Perovskite film preparation system and method with reel-to-reel continuous feeding function

Abstract

The present invention discloses a perovskite film preparation system and method with a roll-tape continuous feeding function. The system includes a roll-tape device, a spraying device, a pre-air drying device, a vacuum drying device, and a vapor deposition device. The roll-tape device includes a roller and a roll-tape. The rotation of the roller drives the roll-tape to rotate in a cycle. Along the direction of the roll-tape rotation, a spraying area, a pre-air drying area, a vacuum drying area, and a vapor deposition area are sequentially defined on the roll-tape. The spraying device provided in the spraying area sprays the precursor solution onto the roll-tape to form a wet film. The pre-air drying device provided in the pre-air drying area pre-air dries the wet film entering the air drying area. The vacuum drying device provided in the vacuum drying area dries the pre-air dried wet film entering the vacuum drying area into a dry film. The vapor deposition device provided in the vapor deposition area sublimates and deposits the dry film on the substrate. The system realizes the continuous transportation of the precursor raw material to the vapor deposition device for preparing the perovskite film, and the replacement of the precursor raw material is easy, greatly improving the utilization rate of the equipment and the production efficiency.

Description

Technical Field

[0001] The present invention belongs to the field of perovskite solar cells, and particularly relates to a perovskite film preparation system and method with a roll-to-roll continuous feeding function. Background Art

[0002] A perovskite solar cell is a solar cell that uses a perovskite-type organometallic halide semiconductor as a light-absorbing material. In recent years, the highest photoelectric conversion efficiency of perovskite solar cells has increased from 3.8% to 25.7%. Its photoelectric conversion efficiency not only exceeds that of other thin-film solar cells developed earlier, but even exceeds that of industrial solar cell technologies such as polycrystalline silicon solar cells that have been developed for many years, showing great industrial development prospects. The preparation methods of the perovskite film layer are divided into a one-step method and a two-step method. In the one-step method, defects in the perovskite layer will be distributed throughout the absorption layer and the interface. In the two-step method, a perovskite precursor film layer can be conformally deposited on a substrate with different roughness or morphology by a vacuum method first, and then a solution method or a vacuum method is used for preparation to finally form a perovskite film layer. Currently, the existing technologies of the vacuum method include thermal evaporation method, sputtering method, close-spaced sublimation method (CSS), vapor transport deposition method (VTD), close-spaced vapor transport deposition method (CSVT), etc. However, no matter which method is used, continuous feeding cannot be satisfied. The materials are all filled inside the vacuum chamber. When the raw materials reach the replacement cycle, it is necessary to break the vacuum for treatment before filling. The material replacement cycle is short, the time for replacing materials is long, production cannot be carried out during material replacement, and there is waste of residual materials every time materials are replaced. There is a risk of air leakage in the vacuum chamber after the material replacement is completed, which seriously reduces the utilization rate of the equipment and increases the costs of raw materials and labor. Summary of the Invention

[0003] The present invention aims to solve at least one of the technical problems in the related technologies to some extent. For this reason, an object of the present invention is to provide a perovskite film preparation system and method with a roll-to-roll continuous feeding function. The system uses a roll to rotate cyclically to prepare a dry film of the precursor on the roll. The preparation process of the dry film can be completed under atmospheric conditions. Then, the dry film is transported to a vacuum sublimation deposition chamber to be sublimated and deposited on a substrate to prepare a perovskite film without breaking the vacuum degree of the vacuum sublimation deposition chamber, thereby realizing the continuous transportation of the precursor raw materials to the vacuum sublimation deposition chamber to prepare the perovskite film, and the precursor raw materials are easy to replace, added as needed, effectively avoiding waste of materials, and greatly improving the utilization rate of the equipment and the production efficiency.

[0004] In one aspect of the present invention, a perovskite film preparation system with a roll-to-roll continuous feeding function is provided. According to an embodiment of the present invention, the perovskite film preparation system includes:

[0005] A tape winding device, the tape winding device includes a roller and a tape, the roller rotates to drive the tape to rotate in a cycle, and along the rotation direction of the tape, a spraying area, a pre-air drying area, a vacuum drying area and an evaporation coating area are sequentially defined on the tape;

[0006] A spraying device, the spraying device is arranged in the spraying area and is used for spraying a precursor solution onto the tape entering the spraying area to form a wet film;

[0007] A pre-air drying device, the pre-air drying device is arranged in the pre-air drying area and is used for pre-air drying the wet film entering the pre-air drying area;

[0008] A vacuum drying device, the vacuum drying device is arranged in the vacuum drying area and is used for drying the pre-air dried wet film entering the vacuum drying area into a dry film;

[0009] An evaporation coating device, the evaporation coating device is arranged in the evaporation coating area, and the evaporation coating device includes:

[0010] A transfer chamber, a conveyor belt is arranged in the transfer chamber, a substrate is placed on the conveyor belt, and along the conveying direction of the conveyor belt, the transfer chamber sequentially includes a feeding area, a deposition area and a discharging area;

[0011] A vacuum sublimation deposition chamber, the vacuum sublimation deposition chamber is communicated with the vacuum drying device, and along the rotation direction of the tape, the vacuum sublimation deposition chamber sequentially includes a feeding area, a sublimation area and a discharging area, the sublimation area is located below and communicated with the deposition area, the tape sends the dry film to the sublimation area, and the dry film sublimates in the sublimation area and is loaded on the substrate in the deposition area.

[0012] According to the perovskite film preparation system with a roll-to-roll continuous feeding function of the present invention, it includes a roll tape device, a spraying device, a pre-air drying device, a vacuum drying device, and an evaporation coating device. The rollers of the roll tape device rotate to drive the roll tape to circulate and rotate. A spraying area, a pre-air drying area, a vacuum drying area, and an evaporation coating area are sequentially defined on the roll tape. The spraying device arranged in the spraying area sprays the precursor solution onto the roll tape entering the spraying area to form a wet film. The pre-air drying device arranged in the pre-air drying area pre-air dries the above-mentioned wet film entering the pre-air drying area. The vacuum drying device arranged in the vacuum drying area dries the above-mentioned pre-air dried wet film into a dry film after it enters the vacuum drying area; the evaporation coating device includes a transfer chamber and a vacuum sublimation deposition chamber. The vacuum sublimation deposition chamber is communicated with the vacuum drying device. The dry film reaches the sublimation area through the feeding area of the vacuum sublimation deposition chamber. The substrate is placed on the conveyor belt in the transfer chamber. The conveyor belt reaches the deposition area through the film feeding area of the transfer chamber. The sublimation area is located below and communicated with the deposition area, and the substrate is located directly above the dry film. The roll tape is heated, and the precursor dry film on the roll tape sublimates and deposits on the substrate. After the substrate deposits the precursor, the conveyor belt carries the substrate out of the system through the film discharging area of the transfer chamber. After the dry film sublimates, the roll tape continues to rotate forward through the discharging area of the vacuum sublimation deposition chamber. This system utilizes the cyclic rotation of the roll tape to prepare a dry film of the precursor on the roll tape. The preparation process of the dry film can be completed under atmospheric conditions. Then, the dry film is transported into the vacuum sublimation deposition chamber without breaking the vacuum degree of the vacuum sublimation deposition chamber and sublimated and deposited on the substrate to prepare the perovskite film. Thus, it realizes the continuous transportation of the precursor raw material to the vacuum sublimation deposition chamber to prepare the perovskite film, and the replacement of the precursor raw material is easy. It can be added as needed, effectively avoiding material waste, and greatly improving the utilization rate and production efficiency of the equipment.

[0013] In addition, the perovskite film preparation system with a roll-to-roll continuous feeding function according to the above embodiment of the present invention may further have the following technical features:

[0014] In some embodiments of the present invention, the spraying device includes a raw material tank, a cleaning tank, and a spray head. A raw material tank one-way valve and a spray head valve are sequentially arranged on the pipeline connecting the raw material tank and the spray head. The outlet of the cleaning tank is communicated with the pipeline between the raw material tank one-way valve and the spray head valve. A cleaning tank valve is arranged at the outlet of the cleaning tank. The spray head is located directly above the roll tape. Thus, the spraying of the precursor and the cleaning and maintenance of the spraying pipeline, the spray head, and the roll tape can be realized.

[0015] In some embodiments of the present invention, the pre-air drying device includes a fan and a fan cover. The fan is arranged inside the fan cover. An air inlet is arranged at the upper end of the fan cover, and an air outlet is arranged at the lower end of the fan cover. The air outlet is located directly above the roll tape. Thus, the wet film can be pre-air dried.

[0016] In some embodiments of the present invention, a protective cover is provided around the spraying device and the pre-air drying device, and a process gas outlet is provided above the protective cover. Thus, the organic gases volatilized during the spraying and pre-air drying processes can be collected and purified.

[0017] In some embodiments of the present invention, the vacuum drying device includes a vacuum chamber. One end of the vacuum chamber is provided with a tape inlet, and the other end of the vacuum chamber is provided with a tape outlet. At the tape inlet and the tape outlet, upper and lower opposing roller wheels are respectively provided. The tape sequentially passes through the opposing roller wheels at the tape inlet and the tape outlet. A heating component and a vacuum port are provided inside the vacuum chamber. Thus, the vacuum degree of the vacuum chamber can be maintained, and the speed of drying the wet film into a dry film can be increased.

[0018] In some embodiments of the present invention, a rectifying plate is provided inside the vacuum chamber along the rotation direction of the tape. The rectifying plate has holes distributed in an array, and the distance between the rectifying plate and the bottom of the vacuum chamber is adjustable. Thus, the airflow in the vacuum drying chamber can be adjusted to ensure the quality of the dry film.

[0019] In some embodiments of the present invention, vacuum ports are provided in the film feeding area, the deposition area, and the film discharging area; vacuum ports are provided in the feeding area, the sublimation area, and the discharging area. Thus, a certain vacuum degree can be maintained in the film feeding area, the deposition area, the film discharging area, the feeding area, the sublimation area, and the discharging area.

[0020] In some embodiments of the present invention, upper and lower opposing roller wheels are respectively provided in the feeding area and the discharging area, and a heating element is provided below the tape in the sublimation area. Thus, the vacuum degree in the feeding area, the sublimation area, and the discharging area can be maintained, which is beneficial to the sublimation of the precursor dry film on the tape.

[0021] In some embodiments of the present invention, a tape deviation correction system is provided on the tape. Thus, the running condition of the tape can be monitored in real time, and the running state of the tape can be adjusted.

[0022] In some embodiments of the present invention, a brush and a collection box are provided at the lower end of the tape device. Thus, the tape after evaporation coating can be effectively cleaned, and the residues can be collected at the same time.

[0023] On the other hand of the present invention, the present invention provides a method for preparing a perovskite film by using the above perovskite film preparation system with a tape-type continuous feeding function. According to an embodiment of the present invention, the method includes:

[0024] (1) Using a spraying device to spray a precursor solution onto the tape entering the spraying area so as to form a wet film on the tape;

[0025] (2) Use a pre-drying device to pre-dry the wet film entering the pre-drying area to obtain a pre-dried wet film;

[0026] (3) Use a vacuum drying device to vacuum-dry the pre-dried wet film entering the vacuum drying area to obtain a dry film;

[0027] (4) The tape transports the dry film to the sublimation area of the evaporation device, and the dry film sublimates in the sublimation area and is loaded on the substrate in the deposition area to obtain a perovskite film.

[0028] Thus, using the above system and this method, the precursor raw materials can be continuously transported into the evaporation device for sublimation deposition to prepare the perovskite film, greatly improving the utilization rate of the equipment and the production efficiency of the perovskite film.

[0029] In addition, the method for preparing a perovskite film according to the above embodiments of the present invention may further have the following technical features:

[0030] In some embodiments of the present invention, in step (1), the precursor solution includes at least one of PbI 2 , PbCl 2 , PbBr 2 , CsI, CsBr, CsCl, FAI, FABr, and FACl, and the thickness of the wet film is 1-1000 μm. Thus, the quality of the dry film can be improved, which is beneficial to the sublimation deposition of the dry film onto the substrate.

[0031] In some embodiments of the present invention, in step (2), the temperature of the pre-drying is 25-100 °C, the wind pressure is 0.1-0.7 MPa, the time is 1-300 s, and the thickness of the pre-dried wet film is 1-1000 μm. Thus, the wet film can be better pre-dried.

[0032] In some embodiments of the present invention, in step (3), the time of the vacuum drying is 1-300 s, the temperature is 25-100 °C, the vacuum degree is 0.1 Pa-1000 Pa, and the thickness of the dry film is 0.1-100 μm. Thus, the energy consumption can be reduced, which is helpful for the sublimation deposition of the precursor.

[0033] In some embodiments of the present invention, in step (4), the temperature of the sublimation area is 50-300 °C, the sublimation time is 1-300 s, the vacuum degree is 0.1 Pa-10 Pa, and the thickness of the perovskite film is 0.3-1 μm. Thus, the precursor can be better sublimated and deposited.

[0034] The additional aspects and advantages of the present invention will be partly given in the following description, partly will become obvious from the following description, or be understood through the practice of the present invention. Description of the Drawings

[0035] The above and / or additional aspects and advantages of the present invention will become apparent and be readily understood from the following description of embodiments in conjunction with the accompanying drawings, in which:

[0036] Figure 1 is a structural framework diagram of a perovskite film preparation system with a roll-to-roll continuous feeding function according to an embodiment of the present invention;

[0037] Figure 2 is a structural detail diagram of a perovskite film preparation system with a roll-to-roll continuous feeding function according to an embodiment of the present invention;

[0038] Figure 3 is a position diagram of a roll-to-roll and deviation rectifying system according to an embodiment of the present invention;

[0039] Figure 4 is a structural diagram of a tensioning wheel according to an embodiment of the present invention;

[0040] Figure 5 is a structural diagram of a spraying device and a pre-air drying device according to an embodiment of the present invention;

[0041] Figure 6 is a structural diagram of a vacuum drying device according to an embodiment of the present invention;

[0042] Figure 7 is a position diagram of a transmission belt and a substrate according to an embodiment of the present invention;

[0043] Figure 8 is a structural diagram of a vapor deposition device according to an embodiment of the present invention. Detailed Description of the Invention

[0044] Embodiments of the present invention will be described in detail below. Examples of the embodiments are shown in the accompanying drawings, where the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary only for explaining the present invention and should not be construed as limiting the present invention.

[0045] In one aspect of the present invention, the present invention provides a perovskite film preparation system with a roll-to-roll continuous feeding function. According to an embodiment of the present invention, referring to Figure 1 , the perovskite film preparation system includes a roll-to-roll device 100, a spraying device 200, a pre-air drying device 300, a vacuum drying device 400, and a vapor deposition device 700.

[0046] According to an embodiment of the present invention, referring to Figure 1 and Figure 2, the winding device 100 includes a roller 120 and a winding belt 110. The rotation of the roller 120 drives the winding belt 110 to rotate in a cycle. Along the rotation direction of the winding belt 110, a spraying area, a pre-air drying area, a vacuum drying area, and an evaporation coating area are sequentially defined on the winding belt 110. To further improve the performance of the winding belt 110, referring to Figure 1 and Figure 3 , a deviation rectification system 130 can be provided on the winding belt to monitor the operation of the winding belt in real time and adjust the running state of the winding belt. Specifically, referring to Figure 1 and Figure 4 , the winding device 100 further includes a tensioning wheel 111. A pressure sensor and a pressure regulating system are provided on the tensioning wheel 111, which can detect the tension of the winding belt 110 in real time and cooperate with the deviation rectification system 130 to adjust and rectify the deviation in real time. Those skilled in the art can understand that the number of rollers and the length of the winding belt can be selected according to the actual situation. For the material of the winding belt, those skilled in the art can also select according to the actual situation. For example, in this application, a winding belt made of stainless steel is selected. The winding belt not only has stable properties and is not easy to react with the precursor, but also is used to heat and sublime the precursor material. According to an embodiment of the present invention, referring to Figure 1 , a brush 30 and a collection box 31 are provided at the lower end of the winding device 100, so as to effectively clean the winding belt 110 after evaporation coating and collect the residue after the dry film sublimes.

[0047] According to an embodiment of the present invention, referring to Figure 1 and Figure 2 , the spraying device 200 is arranged in the spraying area (not shown), and is used to spray the precursor solution onto the winding belt 110 entering the spraying area to form a wet film. According to an embodiment of the present invention, referring to Figure 5, the spraying device 200 includes a raw material tank 210, a cleaning tank 220 and a spray head 230. A raw material tank one-way valve 211 and a spray head valve 231 are successively provided on the pipeline connecting the raw material tank 210 and the spray head 230. The outlet of the cleaning tank 220 is connected to the pipeline between the raw material tank one-way valve 211 and the spray head valve 231. A cleaning tank valve 221 is provided at the outlet of the cleaning tank 220. The spray head 230 is located directly above the winding tape 110. When the spray head valve 231 is opened, the precursor solution in the raw material tank 210 is sprayed on the winding tape 110 through the spray head 230. A raw material tank one-way valve 211 is provided at the outlet of the raw material tank 210. When it is necessary to clean the spraying pipeline or the winding tape, the cleaning tank valve 221 at the outlet of the cleaning tank 220 is opened, and the cleaning liquid in the cleaning tank 220 flows through the pipeline and the spray head 230, so as to achieve the purpose of cleaning, and the cleaning liquid is sprayed on the winding tape 110 through the spray head 230 to clean the winding tape 110. Further, a spray head cover 232 can be added in the spraying area of the spray head 230 to reduce the diffusion of organic substances in the precursor solution to the external environment. It should be noted that the specific spraying method and the number of spraying devices 200 can be selected according to the actual situation. For example, the spraying methods include but are not limited to air spraying, ultrasonic spraying, electrostatic spraying and medium-pressure mixed gas spraying. Preferably, medium-pressure mixed gas spraying is used, which uses compressed air and electricity as power to drive a plunger pump to directly pressurize the raw material and spray it instantaneously through a feeding hose, a spray gun or a nozzle to form an extremely fine mist-like paint liquid, which is quickly sprayed onto the stainless steel winding tape to form a dense coating. This spraying method has high material utilization rate and high working efficiency. A certain amount of air is mixed in the material, optimizing the atomization effect, and the sprayed paint mist is more uniform. At the same time, the air content is small, reducing the content of organic gases and the impact on the environment.

[0048] According to an embodiment of the present invention, refer to Figure 1 , the pre-air drying device 300 is arranged in the pre-air drying area and is used for pre-air drying the wet film entering the pre-air drying area. According to an embodiment of the present invention, refer to Figure 5 , the pre-air drying device 300 includes a fan 310 and a fan cover 320. The fan 310 is arranged inside the fan cover 320. An air inlet (not shown) is provided at the upper end of the fan cover 320, and an air outlet 311 is provided at the lower end of the fan cover 320. The air outlet 311 is located directly above the winding tape 110. Air enters from the air inlet, is blown out from the air outlet 311 by the fan 310, and the blown air pre-air dries the wet film on the winding tape 110. Further, a cleaning device 330 is installed at the air inlet position to purify the air blown onto the wet film and prevent some substances in the air from affecting the wet film.

[0049] According to an embodiment of the present invention, refer to Figure 5, a protective cover 20 is provided around the spraying device 200 and the pre-air drying device 300, and a process gas outlet 21 is provided above the protective cover 20. The protective cover 20 can collect the organic gases volatilized during the spraying process and the pre-air drying process, and by installing an air purification system at the process gas outlet 21, the collected organic gases can be purified.

[0050] According to an embodiment of the present invention, refer to Figure 1 , a vacuum drying device 400 is arranged in the vacuum drying area and is used to dry the pre-air dried wet film entering the vacuum drying area into a dry film. According to an embodiment of the present invention, refer to Figure 6 , the vacuum drying device 400 includes a vacuum chamber 410. One end of the vacuum chamber 410 is provided with a tape inlet 411, and the other end of the vacuum chamber is provided with a tape outlet 412. At the tape inlet 411 and the tape outlet 412, there are opposing roller wheels 413 arranged up and down. The tape 110 sequentially passes through the opposing roller wheels 413 at the tape inlet 411 and the tape outlet 412. A heating component 414 and a vacuum port 415 are provided in the vacuum chamber 410. The pre-air dried wet film on the tape 110 passes through the opposing roller wheels 413 at the tape inlet 411 and enters the vacuum chamber 410. The heating component 414 is turned on, and a vacuum is drawn from the vacuum port 415. In an environment with a certain degree of vacuum, the wet film on the tape 110 is dried into a dry film relatively quickly, and then is transported out of the vacuum chamber 410 through the opposing roller wheels 413 at the tape outlet 412. Further, a rectifying plate 417 can be provided in the vacuum chamber 410 along the rotation direction of the tape 110. The rectifying plate 417 has holes (not shown) distributed in an array, and the distance between the rectifying plate 417 and the bottom of the vacuum chamber 410 is adjustable, so as to adjust the air flow in the vacuum chamber 410 and ensure the quality of the dry film. In order to adjust the vacuum degree of the vacuum chamber 410, an inflation port 416 can also be provided on the vacuum chamber 410, and a valve is provided at the inflation port 416 for control. Those skilled in the art can understand that in order to maintain the vacuum degree of the vacuum chamber 410, one of the opposing roller wheels 413 is an elastic roller wheel, so that the pressing between the two roller wheels can be more dense.

[0051] According to an embodiment of the present invention, refer to Figure 1 and Figure 2, the evaporation device 700 is arranged in the evaporation area. The evaporation device 700 includes a transfer chamber 500 and a vacuum sublimation deposition chamber 600. A conveyor belt 540 is arranged in the transfer chamber 500, and a substrate 10 is placed on the conveyor belt 540. Along the conveying direction of the conveyor belt 540, the transfer chamber 500 sequentially includes a loading area 510, a deposition area 520, and an unloading area 530; the vacuum sublimation deposition chamber 600 is communicated with the vacuum drying device 400. Along the rotation direction of the winding tape 110, the vacuum sublimation deposition chamber 600 sequentially includes a feeding area 610, a sublimation area 620, and a discharging area 630. The sublimation area 620 is located below and communicated with the deposition area 520. The winding tape 110 sends the dry film to the sublimation area 620, and after the dry film sublimates in the sublimation area 620, it is loaded on the substrate 10 in the deposition area 520. Specifically, the dry film reaches the sublimation area 620 through the feeding area 610 of the vacuum sublimation deposition chamber 600. The substrate 10 is placed on the conveyor belt 540 in the transfer chamber 500. The conveyor belt 540 reaches the deposition area 520 through the loading area 510 of the transfer chamber 500. The sublimation area 620 is located below and communicated with the deposition area 520, and the substrate 10 is located directly above the dry film. Heat the winding tape 110, and the precursor dry film on the winding tape 110 sublimates and deposits on the substrate 10. After the substrate 10 deposits the precursor, the conveyor belt 540 carries the substrate 10 and transports it out of the transfer chamber 500 through the unloading area 530. After the dry film sublimates, the winding tape 110 continues to rotate forward through the discharging area 630 of the vacuum sublimation deposition chamber 600. Those skilled in the art can understand that the precursor sublimates and deposits on the back (bottom surface) of the substrate 10. Therefore, when the substrate 10 is placed on the conveyor belt 540, the back of the substrate 10 needs to face the dry film directly. For example, refer to Figure 7 , both sides of the substrate 10 are placed on the rotating wheels 541 on both sides of the conveyor belt 540, and through the rotation of the rotating wheels 541, the substrate 10 moves forward. At the same time, refer to Figure 2 , in order to be able to transfer the dry film in an environment with a certain vacuum degree after the dry film leaves the vacuum drying device 400 and before entering the evaporation device 700, and reduce the influence of the external environment on the dry film, a transition chamber 420 can be arranged between the vacuum drying device 400 and the evaporation device 700, and the vacuum drying device 400 and the transition chamber 420 are communicated through a pipeline. A transition chamber valve 421 is arranged on the pipeline. Because the vacuum chamber 410 of the vacuum drying device 400 can reach a certain vacuum degree through the vacuum device. At this time, only need to open the transition chamber valve 421, and the transition chamber 420 can achieve a certain vacuum degree.

[0052] According to an embodiment of the present invention, refer to Figure 1, evacuation ports are provided in the inlet section 510, deposition section 520, and outlet section 530; evacuation ports are provided in the feeding section 610, sublimation section 620, and discharging section 630, so as to keep the inlet section 510, deposition section 520, outlet section 530, feeding section 610, sublimation section 620, and discharging section 630 at a certain degree of vacuum. Specifically, referring to Figure 8 , the inlet section 510 is divided into a first inlet section 511 and a second inlet section 512, the outlet section 530 is divided into a first outlet section 531 and a second outlet section 532, the feeding section 610 is divided into a first feeding section 611 and a second feeding section 612, the discharging section 630 is divided into a first discharging section 631 and a second discharging section 632, and evacuation ports are respectively provided in the first inlet section 511, second inlet section 512, first outlet section 531, second outlet section 532, first feeding section 611, second feeding section 612, first discharging section 631, and second discharging section 632, so as to better maintain the vacuum degrees of the deposition section 520 and sublimation section 620. According to an embodiment of the present invention, the feeding section 610 and the discharging section 630 are respectively provided with opposed roller wheels arranged up and down, and a heating member 621 is provided below the tape in the sublimation section 620. Specifically, referring to Figure 8 , the first feeding section 611, second feeding section 612, first discharging section 631, and second discharging section 632 are respectively provided with opposed roller wheels 60 arranged up and down, and the tape 110 passes through between the opposed roller wheels 60. The degree of vacuum of each chamber is controlled by the pressing between the two roller wheels of the opposed roller wheels 60. Those skilled in the art can understand that in order to make the pressing between the two roller wheels closer, at least one of the roller wheels of the opposed roller wheels 60 can be set as an elastic roller wheel. It should be noted that since the opposed roller wheels 60 at both ends of the sublimation section 620 are greatly affected by the high temperature of the sublimation section 620, in order to avoid deformation of the elastic roller wheels, the opposed roller wheels 60 at both ends of the sublimation section 620 are made of a stainless steel high-temperature resistant material. In order to prevent the precursor in the sublimation section 620 from sublimating and depositing on the opposed roller wheels 60 at both ends of the sublimation section 620 or the precursor from reacting with the opposed roller wheels 60 at both ends of the sublimation section 620, a baffle 622 is installed on the side of the roller wheels. At the same time, in order to monitor the sublimation rate of the precursor in the sublimation section 620 in real time, a crystal oscillator e can be provided in the sublimation section 620, so that the sublimation temperature can be adjusted in a timely manner according to the sublimation rate of the precursor. In order to facilitate grasping and placing the substrate 10, the machine gripper 50 can be used to place the substrate 10 on the conveyor belt 540, or the machine gripper 50 can be used to take the deposited substrate 10 off the conveyor belt 540. Further, an XRF film layer monitoring device can be installed above the conveyor belt 540 in the area outside the outlet section 53 to monitor the process condition of the deposited substrate, so as to feedback to the process personnel to adjust the evaporation process.

[0053] Thus, the system utilizes the cyclic rotation of the tape to prepare a dry film of the precursor on the tape. The preparation process of the dry film can be completed under atmospheric conditions. Then, the dry film is transported into the vacuum sublimation deposition chamber without breaking the vacuum degree of the vacuum sublimation deposition chamber and sublimated and deposited on the substrate to prepare the perovskite film. Thus, the precursor raw material can be continuously transported into the vacuum sublimation deposition chamber to prepare the perovskite film, and the precursor raw material is easy to replace, can be added as needed, effectively avoiding material waste, and greatly improving the utilization rate and production efficiency of the equipment.

[0054] In another aspect of the present invention, the present invention provides a method for preparing a perovskite film using the above perovskite film preparation system with a tape-type continuous feeding function. According to an embodiment of the present invention, the above method includes:

[0055] S100: Using a spraying device to spray a precursor solution onto the tape entering the spraying area

[0056] In this step, the precursor is dissolved in an organic solvent to prepare a precursor solution, which is placed in a raw material tank. The spraying device is used to spray the precursor solution onto the tape entering the spraying area to form a wet film on the tape.

[0057] According to an embodiment of the present invention, the thickness of the above wet film is 1 - 1000 μm. The inventor found that if the thickness of the wet film is too thick, the wet film is not sufficiently air-dried, and the solvent residue affects the subsequent film formation. Secondly, the ripples formed during the air-drying process affect the subsequent dry film formation quality, resulting in uneven evaporation coating; if the thickness of the wet film is too thin, it cannot provide enough sublimation source to sublimate and deposit on the substrate. Thus, using the wet film with a thickness of 1 - 1000 μm in this application can improve the quality of the dry film and is beneficial to the sublimation deposition of the dry film on the substrate. It should be noted that the precursor solution is a conventional material in the art, and those skilled in the art can select the specific type of the precursor solution according to the actual situation. For example, the precursor solution includes PbI 2 , PbCl 2 , PbBr 2 , CsI, CsBr, CsCl, FAI, FABr, and FACl, at least one of them.

[0058] S200: Using a pre-air-drying device to pre-air-dry the wet film entering the pre-air-drying area

[0059] In this step, after the above wet film continues to run on the tape to the pre-air-drying area, the pre-air-drying device is used to pre-air-dry the wet film to obtain a pre-air-dried wet film.

[0060] According to an embodiment of the present invention, the thickness of the pre-dried wet film is 1 - 1000 μm. It should be noted that those skilled in the art can select the temperature, air pressure or time of the pre-drying process according to the thickness of the pre-dried wet film. For example, the temperature of pre-drying is 25 - 100 °C, the air pressure is 0.1 - 0.7 MPa, and the time is 1 - 300 s.

[0061] S300: Vacuum-dry the pre-dried wet film entering the vacuum drying area by using a vacuum drying device

[0062] In this step, after the above-mentioned pre-dried wet film runs with the tape to the vacuum drying area, the pre-dried wet film is vacuum-dried by using a vacuum drying device, and the organic solution in the wet film is completely evaporated to obtain a dry film.

[0063] According to an embodiment of the present invention, the thickness of the dry film is 0.1 - 100 μm. The inventor found that if the thickness of the dry film is too thick, the sublimation temperature needs to be increased, resulting in large energy consumption; if the dry film is too thin, it cannot provide enough sublimation source for sublimation deposition on the substrate. Therefore, by using the dry film with a thickness of 0.1 - 100 μm in this application, the energy consumption can be reduced, which is helpful for the sublimation deposition of the precursor. It should be noted that those skilled in the art can select the time, temperature or vacuum degree of vacuum drying according to the thickness of the dry film. For example, the time of vacuum drying is 1 - 300 s, the temperature is 25 - 100 °C, and the vacuum degree is 0.1 Pa - 1000 Pa.

[0064] S400: Heat and sublime the dry film on the substrate by using an evaporation and coating device

[0065] In this step, the tape sends the above-mentioned dry film to the sublimation area of the evaporation and coating device. The tape is heated by the heating element below the tape. The dry film on the tape is heated and sublimated in the sublimation area and then loaded on the substrate in the deposition area to form a perovskite film on the substrate. It should be noted that those skilled in the art can select the temperature, time or vacuum degree of the sublimation area according to the thickness of the above-mentioned dry film. For example, the temperature of the sublimation area is 50 - 300 °C, the sublimation time is 1 - 300 s, the vacuum degree is 0.1 Pa - 10 Pa, and the thickness of the formed perovskite film is 0.3 - 1 μm.

[0066] Therefore, by using the above system and this method, the precursor raw material can be continuously transported into the evaporation and coating device for sublimation deposition to prepare the perovskite film, which greatly improves the utilization rate of the equipment and the production efficiency of the perovskite film.

[0067] Next, the present invention will be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0068] Example 1

[0069] Reference Figure 2, put PbI in both raw material tanks of the spraying device 2 organic solution. Under the action of a set of spraying devices, spray the PbI 2 solution evenly on the stainless-steel coil tape to form a wet film with a thickness of 10 - 30 μm. Subsequently, through a pre-air drying device, control the air volume of pre-air drying to preliminarily dry the wet film and make the wet film more uniform. Among them, the temperature of pre-air drying is 30 °C, the air pressure is 0.1 MPa, and the time is 5 s. The thickness of the pre-air dried wet film obtained is 8 - 25 μm. Then, through a vacuum drying device (VCD), make the solvent fully volatilize through a rapid vacuum pumping / heating process, and the wet film completely becomes a dry film. Among them, the time of vacuum drying is 20 s, the temperature is 30 °C, and the vacuum degree is 1 Pa. The thickness of the obtained dry film is 5 - 20 μm. The dry film continues to be conveyed into the evaporation coating device. At the same time, the TCO glass (TCO glass) coated with the first carrier transport layer enters the evaporation coating device through a conveyor belt and is located directly above the stainless-steel coil tape of the dry film. The distance between the stainless-steel coil tape and the TCO glass is adjustable within the range of 1 - 10 cm. The heating component of the vacuum sublimation deposition chamber of the evaporation coating device makes the temperature of the dry film 70 °C, and the air pressure in the vacuum sublimation deposition chamber is maintained at 10 -1 Pa or so, and the sublimation time is 20S. At this time, the PbI of the dry film 2 vaporizes and deposits on the TCO glass substrate, making the PbI on the TCO glass substrate 2 film thickness is 0.3 μm. After reaching a sufficient thickness, the TCO glass is conveyed out of the evaporation coating device. The stainless-steel coil tape continues to be circulated and conveyed back to the spraying device for secondary spraying and recycled. The TCO glass coated with the PbI 2 film is then prepared with a FAI organic halide film by processes such as spin coating or slot coating or vacuum. FAI and PbI 2 chemically react to form a perovskite FAPbI 3 film, and then annealing is carried out to complete the perovskite crystallization process.

[0070] In Example 1, the efficiency of preparing perovskite films using the system of the present application can reach 120 pieces / h.

[0071] Example 2

[0072] Reference Figure 2 , put the organic solution of PbI 2 and the organic solution of CsI in the two raw material tanks of the spraying device respectively, or add a mixed solution of PbI 2 and CsI in one raw material tank. Under the action of the spraying device, make the PbI 2PbI₂ and CsI are sprayed onto the stainless-steel strip successively or simultaneously to form a wet film, and the thickness of the wet film is 300 - 500 μm. Subsequently, it passes through a pre-drying device, and the wet film is preliminarily dried by controlling the air volume of pre-drying. Among them, the temperature of pre-drying is 50 °C, the air pressure is 0.3 MPa, and the time is 20 s. The thickness of the pre-dried wet film obtained is 250 - 400 μm. Then it passes through a VCD device, and the solvent is fully volatilized through a rapid vacuum pumping / heating process, and the wet film is completely turned into a dry film. Among them, the time of vacuum drying is 50 s, the temperature is 50 °C, and the vacuum degree is 10 Pa. The thickness of the obtained dry film is 20 - 30 μm. The dry film continues to be conveyed into the evaporation coating device, and at the same time, the TCO glass enters the evaporation coating device through a conveyor belt and is located directly above the stainless-steel strip with the dry film. The distance between the stainless-steel strip and the TCO glass is adjustable within the range of 1 - 10 cm. The heating component in the vacuum sublimation deposition chamber of the evaporation coating device makes the temperature of the dry film 100 °C, and the air pressure in the vacuum sublimation deposition chamber is maintained at about 10 -1 Pa, and the sublimation time is 50 s. At this time, PbI₂ 2 and CsI are vaporized and deposited on the TCO glass substrate, so that the thickness of the PbI₂ 2 and CsI mixed film on the TCO glass substrate is 0.5 μm. After reaching the sufficient thickness, the TCO glass is conveyed out of the evaporation coating device, and the stainless-steel strip is circulated and conveyed back to the spraying device for secondary spraying and recycled. The TCO glass coated with the PbI₂ 2 film is further processed by processes such as scraping coating, slit coating, or vacuum to prepare the FAI organic halide film. FAI chemically reacts with PbI₂ 2 and CsI to form the perovskite CsFAPbI₃ 3 film, and then annealing is carried out to complete the perovskite crystallization process.

[0073] In Example 2, the efficiency of preparing the perovskite film using the system of the present application can reach 120 pieces / h.

[0074] Example 3

[0075] Reference Figure 1 , according to the method of Example 1 or Example 2, the TCO glass coated with PbI₂ 2 or PbI₃ 2The TCO glass with the mixed film of CsI is transported into the evaporation device. Meanwhile, the organic solution of FAI is placed in two raw material boxes. Under the action of the spraying equipment, the FAI solution is evenly sprayed on the stainless-steel coil belt to form a wet film with a thickness of 800 - 1000 μm. Subsequently, it passes through the pre-air drying device, and the wet film is preliminarily dried by controlling the air volume of pre-air drying. Among them, the temperature of pre-air drying is 70 °C, the wind pressure is 0.7 MPa, and the time is 100 s. The thickness of the pre-air dried wet film obtained is 750 - 920 μm. Then, through the VCD process, the solvent is fully volatilized by the rapid vacuum pumping / heating process, and the wet film is completely turned into a dry film. Among them, the time of vacuum drying is 100 s, the temperature is 60 °C, and the vacuum degree is 500 Pa. The thickness of the dry film obtained is 61 - 80 μm. The dry film continues to be transported into the evaporation device. Meanwhile, the TCO glass coated with PbI 2 or PbI 2 The TCO glass with the mixed film of CsI enters the evaporation device through the conveyor belt and is located directly above the dry film stainless-steel coil belt. The distance between the stainless-steel coil belt and the TCO glass is adjustable within the range of 1 - 10 cm. The heating component in the vacuum sublimation deposition chamber keeps the temperature of the dry film at 150 °C, and the air pressure in the vacuum sublimation deposition chamber is maintained at 10 -1 Pa or so, and the sublimation time is 100 S. At this time, the FAI in the dry film is vaporized and deposited on the PbI 2 or PbI 2 mixed film with CsI to form a FAPbI 3 or CsFAPbI 3 film with a thickness of 1 μm. After reaching a sufficient thickness, the TCO glass is transported out of the evaporation device, and the stainless-steel coil belt is circulated and transported back to the spraying device for secondary spraying and recycled.

[0076] In Example 3, the efficiency of preparing the perovskite film using the system of the present application can reach 120 pieces / h.

[0077] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0078] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A perovskite film preparation system with a function of continuous feeding of a roll tape, characterized in that, it includes: A roll tape device, the roll tape device includes a roller and a roll tape, the roller rotates to drive the roll tape to rotate in a cycle, along the rotation direction of the roll tape, a spraying area, a pre-air drying area, a vacuum drying area and an evaporation coating area are sequentially defined on the roll tape; A spraying device, the spraying device is arranged in the spraying area and is used to spray a precursor solution onto the roll tape entering the spraying area to form a wet film; A pre-air drying device, the pre-air drying device is arranged in the pre-air drying area and is used to pre-air dry the wet film entering the pre-air drying area; A vacuum drying device, the vacuum drying device is arranged in the vacuum drying area and is used to dry the pre-air dried wet film entering the vacuum drying area into a dry film; An evaporation coating device, the evaporation coating device is arranged in the evaporation coating area, and the evaporation coating device includes: A transfer chamber, a conveyor belt is arranged in the transfer chamber, a substrate is placed on the conveyor belt, along the conveying direction of the conveyor belt, the transfer chamber sequentially includes a feeding area, a deposition area and a discharging area; A vacuum sublimation deposition chamber, the vacuum sublimation deposition chamber is communicated with the vacuum drying device, along the rotation direction of the roll tape, the vacuum sublimation deposition chamber sequentially includes a feeding area, a sublimation area and a discharging area, the sublimation area is located below and communicated with the deposition area, the roll tape sends the dry film to the sublimation area, and the dry film sublimates in the sublimation area and is loaded on the substrate in the deposition area, The feeding area, the deposition area and the discharging area are provided with vacuum extraction ports; The feeding area, the sublimation area and the discharging area are provided with vacuum extraction ports; The feeding area and the discharging area are respectively provided with counter-rotating rollers arranged up and down, a heating element is arranged below the roll tape in the sublimation area, and the roll tape passes through between the two rollers of the counter-rotating rollers, and the vacuum degree of each chamber is controlled by the pressing between the two rollers of the counter-rotating rollers.

2. The system according to claim 1, characterized in that, The spraying device includes a raw material tank, a cleaning tank and a spray head. A raw material tank one-way valve and a spray head valve are sequentially arranged on the pipeline connecting the raw material tank and the spray head. The outlet of the cleaning tank is communicated with the pipeline between the raw material tank one-way valve and the spray head valve, and a cleaning tank valve is arranged at the outlet of the cleaning tank. The spray head is located directly above the roll tape.

3. The system according to claim 1 or 2, characterized in that, The pre-air drying device includes a blower and a blower cover. The blower is arranged in the blower cover. An air inlet is arranged at the upper end of the blower cover, and an air outlet is arranged at the lower end of the blower cover. The air outlet is located directly above the roll tape.

4. The system according to claim 3, characterized in that, A protective cover is arranged outside the spraying device and the pre-air drying device, and a process gas outlet is arranged above the protective cover.

5. The system according to claim 1, characterized in that, The vacuum drying device includes a vacuum chamber, one end of the vacuum chamber is provided with a tape inlet, the other end of the vacuum chamber is provided with a tape outlet, the tape inlet and the tape outlet are respectively provided with opposing roller wheels arranged up and down, the tape sequentially passes through the opposing roller wheels at the tape inlet and the tape outlet, and a heating component and a vacuum port are provided in the vacuum chamber.

6. The system according to claim 5, wherein, a rectifying plate is arranged in the vacuum chamber along the rotation direction of the tape, the rectifying plate has holes distributed in an array, and the distance between the rectifying plate and the bottom of the vacuum chamber is adjustable.

7. The system according to claim 1, wherein, a deviation correction system is provided on the tape.

8. The system according to claim 1, wherein, a brush and a collection box are provided at the lower end of the tape device.

9. A method for preparing a perovskite film using the perovskite film preparation system with a tape-type continuous feeding function according to any one of claims 1-8, wherein, it includes: (1) Using a spraying device to spray a precursor solution onto the tape entering the spraying area so as to form a wet film on the tape; (2) Using a pre-air drying device to pre-air dry the wet film entering the pre-air drying area so as to obtain a pre-air dried wet film; (3) Using a vacuum drying device to vacuum dry the pre-air dried wet film entering the vacuum drying area so as to obtain a dry film; (4) The tape sends the dry film to the sublimation area of the evaporation device, and the dry film sublimates in the sublimation area and is loaded on the substrate in the deposition area so as to obtain a perovskite film.

10. The method according to claim 9, wherein, In step (1), the precursor solution includes PbI 2 , PbCl 2 , PbBr 2 , at least one of CsI, CsBr, CsCl, FAI, FABr, and FACl, and the thickness of the wet film is 1-1000 μm.

11. The method according to claim 9, wherein, In step (2), the temperature of the pre-air drying is 25-100 °C, the wind pressure is 0.1-0.7 MPa, the time is 1-300 s, and the thickness of the pre-air dried wet film is 1-1000 μm.

12. The method according to claim 9, wherein, In step (3), the time of the vacuum drying is 1-300 s, the temperature is 25-100 °C, the vacuum degree is 0.1 Pa-1000 Pa, and the thickness of the dry film is 0.1-100 μm.

13. The method according to claim 9, wherein, In step (4), the temperature of the sublimation area is 50-300 °C, the sublimation time is 1-300 s, the vacuum degree is 0.1 Pa-10 Pa, and the thickness of the perovskite film is 0.3-1 μm.

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