipment of the present application disassembles the steps of roll-to-roll preparation of perovskite solar cells, realizes the functions of ozone, thin film deposition and annealing separately, thereby improving the stability and simplicity of the equipment and reducing process errors.

Description

Technical Field

[0001] This invention belongs to the field of solar photovoltaic technology, specifically relating to roll-to-roll slot coating perovskite thin film deposition equipment. Background Technology

[0002] Perovskite optoelectronic materials, as star materials in the optoelectronic field, boast superior performance, low cost, and simple processing and manufacturing processes. Breakthroughs have been achieved in thin-film solar cells, light-emitting devices, and detectors based on perovskite materials, demonstrating significant application prospects. In just 10 years, the photoelectric conversion efficiency of perovskite thin-film solar cells has increased from 3.8% to over 25.7%, with double-junction perovskite cells exceeding 31%, showcasing enormous commercial potential. Therefore, the industry is accelerating its industrialization efforts.

[0003] Perovskite thin films are a core component of perovskite thin-film devices, and their quality directly determines the performance of these devices. Solution spin coating is a conventional laboratory method for preparing perovskite thin films and devices, offering high-quality films with good controllability. However, it is only suitable for small-area, small-batch production of perovskite thin films and devices, and is not compatible with large-area, large-scale industrial manufacturing processes. High-efficiency, large-batch preparation of high-quality, uniform, large-area perovskite thin films using printing technology is a crucial pathway to advancing the industrialization of perovskite optoelectronic devices.

[0004] In the rapid commercialization of perovskite solar cells, roll-to-roll (R2R) printing has shown promising prospects due to its rapid mass production capabilities. R2R printing offers numerous advantages, such as improved volume, stability, and repeatability, which have been well-proven in organic solar cells. The fabrication process of perovskite solar cells involves etching, cleaning, drying, coating, drying, and re-etching. Integrating these processes into a single R2R device results in a larger equipment and longer flexible films, significantly amplifying errors in the fabrication process and placing more stringent demands on equipment development. Summary of the Invention

[0005] The purpose of this invention is to provide a roll-to-roll slit coating perovskite thin film deposition equipment with good stability and small process error.

[0006] The roll-to-roll slit coating perovskite thin film deposition equipment provided by this invention deconstructs the existing perovskite solar cell fabrication process, achieving separate ozone, thin film deposition, and annealing functions, thereby improving the stability and simplicity of the equipment and ensuring smaller process errors. Its structure is described in [reference needed]. Figure 1 As shown, it specifically includes, from left to right, an unwinding device, a UV ozone generator, a slot coating device, a drying and annealing device, and a winding device; wherein:

[0007] The unwinding device is an unwinding driven wheel used to wind the flexible thin film of perovskite solar cells;

[0008] The ultraviolet ozone generator is located to the right of the unwinding device and is used to ozone treat the surface of the hygienic film.

[0009] The slit coating apparatus includes a tensioning wheel and a slit coating machine. The tensioning wheel consists of two large rollers on the same horizontal line and a small pressing roller located between the two large rollers, used to achieve the tensioning function of the flexible film. The lower surface of the flexible film passes over the two large rollers, and the upper surface of the flexible film passes under the small pressing roller and is pressed downward by the small pressing roller. The small pressing roller can be adjusted in its longitudinal position to achieve different degrees of tension.

[0010] The slot coater is a detachable and flexible component that can be located directly above the first large roller on the left or above the second large roller. The coating liquid is pre-filled in the slot coater, and the liquid outlet pressure is provided by a peristaltic pump to control the amount of coating liquid output. The coating liquid flows out from the outlet at a certain speed to the surface of the flexible film, while the flexible film moves to the right at a certain speed to make the liquid evenly spread on the surface of the flexible film.

[0011] The drying and annealing apparatus includes an anti-solvent gas air knife, a nitrogen air knife, and an infrared annealing machine, arranged sequentially from left to right on the right side of the slot coating device and directly above the film. The flexible film containing liquid is first transported to the area directly below the anti-solvent gas air knife station. The anti-solvent gas air knife continuously blows anti-solvent gas onto the flexible film while the film moves to the right until it reaches the area directly below the nitrogen air knife station. The nitrogen air knife continuously blows high-purity nitrogen gas onto the flexible film at a certain pressure, causing the liquid on the film to initially evaporate and dry. The anti-solvent gas air knife and the nitrogen air knife can be adjusted in deflection angle to achieve different drying effects. After being purged with nitrogen, the flexible film reaches the infrared annealing machine station for high-temperature heating and annealing.

[0012] The winding device is a winding drive wheel located on the far right of the equipment, used to wind up the flexible film; the winding drive wheel is controlled by a motor to drive the unwinding driven wheel.

[0013] Between the unwinding device and the ultraviolet ozone generator, and between the drying and annealing device and the winding device, there are several (usually two) guide rollers. The guide rollers are used to tension the flexible film on one hand, and to change the running direction of the flexible film on the other hand, guiding the flexible film at the previous station to the next station.

[0014] The operating process of the device of this invention is as follows:

[0015] The flexible film is fixed to the unwinding driven roller and the winding drive roller at both ends. The winding drive roller is driven by a motor, which in turn drives the unwinding driven roller, various guide rollers, and tension rollers, causing the flexible film to move from left to right. The flexible film first reaches the ultraviolet ozone device station, where the ultraviolet ozone treats the surface of the flexible film. Then it reaches the slot coating device station, where the slot coating device evenly deposits the coating liquid onto the surface of the flexible film. Next, it reaches the drying and annealing device station, where the liquid deposition is promoted by an anti-solvent gas air knife, the drying is assisted by a nitrogen air knife, and the film is further heated by an infrared annealing machine. Finally, it is collected by the winding drive roller.

[0016] In this invention, the movement speed of the flexible thin film substrate is controlled to be 20~60 mm / s.

[0017] In this invention, the working range of the ultraviolet ozone generator can be designed to be 20*30 cm. 2 ~20*60 cm 2 The effectiveness of ultraviolet ozone can be altered by adjusting the number and power of the ultraviolet lamps.

[0018] In this invention, the liquid discharge rate of the slot coater can be 40~250 μL / s.

[0019] In this invention, the deflection angle of the slit coating machine is 0° to the vertical direction and 45° to the left and 45° to the right; the distance between the liquid outlet of the slit coating machine and the flexible film is 10~200 μm.

[0020] In this invention, the deflection angles of the antisolvent gas air knife and the nitrogen air knife are 0° to the left and 45° to the right; the gas pressure is 0.05 to 0.2 MPa.

[0021] In this invention, the heating temperature of the infrared annealing machine is 80~150 ℃.

[0022] The features of this invention are: it combines functional completeness with equipment simplicity: the equipment has complete flexible perovskite thin film deposition functions (UV ozone, slot coating, gas-assisted drying, and heating annealing); the simple equipment has a total length of 1.8 m to 2.2 m, which is more conducive to transfer, transportation and maintenance compared to complete perovskite preparation equipment of more than ten meters; the short roll-to-roll distance can ensure the straightness and stability of the flexible substrate winding; the invention incorporates an antisolvent gas air knife, which blows the antisolvent onto the liquid surface of the flexible substrate that is about to crystallize in the form of gas, solving the problem that it is inconvenient to drop antisolvent in slot coating. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the roll-to-roll slit coating perovskite thin film deposition apparatus of the present invention.

[0024] Figure 2This is a diagram illustrating a perovskite film segment prepared by the roll-to-roll slit coating perovskite film deposition apparatus of the present invention.

[0025] The numbers in the diagram are: 1-unwind driven roller, 2-guide roller, 3-flexible film, 4-ozone machine, 5-slit coating machine, 6-antisolvent gas air knife, 7-nitrogen air knife, 8-infrared annealing machine, 9-rewind drive roller, 10-tension roller. Implementation

[0026] The preferred embodiments of the present invention are given below with reference to the accompanying drawings and described in detail.

[0027] like Figure 1 As shown, a roll-to-roll slot coating perovskite thin film deposition apparatus according to the present invention mainly includes an unwinding device, an ultraviolet ozone generator, a slot coating device, a drying and annealing device, and a winding device. The unwinding device includes an unwinding driven roller and guide rollers; the slot coating device includes a tensioning roller and a slot coating machine; the drying and annealing device includes an anti-solvent gas air knife, a nitrogen air knife, and an infrared annealing machine; and the winding device includes a winding drive roller and guide rollers.

[0028] The flexible film 3 is fixed at both ends to the unwinding driven roller 1 and the winding drive roller 9, respectively. The motor drives the winding drive roller to move the unwinding driven roller, each guide roller, and the tension roller, causing the flexible film to move from left to right at a speed of 20 mm / s. The guide roller 2 tensions and changes the direction of movement of the flexible film. The flexible film moves to a position directly below the ultraviolet ozone generator for ultraviolet ozone treatment. Subsequently, the flexible film is further tensioned by tensioning roller 10 to maintain a smooth and flat contact between the flexible film and the large roller. The distance between the liquid outlet of the slot coater 5 and the surface of the second large roller is adjusted to 100 μm, and the slot coater is tilted 30° to the right. Solution is injected into the slot coater, and the internal air pressure of the slot coater is controlled by a peristaltic pump to make the liquid flow out of the slot coater at 40 μL / s. The flexible film is kept moving to the right to ensure that the liquid is evenly spread on the flexible film. Then, chlorobenzene gas is blown onto the flexible film through anti-solvent gas air knife 6 to promote perovskite film deposition. The purging gas pressure is 0.2 MPa and the rightward deflection angle is 10°. After being purged by chlorobenzene gas, the flexible film is moved to nitrogen air knife 7, and high-purity nitrogen is blown onto the flexible film through nitrogen air knife to assist in liquid drying. The purging gas pressure is 0.1 MPa and the rightward deflection angle is 10°. Finally, the flexible film is annealed at 120° using infrared annealing machine 8. The flexible film is heated and annealed at ℃, during which it is continuously moved to the right; finally, the flexible film is wound up by the winding drive wheel 9 to complete the perovskite film deposition process. The flexible perovskite film deposited by the roll-to-roll slot coating perovskite film deposition equipment of this invention is as follows: Figure 2 As shown, a uniform, large-area perovskite thin film was obtained.

[0029] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A roll-to-roll slit coating perovskite thin film deposition apparatus, characterized in that, Specifically, it includes, from left to right, an unwinding device, a UV ozone generator, a slot coating device, a drying and annealing device, and a winding device; wherein: The unwinding device is an unwinding driven wheel used to wind the flexible thin film of perovskite solar cells; The ultraviolet ozone generator is located to the right of the unwinding device and is used to ozone treat the surface of the hygienic film. The slot coating apparatus includes a tensioning wheel and a slot coating machine. The tensioning wheel consists of two large rollers on the same horizontal line and a small pressing roller located between the two large rollers, used to achieve the tensioning function of the flexible film. The lower surface of the flexible film passes over the two large rollers, and the upper surface of the flexible film passes under the small pressing roller and is pressed downward by the small pressing roller. The small pressing roller can achieve different degrees of tension by adjusting its longitudinal position. The slot coater is a detachable component located directly above the first large roller on the left or above the second large roller. The coating liquid is pre-filled in the slot coater, and the liquid outlet pressure is provided by a peristaltic pump to control the liquid outlet volume. The coating liquid flows out from the outlet at a certain speed to the surface of the flexible film, while the flexible film moves to the right at a certain speed to make the liquid evenly spread on the surface of the flexible film. The drying and annealing apparatus includes an anti-solvent gas air knife, a nitrogen air knife, and an infrared annealing machine, arranged sequentially from left to right on the right side of the slot coating device and directly above the film. The flexible film containing liquid is first transported to the area directly below the anti-solvent gas air knife station. The anti-solvent gas air knife continuously blows anti-solvent gas onto the flexible film while the film moves to the right until it reaches the area directly below the nitrogen air knife station. The nitrogen air knife continuously blows high-purity nitrogen gas onto the flexible film at a certain pressure, causing the liquid on the film to initially evaporate and dry. The anti-solvent gas air knife and the nitrogen air knife can be adjusted in deflection angle to achieve different drying effects. After being purged with nitrogen, the flexible film reaches the infrared annealing machine station for high-temperature heating and annealing. The winding device is a winding drive wheel located on the far right of the equipment, used to wind up the flexible film; the winding drive wheel is controlled by a motor to drive the unwinding driven wheel. Several guide rollers are respectively provided between the unwinding device and the ultraviolet ozone generator, and between the drying and annealing device and the winding device. The guide rollers are used to tension the flexible film on the one hand, and to change the running direction of the flexible film on the other hand, guiding the flexible film at the previous station to the next station.

2. The roll-to-roll slit coating perovskite thin film deposition apparatus according to claim 1, characterized in that, The equipment operation process is as follows: The flexible film is fixed on the unwinding driven wheel and the winding drive wheel at both ends. The winding drive wheel is driven by a motor, which drives the unwinding driven wheel, each guide wheel and tension wheel, so that the flexible film moves from left to right. The flexible film first reaches the ultraviolet ozone device station, where ultraviolet ozone treats the surface of the flexible film; then it reaches the slot coating device station, where the coating liquid is uniformly deposited onto the surface of the flexible film; then it reaches the drying and annealing device station, where anti-solvent gas air knife promotes liquid deposition, nitrogen air knife assists in purging and drying, and infrared annealing machine further heats it; finally, it is collected by the winding drive wheel.

3. The roll-to-roll slit coating perovskite thin film deposition apparatus according to claim 2, characterized in that, The movement speed of the flexible thin film substrate is controlled to be 20~60 mm / s.

4. The roll-to-roll slit coating perovskite thin film deposition apparatus according to claim 2, characterized in that, The working range of the UV ozone generator is designed to be 20*30 cm. 2 ~20*60 cm 2 The effect of ultraviolet ozone can be changed by adjusting the number and power of ultraviolet lamps.

5. The roll-to-roll slit coating perovskite thin film deposition apparatus according to claim 2, characterized in that, The liquid discharge rate of the slot coater is controlled at 40~250 μL / s; the deflection angle of the slot coater is 45° to the left and 45° to the right with the vertical direction as 0°; the distance between the liquid outlet of the slot coater and the flexible film is 10~200 μm.

6. The roll-to-roll slit coating perovskite thin film deposition apparatus according to claim 2, characterized in that, The deflection angles of the antisolvent gas air knife and the nitrogen air knife are 0° to the left and 45° to the right; the gas pressure is 0.05~0.2MPa.

7. The roll-to-roll slit coating perovskite thin film deposition apparatus according to claim 2, characterized in that, The heating temperature of the infrared annealing machine is 80~150 ℃.

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