Perovskite film layer preparation system and method with continuous feeding function

Abstract

The present invention discloses a perovskite film layer preparation system and method with a continuous feeding function. The system includes: a transmission device, a substrate holder device, a spraying device, a pre-air drying device, a vacuum drying device, and an evaporation device. The substrate holder device moves driven by the transmission device. The substrate holder device has an installation cavity. The upper side of the installation cavity has a first opening, and the lower side of the installation cavity has a second opening. A spraying plate is installed at the second opening, and the spraying plate covers the second opening. A substrate is placed at the first opening, and the substrate covers the first opening. The substrate is located directly above the spraying plate. The spraying device sprays a precursor solution onto the spraying plate to form a wet film. The pre-air drying device pre-air dries the wet film. The vacuum drying device dries the pre-air dried wet film into a dry film. The evaporation device heats and sublimes the dry film on the spraying plate and then deposits it on the lower surface of the substrate. The process of preparing the perovskite film layer by this system does not require breaking the vacuum, and the raw materials are added as needed.

Description

Technical Field

[0001] The present invention belongs to the field of perovskite solar cells, and particularly relates to a perovskite film layer preparation system and method with a 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. A perovskite solar cell generally includes: a front electrode, which is a transparent conductive glass or a flexible transparent conductive film; a first carrier transport layer, which is a P-type or N-type semiconductor material, and is a metal oxide or an organic semiconductor material; a perovskite light absorption layer ABX 3 material, where A is a monovalent group or ion such as methylammonium MA, formamidinium FA, cesium Cs, etc., B is a divalent element such as lead Pb, tin Sn, etc. or two monovalent element ions, and X is a halogen element or other monovalent negative group; a second carrier transport layer, which is an N-type or P-type semiconductor material, and is a metal oxide or an organic semiconductor material; a back electrode, which can be a metal material, graphite or a conductive oxide. When preparing a perovskite layer on a large scale, it is difficult for the solution method to achieve complete coverage on a rough or defective substrate, so it is not suitable for preparing a uniform film layer on a textured substrate and an uneven substrate. The two-step method can first deposit a perovskite precursor film layer on substrates with different roughnesses or morphologies by a vacuum method, and then use a solution method or a vacuum method for preparation to finally form a perovskite layer.

[0003] Currently, the existing technologies of the vacuum method include thermal evaporation, sputtering, close-spaced sublimation (CSS), vapor transport deposition (VTD), close-spaced vapor transport (CSVT), etc. However, no matter which method is used, it cannot meet continuous feeding. The materials are all filled inside the vacuum chamber. When the raw materials reach the replacement cycle, it is necessary to break the vacuum before filling the materials. 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

[0004] The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present invention is to provide a perovskite film layer preparation system and method with a continuous feeding function. The system can spray a precursor solution onto a spraying plate of a substrate holder device in the atmosphere to form a wet film, and then the spraying plate is sequentially subjected to pre-air drying and vacuum drying treatments to form a dry film. Then, the substrate is placed at the first opening of the substrate holder device and covers the first opening. Finally, through an evaporation device, the dry film is heated and sublimated and deposited on the substrate to obtain a perovskite film layer. The whole process does not require breaking the vacuum, and the raw materials are added as needed, effectively avoiding material waste and improving the utilization rate of the equipment. In particular, the material atmosphere during the sublimation of the dry film is within the installation cavity defined by the substrate holder device, avoiding or reducing the escape of the dry film sublimation material atmosphere into the chamber of the evaporation device and extending the service life of the evaporation device.

[0005] In one aspect of the present invention, there is provided a perovskite film layer preparation system with a continuous feeding function.

[0006] The system includes:

[0007] A substrate holder device, which is driven by a transmission device to move. The substrate holder device has an installation cavity. The upper side of the installation cavity has a first opening, and the lower side has a second opening. A spraying plate is installed at the second opening, and the spraying plate covers the second opening. A substrate is placed at the first opening, and the substrate covers the first opening. The substrate is located directly above the spraying plate;

[0008] A spraying device, which sprays a precursor solution onto the spraying plate to form a wet film;

[0009] A pre-air drying device, which pre-air dries the wet film;

[0010] A vacuum drying device, which dries the pre-air dried wet film into a dry film;

[0011] An evaporation device, which heats and sublimates the dry film on the spraying plate and then deposits it on the lower surface of the substrate;

[0012] A transmission device, which drives the substrate holder device to sequentially pass through the spraying device, the pre-air drying device, the vacuum drying device, and the evaporation device.

[0013] The perovskite film layer preparation system with a continuous feeding function according to the above embodiments of the present invention includes a transmission device, a substrate holder device, a spraying device, a pre-air drying device, a vacuum drying device, and an evaporation device. The transmission device drives the substrate holder device to sequentially pass through the spraying device, the pre-air drying device, the vacuum drying device, and the evaporation device. Specifically, the substrate holder device has an installation cavity. There is a first opening on the upper side of the installation cavity and a second opening on the lower side of the installation cavity. A spraying plate is installed at the second opening, and the spraying plate covers the second opening. The substrate holder device moves under the drive of the transmission device. When the substrate holder device moves to the spraying device, the spraying device sprays the precursor solution onto the above-mentioned spraying plate to form a wet film. The substrate holder device continues to move to the pre-air drying device under the drive of the transmission device, and the pre-air drying device pre-air dries the above-mentioned wet film to volatilize most of the solvent. The substrate holder device moves into the vacuum drying device under the drive of the transmission device, and the vacuum drying device dries the pre-air dried wet film into a dry film. Then, the substrate is placed at the first opening of the substrate holder device, and the substrate covers the first opening. The substrate is located directly above the spraying plate. Finally, the substrate holder device carrying the substrate is moved into the evaporation device under the drive of the transmission device, and the evaporation device heats and sublimates the dry film on the spraying plate and then deposits it on the lower surface of the substrate. This system can spray the precursor solution onto the spraying plate of the substrate holder device in the atmosphere to form a wet film, and then the spraying plate undergoes pre-air drying and vacuum drying treatments in sequence to form a dry film. Then, the substrate is placed at the first opening of the substrate holder device and covers the first opening. Finally, through the evaporation device, the dry film is heated and sublimated and deposited on the substrate to obtain a perovskite film layer. The whole process does not require breaking the vacuum, and the raw materials are added as needed, effectively avoiding material waste and improving the utilization rate of the equipment. In particular, the material atmosphere of the sublimated dry film is within the installation cavity defined by the substrate holder device, avoiding or reducing the escape of the dry film sublimation material atmosphere into the chamber of the evaporation device and extending the service life of the evaporation device.

[0014] In addition, the perovskite film layer preparation system with a continuous feeding function according to the above embodiments of the present invention may further have the following technical features:

[0015] In some embodiments of the present invention, the substrate holder device includes a lower substrate holder, a surrounding plate, and an upper substrate holder. The upper substrate holder is located directly above the lower substrate holder. The surrounding plate circumferentially surrounds the lower substrate holder and the upper substrate holder. The upper substrate holder, the lower substrate holder, and the surrounding plate define the installation cavity. The spraying plate is placed on the lower substrate holder, and the substrate is placed on the upper substrate holder.

[0016] In some embodiments of the present invention, the substrate holder device further includes a shock-absorbing shrapnel, an adjusting screw, and a pin. The shock-absorbing shrapnel is placed between the spraying plate and the side wall of the lower substrate holder. The adjusting screw is located between the lower substrate holder and the upper substrate holder. The pin is located on the upper substrate holder and is used to fix the substrate. Thus, the spraying plate and the substrate can be fixed, and the distance between the spraying plate and the substrate can be adjusted.

[0017] In some embodiments of the present invention, the spraying device includes a raw material tank, a cleaning tank, a spray head, and a spraying track. A raw material tank one-way valve and a spray head valve are sequentially provided on the pipeline connecting the raw material tank and the spray head. The outlet of the cleaning tank is connected to the pipeline between the raw material tank one-way valve and the spray head valve. A cleaning tank valve is provided at the outlet of the cleaning tank. The spray head is placed in the middle of the two spraying tracks. When the substrate holder device moves below the spraying track, the spray head starts to move along the spraying track to spray on the spraying plate. Thus, the spraying of the precursor solution and the cleaning and maintenance of the spraying device can be realized.

[0018] In some embodiments of the present invention, the vacuum drying device includes a vacuum chamber, a vacuum pump, and an inflation valve. A vacuum valve is provided on the pipeline connecting the vacuum chamber and the vacuum pump. The inflation valve is provided on the vacuum chamber. Thus, the wet film can be dried into a dry film better.

[0019] In some embodiments of the present invention, the evaporation coating device includes: a wafer loading chamber, an evaporation coating chamber, and a wafer unloading chamber. The wafer loading chamber is connected with a vacuum pump; the evaporation coating chamber communicates with the wafer loading chamber. A heating device is provided at the lower part of the evaporation coating chamber. The heating device is located directly below the spraying plate. A cold trap is provided at the upper part of the evaporation coating chamber. The cold trap is located directly above the substrate, which can accelerate the speed of material deposition on the substrate; the evaporation coating chamber is connected with a vacuum pump; the wafer unloading chamber communicates with the evaporation coating chamber. The wafer unloading chamber is connected with a vacuum pump. Thus, the dry film can be heated and sublimated and deposited on the substrate.

[0020] In some embodiments of the present invention, it further includes a loading device and an unloading device. After the substrate holder device passes through the vacuum drying device, the loading device places the substrate on the substrate holder device, and the unloading device takes the deposited substrate off the substrate holder device. Thus, the substrate can be efficiently placed on or taken off the substrate holder device.

[0021] In some embodiments of the present invention, it further includes an XRF film layer monitoring device. Thus, the process conditions of the deposited substrate can be effectively monitored.

[0022] In some embodiments of the present invention, a susceptor buffer device is further included. The susceptor buffer device can buffer the susceptor device after being dried by the vacuum drying device or the susceptor device before spraying. Thus, the continuous operation of the entire system can be ensured.

[0023] In another aspect of this aspect, the present invention provides a method for preparing a perovskite film layer by using the above perovskite film layer preparation system with a 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 a spraying plate to form a wet film on the spraying plate;

[0025] (2) Using a pre-air drying device to pre-air dry the wet film to obtain a pre-air dried wet film;

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

[0027] (4) Placing a substrate on a susceptor device with a dry film so that the substrate is directly above the dry film;

[0028] (5) Transmitting the susceptor device obtained in (4) to an evaporation device, and the dry film is heated and sublimated and deposited on the lower surface of the substrate to obtain a perovskite film layer.

[0029] Thus, by using the above system and this method, the material can be transported to the evaporation device and deposited on the substrate at any time without breaking the vacuum to prepare a perovskite film layer, effectively avoiding material waste, improving the utilization rate of the equipment, and extending the service life of the equipment.

[0030] The additional aspects and advantages of the present invention will be partially given in the following description, partially become obvious from the following description, or be understood through the practice of the present invention. Description of the Drawings

[0031] The above and / or additional aspects and advantages of the present invention will become obvious and easy to understand from the description of the embodiments in conjunction with the following drawings, where:

[0032] Figure 1 is the structural framework diagram of the perovskite film layer preparation system with a continuous feeding function according to an embodiment of the present invention;

[0033] Figure 2 is the structural diagram of the susceptor device according to an embodiment of the present invention;

[0034] Figure 3 is the three-dimensional structural diagram of the susceptor device according to an embodiment of the present invention;

[0035] Figure 4 It is a cross-sectional view of the substrate holder device according to an embodiment of the present invention;

[0036] Figure 5 It is a cross-sectional view of the substrate holder device according to an embodiment of the present invention;

[0037] Figure 6 It is an exploded view of the substrate holder device according to an embodiment of the present invention;

[0038] Figure 7 It is a structural diagram of the spraying device according to an embodiment of the present invention;

[0039] Figure 8 It is a structural diagram of the pre-air drying device and the vacuum drying device according to an embodiment of the present invention;

[0040] Figure 9 It is a structural diagram of the evaporation device according to an embodiment of the present invention;

[0041] Figure 10 It is a partial structural diagram of the evaporation device according to an embodiment of the present invention. Detailed implementation manners

[0042] The embodiments of the present invention will be described in detail below, which are intended to explain the present invention and should not be construed as a limitation to the present invention.

[0043] In one aspect of the present invention, the present invention provides a perovskite film layer preparation system with a continuous feeding function. Refer to Figure 1 , the system includes: a transmission device 100, a substrate holder device 200, a spraying device 300, a pre-air drying device 400, a vacuum drying device 500, and an evaporation device 600. The transmission device 100 drives the substrate holder device 200 to sequentially pass through the spraying device 300, the pre-air drying device 400, the vacuum drying device 500, and the evaporation device 600.

[0044] According to an embodiment of the present invention, refer to Figure 1 and Figure 2 , the substrate holder device 200 moves driven by the transmission device 100. The substrate holder device 200 has an installation cavity 201. The upper side of the installation cavity 201 has a first opening, and the lower side of the installation cavity 201 has a second opening. A spraying plate is installed at the second opening, and the spraying plate covers the second opening. A substrate is placed at the first opening, and the substrate covers the first opening. The substrate is located directly above the spraying plate. Those skilled in the art can understand that for the specific three-dimensional shape of the substrate holder device 200, those skilled in the art can select according to the actual situation as long as the substrate holder device 200 has an installation cavity, and the spraying plate and the substrate satisfy the above-mentioned conditions of being respectively located at the lower and upper parts of the installation cavity 201, and the substrate is located directly above the spraying plate.

[0045] According to an embodiment of the present invention, refer toFigure 3 , Figure 4 , Figure 5 and Figure 6 , the susceptor device 200 includes a lower susceptor 203, a shroud 205, and an upper susceptor 204. The upper susceptor 204 is located directly above the lower susceptor 203. The shroud 205 circumferentially surrounds the lower susceptor 203 and the upper susceptor 204. The upper susceptor 204, the lower susceptor 203, and the shroud 205 define an installation cavity 201. The spraying plate 202 is placed on the lower susceptor 203, and the substrate 209 is placed on the upper susceptor 204. When the susceptor device 200 is moved to the spraying device driven by the transmission device 100, the spraying device sprays the precursor solution onto the spraying plate 202 to form a wet film. Those skilled in the art can understand that when the spraying device sprays the spraying plate 202, the substrate 209 is not placed on the susceptor device 200, and for the specific material of the spraying plate, those skilled in the art can select according to the actual situation. For example, in this application, a high-purity ultra-thin graphite plate is selected because the high-purity ultra-thin graphite plate has strong chemical stability, corrosion resistance, and low permeability, has good thermal conductivity and heat resistance, can well carry the sprayed solution, and can quickly heat up to evaporate and sublime the dry film onto the substrate.

[0046] According to an embodiment of the present invention, referring to Figure 3 , Figure 4 , Figure 5 and Figure 6 , the susceptor device 200 further includes a shock-absorbing elastic piece 207, an adjusting screw 206, and a pin 208. The shock-absorbing elastic piece 207 is placed between the spraying plate 202 and the side wall of the lower susceptor 203. The adjusting screw 206 is located between the lower susceptor 203 and the upper susceptor 204. The pin 208 is located on the upper susceptor 204 and is used to fix the substrate 209. Among them, the shock-absorbing elastic piece 207 is responsible for fixing and protecting the spraying plate 202, preventing the spraying plate 202 from vibrating and shifting during transmission. At the same time, because it is an elastic mechanism, when the spraying plate 202 expands due to heat, it ensures that the spraying plate 202 is not damaged, and when it expands and contracts due to the alternation of heat and cold, it always ensures that the spraying plate 202 is in the middle position. The adjusting screw 206 can adjust the distance between the lower susceptor 203 and the upper susceptor 204 to keep a proper distance between the spraying plate 202 and the substrate 209. The pin 208 can fix the substrate 209 to prevent the substrate 209 from moving.

[0047] According to an embodiment of the present invention, referring to Figure 7, the spraying device 300 includes a raw material tank 301, a cleaning tank 302, a spray head 303, and a spraying track 304. A raw material tank one-way valve 305 and a spray head valve 306 are sequentially provided on the pipeline connecting the raw material tank 301 and the spray head 303. The outlet of the cleaning tank 302 is connected to the pipeline between the raw material tank one-way valve 305 and the spray head valve 306. A cleaning tank valve 307 is provided at the outlet of the cleaning tank 302. The spray head 303 is placed in the middle of the two spraying tracks 304. When the substrate holder device 200 moves below the spraying track 304, the spray head 303 starts to move along the spraying track 304 towards the spraying plate 202 for spraying. When the spray head valve 306 is opened, the precursor solution in the raw material tank 301 is sprayed on the spraying plate 202 through the spray head 303. A raw material tank one-way valve 305 is provided at the outlet of the raw material tank 301. When it is necessary to clean the spraying pipeline, the cleaning tank valve 307 at the outlet of the cleaning tank 302 is opened, and the cleaning liquid in the cleaning tank 302 flows through the pipeline and the spray head 303, thereby achieving the purpose of cleaning. Further, an exhaust gas treatment device 308 can be added in the spraying area of the spray head 303 to reduce the diffusion of organic substances in the precursor solution to the external environment. It should be noted that for the specific spraying method and the number of the raw material tank 301, the cleaning tank 302, and the spray head 303 of the spraying device 300, they 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 air mixing spraying. Preferably, medium-pressure air mixing spraying is used. It 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 spraying plate to form a dense coating. This spraying method has high material utilization rate and high working efficiency. A certain amount of air is mixed into the material to optimize 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 8 , the pre-air drying device 400 includes a blower 401 and a blower cover 402. The blower 401 is arranged inside the blower cover 402. When the sprayed substrate holder device enters the pre-air drying device 400, the blower 401 starts, and the blown air pre-air dries the wet film on the spraying plate. It should be noted that a heater and an exhaust gas processor can be installed in the pre-air drying device 400 to assist in better pre-air drying of the wet film and play a role in protecting the environment.

[0049] According to an embodiment of the present invention, refer to Figure 8, the vacuum drying device 500 includes a vacuum chamber 501, a vacuum pump 502 and an inflation valve 503. A vacuum valve 504 is provided on the pipeline connecting the vacuum chamber 501 and the vacuum pump 502, and the inflation valve 503 is provided on the vacuum chamber 501. When the substrate holder device moves into the vacuum drying device 500 driven by the transmission device, the vacuum valve 504 is opened, and the vacuum pump 502 starts to evacuate the air to make the vacuum chamber 501 reach an appropriate vacuum degree. Then, the heating component (not shown) is turned on. In an environment with a certain vacuum degree, the wet film on the spraying plate is dried into a dry film relatively quickly. The inflation valve 503 can adjust the vacuum degree of the vacuum chamber 501. Those skilled in the art can understand that for the temperature and vacuum degree of the vacuum chamber 501 and the number of vacuum pumps 502, those skilled in the art can make selections according to the actual situation.

[0050] According to an embodiment of the present invention, referring to Figure 1 , Figure 9 and Figure 10, the evaporation coating device 600 includes: a wafer loading chamber 601, an evaporation coating chamber 602, and a wafer unloading chamber 603. A vacuum pump 604 is connected to the wafer loading chamber 601; the evaporation coating chamber 602 communicates with the wafer loading chamber 601. A heating device 605 is provided at the lower part of the evaporation coating chamber 602, and the heating device 605 is located directly below the spraying plate 202. A cold trap 606 is provided at the upper part of the evaporation coating chamber 602, and the cold trap 606 is located directly above the substrate 209. The evaporation coating chamber 602 is connected to a vacuum pump 607; the wafer unloading chamber 603 communicates with the evaporation coating chamber 602, and the wafer unloading chamber 603 is connected to a vacuum pump 608. The vacuum drying device 500 dries the wet film after pre-air drying into a dry film, and then places the substrate at the first opening of the substrate holder device 200, and the substrate covers the first opening. The substrate is located directly above the spraying plate. Finally, the substrate holder device carrying the substrate is moved into the evaporation coating device 600 driven by the transmission device. The evaporation coating device 600 heats and sublimes the dry film on the spraying plate 202, and then deposits it on the lower surface of the substrate 209. Specifically, the wafer loading chamber 601 is evacuated by the vacuum pump 604 to have a certain degree of vacuum. The substrate holder device 200 first enters the wafer loading chamber 601, and then the evaporation coating chamber 602 is evacuated by the vacuum pump 607 to make the evaporation coating chamber 602 have an appropriate degree of vacuum. The valve between the wafer loading chamber 601 and the evaporation coating chamber 602 is opened, and the substrate holder device 200 enters the evaporation coating chamber 602. A heating device 605 is provided at the lower part of the evaporation coating chamber 602, and the heating device 605 is located directly below the spraying plate 202. The heating device 605 heats the spraying plate 202 to sublime the dry film on the spraying plate 202, and then deposits it on the lower surface of the substrate 209. A cold trap 606 is provided directly above the substrate 209, which can make the precursor material deposit on the substrate 209 faster. The wafer unloading chamber 603 is evacuated by the vacuum pump 608 to have a certain degree of vacuum, and then the deposited substrate enters the wafer unloading chamber 603 and finally exits the evaporation coating device 600 through the wafer unloading chamber 603.

[0051] It should be noted that those skilled in the art can select the degree of vacuum of the wafer loading chamber 601, the evaporation coating chamber 602, and the wafer unloading chamber 603 of the evaporation coating device 600 and the number of vacuum pumps according to the actual situation. Further, refer to Figure 9, the film feeding chamber 601 includes an LL chamber 6011, a BF1 chamber 6012 and a TM1 chamber 6013, and the film discharging chamber 603 includes a TM2 chamber 6031, a BF2 chamber 6032 and a UL chamber 6033; the LL chamber 6011 and the UL chamber 6033 mainly function to isolate the atmosphere. The LL chamber 6011 balances the vacuum degrees of the LL chamber 6011 and the BF1 chamber 6012, and the UL chamber 6033 balances the vacuum degrees of the UL chamber 6033 and the BF2 chamber 6032. The BF1 chamber 6012 buffers the pressure between the LL chamber 6011 and the TM1 chamber 6013, and the BF2 chamber 6032 buffers the pressure between the TM2 chamber 6031 and the UL chamber 6033. Preferably, baffles are provided at the chamber wall, transmission, air extraction position, etc. of the evaporation chamber 602, which can effectively block the diffusion of the evaporation material, reduce the damage to the main body of the equipment, and extend the service life of the equipment.

[0052] Thus, the system can spray the precursor solution onto the spraying plate of the substrate holder device under the atmosphere to form a wet film, and then the spraying plate is successively subjected to pre-air drying and vacuum drying treatments to form a dry film. Then, the substrate is placed at the first opening of the substrate holder device and covers the first opening. Finally, through the evaporation device, the dry film is heated and sublimated and deposited on the substrate to obtain a perovskite film layer. The whole process does not require breaking the vacuum, and the raw materials are added as needed, effectively avoiding the waste of materials and improving the utilization rate of the equipment. In particular, the material atmosphere sublimated from the dry film is within the installation cavity defined by the substrate holder device, avoiding or reducing the escape of the dry film sublimated material atmosphere into the chamber of the evaporation device and extending the service life of the evaporation device. Those skilled in the art can understand that after the substrate completes the evaporation deposition and enters the next process, the substrate holder device with the spraying plate continues to cycle under the drive of the transmission device, that is, it enters the spraying device, pre-air drying device, vacuum drying device and evaporation device in turn for cyclic operation.

[0053] According to an embodiment of the present invention, referring to Figure 1 , the system further includes a loading device 701 and an unloading device 702. After the substrate holder device 200 passes through the vacuum drying device 500 and before entering the evaporation device 600, the loading device 701 places the substrate on the substrate holder device 200, and then enters the evaporation device 600 for sublimation deposition. The unloading device 702 removes the substrate deposited by the evaporation device 600 from the substrate holder device 200. Thus, the substrate can be efficiently placed on or removed from the substrate holder device. Further, it also includes an XRF film layer monitoring device 800, which can effectively monitor the process conditions of the deposited substrate. For example, the nozzle of the spraying device 300 can adjust the capacity of the spraying liquid, and the spraying amount can be controlled in a closed loop according to the information fed back by the XRF film layer monitoring device 800, or manual intervention can be performed to achieve manual setting of the spraying amount.

[0054] According to an embodiment of the present invention, referring toFigure 1 The system further includes a susceptor buffer device 900, which can buffer the susceptor device 200 dried by the vacuum drying device 500 or the susceptor device 200 before spraying. Thus, the continuous operation of the entire system can be ensured. For example, the susceptor buffer device 900 has a vertical lifting function. If the evaporation device 600 has not completed the operation while the vacuum drying device 500 has completed the drying of the wet film into a dry film, at this time, the susceptor device 200 with the dry film is buffered by the susceptor buffer device 900 and does not enter the evaporation device. This process can continuously buffer the susceptor device 200 with the dry film until the process of the evaporation device 600 is completed, and the new susceptor device 200 with the dry film is removed from the susceptor buffer device 900 and then enters the evaporation device 600. It should be noted that for the installation position of the susceptor buffer device 900, those skilled in the art can determine it according to the specific circuit operation process. For example, it can also be installed in front of the spraying device 300.

[0055] In another aspect of this aspect, the present invention provides a method for preparing a perovskite film layer by using the above perovskite film layer preparation system with a continuous feeding function. According to an embodiment of the present invention, the method includes:

[0056] S100: Spraying a precursor solution onto a spraying plate by using a spraying device

[0057] In this step, first, a precursor solution is prepared. The spraying plate is placed in the susceptor buffer device and moves to the spraying device under the drive of the transmission device. The spraying plate is located under the nozzle of the spraying device, and then spraying is carried out to form a wet film with a certain thickness on the spraying plate. 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, and at the same time, those skilled in the art can select the spraying time, pressure, rate, etc. according to the actual situation to obtain a wet film with a suitable thickness.

[0058] S200: Pre-air drying the wet film by using a pre-air drying device

[0059] In this step, the wet film prepared in step (1) is transported to the pre-air drying device to pre-air dry the wet film to obtain a pre-air dried wet film. It should be noted that those skilled in the art can select the pre-air drying temperature and time according to the actual situation.

[0060] S300: Vacuum drying the pre-air dried wet film by using a vacuum drying device

[0061] In this step, the pre-air-dried wet film prepared in step (2) is transferred to a vacuum drying device, and then vacuum-heated and dried to completely volatilize the solvent in the wet film, obtaining a dry film. Those skilled in the art can select the vacuum degree, heating temperature, and time for vacuum drying according to the actual situation.

[0062] S400: Place the substrate on the substrate holder device with the dry film

[0063] In this step, place the substrate on the substrate holder device with the dry film obtained in step (3) so that the substrate is directly above the dry film. It should be noted that for the distance between the substrate and the dry film and the placement method of the substrate, those skilled in the art can make selections according to the actual situation. For example, a manipulator or manual labor can be used to place the substrate on the substrate holder device.

[0064] S500: Transfer the substrate holder device obtained in S400 to an evaporation device for heating sublimation deposition

[0065] In this step, transfer the substrate holder device obtained in S400 to an evaporation device for heating sublimation deposition. After the dry film precursor material is heated and sublimated, it is deposited on the lower surface of the substrate directly above the dry film, thereby obtaining a perovskite film layer. It should be noted that for the heating temperature, time, and thickness of the dry film, those skilled in the art can make selections according to the actual situation.

[0066] Thus, by using the above system and this method, the material can be transported to the evaporation device and deposited on the substrate at any time without breaking the vacuum, preparing a perovskite film layer, effectively avoiding material waste, improving the utilization rate of the equipment, and extending the service life of the equipment.

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

[0068] Example 1

[0069] Refer to Figure 1 , and put the organic solution of PbI 2 in both raw material tanks, and under the action of a set of spraying devices, spray PbI 2The solution is evenly sprayed on the graphite substrate of the substrate holder device, and then transferred to the pre-air drying device. The wet film is preliminarily dried by controlling the change of pre-air drying air volume and temperature to make the wet film more uniform. Then it passes through the vacuum drying device, and the solvent in the pre-air dried wet film is fully volatilized by rapid vacuum pumping, and the wet film is completely turned into a dry film. The temperature of the vacuum drying is controlled at 50 - 100 °C. Then the TCO glass with the first carrier transport layer (hereinafter referred to as TCO glass or chip) is placed on the substrate holder device, directly above the dry film graphite substrate. The substrate holder device is continuously transferred into the evaporation device. The distance between the dry film graphite substrate and the TCO glass is adjustable within the range of 1 - 10 cm. The heating system in the evaporation device makes the temperature of the dry film at 100 - 300 °C, and the air pressure in the evaporation device is maintained at 10 -1 Pa or so. At this time, the PbI 2 in the dry film is vaporized and deposited on the TCO glass substrate, so that the thickness of the PbI 2 film on the TCO substrate is 300 - 500 nm. After reaching the sufficient thickness, the TCO glass is transferred out of the evaporation device, and the graphite plate substrate is transferred back to the spraying device with the substrate holder device for secondary spraying and recycled. The TCO glass coated with the PbI 2 film undergoes processes such as blade coating and slot coating to achieve the chemical reaction between FAI and PbI 2 to form the perovskite FAPbI 3 film, and then annealing is carried out to complete the perovskite crystallization process.

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

[0071] Example 2

[0072] Refer to Figure 1 , put the organic solution of PbI 2 and the organic solvent of CsI into two raw material tanks respectively. Under the action of a set of spraying devices, the PbI 2 solution and the CsI solution are successively and evenly sprayed on the graphite substrate of the substrate holder device, and then transferred to the pre-air drying device. The wet film is preliminarily dried by controlling the change of pre-air drying air volume and temperature to make the wet film more uniform. Then it passes through the vacuum drying device, and the solvent in the pre-air dried wet film is fully volatilized by rapid vacuum pumping, and the wet film is completely turned into a dry film. The temperature of the vacuum drying is controlled at 50 - 100 °C. Then the TCO glass with the first carrier transport layer is placed on the substrate holder device, directly above the dry film graphite substrate. The substrate holder device is continuously transferred into the evaporation device. The distance between the dry film graphite substrate and the TCO glass is adjustable within the range of 1 - 10 cm. The heating system in the evaporation device makes the temperature of the dry film at 100 - 500 °C, and the air pressure in the evaporation device is maintained at 10 -1 Pa or so. At this time, the PbI2 and CsI are vaporized and deposited onto the TCO glass substrate, causing the PbI on the TCO substrate 2 and CsI mixed film to have a thickness of 300 - 500 nm. After reaching a sufficient thickness, the TCO glass is conveyed out of the evaporation device, and the graphite plate substrate is conveyed back to the spraying device along with the substrate holder device for secondary spraying and recycling. The TCO glass coated with the PbI 2 and CsI film then undergoes processes such as doctor blading and slot die coating to achieve the chemical reaction between FAI and PbI 2 and CsI to form the perovskite CsFAPbI 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] According to the method of Example 1 or Example 2, an organic solution of FAI is placed in two raw material tanks of the spraying device. Under the spraying of the spraying device, the FAI solution is evenly sprayed onto the graphite plate substrate, and then conveyed to the pre-air drying device. The wet film is preliminarily dried by controlling the change of the pre-air drying air volume and temperature to make the wet film more uniform. Then, through the vacuum drying device, the solvent in the pre-air dried wet film is fully volatilized by rapid vacuum pumping, and the wet film is completely turned into a dry film. The temperature of the vacuum drying is controlled at 50 - 100 °C. Then, the TCO glass coated with the PbI 2 film or the mixed film of PbI 2 and CsI is placed on the substrate holder device directly above the dry film graphite plate substrate. The dry film continues to be conveyed into the evaporation chamber. The distance between the dry film graphite plate substrate and the TCO glass is adjustable within the range of 1 - 10 cm. The heating system in the evaporation device keeps the temperature of the dry film at 100 - 200 °C, and the air pressure in the evaporation device is maintained at 10 -1 Pa or so. At this time, the vaporized FAI of the dry film is deposited onto the PbI 2 film or the mixed film of PbI 2 and CsI to form the FAPbI 3 or CsFAPbI 3 film. The thickness of the FAPbI 3 or CsFAPbI 3 film is 300 - 800 nm. After reaching a sufficient thickness, the TCO glass is conveyed out of the evaporation device, and the graphite plate substrate is conveyed back to the spraying device along with the substrate holder device for secondary spraying and recycling.

[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 descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples", etc. mean 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 expressions 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 can 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 layer preparation system with a continuous feeding function, characterized in that, it includes: a substrate holder device, the substrate holder device moves under the drive of a transmission device, the substrate holder device has an installation cavity, the upper side of the installation cavity has a first opening, the lower side of the installation cavity has a second opening, a spraying plate is installed at the second opening, the spraying plate covers the second opening, a substrate is placed at the first opening, the substrate covers the first opening, and the substrate is located directly above the spraying plate; a spraying device, the spraying device sprays a precursor solution onto the spraying plate to form a wet film; a pre-air drying device, the pre-air drying device pre-air dries the wet film; a vacuum drying device, the vacuum drying device dries the pre-air dried wet film into a dry film; a vapor deposition device, the vapor deposition device heats and sublimates the dry film on the spraying plate, and then deposits it on the lower surface of the substrate; a transmission device, the transmission device drives the substrate holder device to sequentially pass through the spraying device, the pre-air drying device, the vacuum drying device and the vapor deposition device, the substrate holder device includes a lower substrate holder, a surrounding plate and an upper substrate holder, the upper substrate holder is located directly above the lower substrate holder, the surrounding plate circumferentially surrounds the lower substrate holder and the upper substrate holder, the upper substrate holder, the lower substrate holder and the surrounding plate define the installation cavity, the spraying plate is placed on the lower substrate holder, and the substrate is placed on the upper substrate holder; the vapor deposition device includes: a film inlet chamber, the film inlet chamber is connected with a vacuum pump; a vapor deposition chamber, the vapor deposition chamber communicates with the film inlet chamber, a heating device is arranged at the lower part of the vapor deposition chamber, the heating device is located directly below the spraying plate, and the vapor deposition chamber is connected with a vacuum pump; a film outlet chamber, the film outlet chamber communicates with the vapor deposition chamber, and the film outlet chamber is connected with a vacuum pump, it further includes a feeding device and a discharging device. After the substrate holder device passes through the vacuum drying device, the feeding device places a substrate on the substrate holder device, and the discharging device takes the deposited substrate off the substrate holder device.

2. The system according to claim 1, characterized in that, the substrate holder device further includes shock-proof elastic pieces, height-adjusting screws and pins, the shock-proof elastic pieces are placed between the spraying plate and the side wall of the lower substrate holder, the height-adjusting screws are located between the lower substrate holder and the upper substrate holder, and the pins are located on the upper substrate holder.

3. The system according to claim 1, characterized in that, the spraying device includes a raw material tank, a cleaning tank, a nozzle and a spraying track. A raw material tank check valve and a nozzle valve are sequentially arranged on the pipeline connecting the raw material tank and the nozzle. The outlet of the cleaning tank communicates with the pipeline between the raw material tank check valve and the nozzle valve. A cleaning tank valve is arranged at the outlet of the cleaning tank. The nozzle is placed between two spraying tracks. When the substrate holder device moves below the spraying track, the nozzle starts to move along the spraying track to spray onto the spraying plate.

4. The system according to claim 1, characterized in that, The vacuum drying device includes a vacuum chamber, a vacuum pump, and an inflation valve. A vacuum valve is provided on the pipeline connecting the vacuum chamber and the vacuum pump, and the inflation valve is provided on the vacuum chamber.

5. The system according to claim 1, characterized in that, a cold trap is provided above the evaporation chamber, and the cold trap is located directly above the substrate.

6. The system according to claim 1, characterized in that, it further includes an XRF film layer monitoring device.

7. The system according to claim 1, characterized in that, it further includes a substrate holder caching device, and the substrate holder caching device can cache the substrate holder device after being dried by the vacuum drying device or the substrate holder device before spraying.

8. A method for preparing a perovskite film layer by using the perovskite film layer preparation system with continuous feeding function according to any one of claims 1-7, characterized in that, it includes: (1) Using a spraying device to spray a precursor solution onto a spraying plate to form a wet film on the spraying plate; (2) Using a pre-air drying device to pre-air dry the wet film to obtain a pre-air dried wet film; (3) Using a vacuum drying device to vacuum dry the pre-air dried wet film to obtain a dry film; (4) Placing a substrate on the substrate holder device with the dry film so that the substrate is located directly above the dry film; (5) Transmitting the substrate holder device obtained in (4) to an evaporation device, and the dry film is heated and sublimated and deposited on the lower surface of the substrate to obtain a perovskite film layer.

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