Perovskite layer gas-phase transport deposition equipment and method with continuous feeding function

Abstract

The present invention discloses a perovskite layer vapor transport deposition device and method with a continuous feeding function. The device includes a vacuum deposition device, an evaporation device, and a feeding device; the vacuum deposition device includes a vacuum deposition chamber and a vapor distribution chamber, the substrate is arranged in the vacuum deposition chamber, the vapor distribution chamber is arranged in the vacuum deposition chamber, a vapor distribution outlet is provided on the lower side surface of the vapor distribution chamber, the substrate is located below the vapor distribution outlet, and the vapor distribution chamber is provided with a vapor inlet; the evaporation device includes a heating evaporation chamber, a crucible is arranged in the heating evaporation chamber, a vapor outlet is provided at the upper end of the heating evaporation chamber, a vapor transport pipeline is connected between the vapor inlet and the vapor outlet, and the feeding device is arranged at the upper end of the heating evaporation chamber and is communicated with the heating evaporation chamber. This device avoids the blockage of the vapor distribution chamber, and can realize the transformation, addition of raw materials and the maintenance of the device without breaking the vacuum during the vacuum deposition process, saving time and labor costs, and having a high production efficiency.

Description

Technical Field

[0001] The present invention belongs to the field of perovskite solar cells, and particularly relates to a perovskite layer vapor transport deposition device 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. In recent years, the highest power conversion efficiency of perovskite solar cells has increased from 3.8% to 25.7%. This power conversion efficiency not only exceeds that of other thin-film solar cells developed earlier, but also has even caught up with or exceeded the industrialized solar cell technologies that have been developed for many years, such as polycrystalline silicon solar cells, showing great industrial development prospects.

[0003] 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; a perovskite light absorption layer ABX3 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, or two monovalent element ions; 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, a metal oxide or an organic semiconductor material; and a back electrode, which can be a metal material, graphite, or a conductive oxide. When preparing the perovskite layer on a large scale for mass production, 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.

[0004] The current vapor transport deposition device combines raw material powder with a carrier gas, and injects the raw material powder into the heating cylinder of the evaporation distributor through the purging of the carrier gas. The material is evaporated in the cylinder and the evaporated material is guided and collected through the vapor distributor. The opening of the vapor distributor faces the substrate so that the thin film material is deposited on the substrate. Since the raw material is evaporated in the vapor distributor, the vapor distributor contains solid powder and gas. The gas can pass through the porous wall of the vapor distributor, but the solid powder cannot. The solid powder will cause the pores of the vapor distributor to be blocked. After the vapor distributor is blocked, it is necessary to break the vacuum for maintenance to repair the vapor distributor, thereby reducing the production efficiency and increasing the labor cost. Therefore, the existing vapor deposition device needs to be improved. Summary of the Invention

[0005] 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 layer vapor transport deposition device and method with a continuous feeding function. The device avoids clogging of the vapor distribution chamber, and can realize the transformation and addition of raw materials and the maintenance of the device without breaking the vacuum during the vacuum deposition process, saving time and labor costs, and having high production efficiency.

[0006] In one aspect of the present invention, there is provided a perovskite layer vapor transport deposition device with a continuous feeding function. According to an embodiment of the present invention, the device includes:

[0007] A vacuum deposition device, the vacuum deposition device includes:

[0008] A vacuum deposition chamber, a substrate is disposed in the vacuum deposition chamber;

[0009] A vapor distribution chamber, the vapor distribution chamber is disposed in the vacuum deposition chamber, a vapor distribution outlet is provided on the lower side surface of the vapor distribution chamber, the substrate is located below the vapor distribution outlet, and the vapor distribution chamber is provided with a vapor inlet;

[0010] An evaporation device, the evaporation device includes a heating evaporation chamber, a crucible is disposed in the heating evaporation chamber, a vapor outlet is provided at the upper end of the heating evaporation chamber, a vapor transport pipeline is connected between the vapor inlet and the vapor outlet, and a first valve is provided on the vapor transport pipeline; the heating evaporation chamber is connected with a first vacuum pump and a first carrier gas pipeline, and a first carrier gas valve is provided on the first carrier gas pipeline;

[0011] A feeding device, the feeding device is disposed at the upper end of the heating evaporation chamber and is communicated with the heating evaporation chamber.

[0012] The device according to the above embodiments of the present invention includes a vacuum deposition device, an evaporation device, and a feeding device. Specifically, the vacuum deposition device includes a vacuum deposition chamber and a vapor distribution chamber. The substrate is disposed in the vacuum deposition chamber, and the vapor distribution chamber is disposed in the vacuum deposition chamber. The lower side of the vapor distribution chamber is provided with a vapor distribution outlet, and the substrate is located below the vapor distribution outlet. The vapor distribution chamber is provided with a vapor inlet; the evaporation device includes a heating evaporation chamber, a crucible is disposed in the heating evaporation chamber, a vapor outlet is provided at the upper end of the heating evaporation chamber, a vapor transmission pipeline is connected between the vapor inlet and the vapor outlet, and a first valve is provided on the vapor transmission pipeline; the heating evaporation chamber is connected to a first vacuum pump and a first carrier gas pipeline, and a first carrier gas valve is provided on the first carrier gas pipeline. The feeding device is disposed at the upper end of the heating evaporation chamber and communicates with the heating evaporation chamber. First, the raw material is fed into the crucible in the heating evaporation chamber through the feeding device. Then, by controlling the first carrier gas valve, the gas flow rate and size in the first carrier gas pipeline are adjusted, the first vacuum pump is started, and after the air in the heating evaporation chamber is exhausted, the first carrier gas valve is closed, and the first vacuum pump starts to pump vacuum to make the heating evaporation chamber reach a predetermined vacuum degree. The crucible heats the raw material to evaporate the raw material into a gas. At this time, the first valve on the vapor transmission pipeline is opened simultaneously, and the raw material vapor enters the vapor distribution chamber successively through the vapor outlet, the vapor transmission pipeline, and the vapor inlet, and is finally deposited on the substrate through the vapor distribution outlet. Because in this application, the vacuum deposition device and the evaporation device are independently arranged respectively, that is, the solid or powder raw material is first evaporated into a gas in the evaporation device, and then the raw material gas is transported to the vacuum deposition device through the vapor transmission pipeline for deposition, thereby avoiding the blockage of the vapor distribution chamber. At the same time, if it is necessary to change the raw material type or add materials and perform maintenance on equipment such as the evaporation device, only the first valve on the vapor transmission pipeline needs to be closed, and the vacuum deposition device can operate normally, thus not affecting the normal deposition of the substrate. Therefore, this device avoids the blockage of the vapor distribution chamber, and on the premise of not breaking the vacuum during the vacuum deposition process, it can realize the transformation and addition of raw materials and the maintenance of equipment, saving time and labor costs, and having high production efficiency.

[0013] In addition, the perovskite layer gas-phase transport deposition device with a continuous feeding function according to the above embodiments of the present invention may further have the following technical features:

[0014] In some embodiments of the present invention, a gas transmission plate is disposed in the vacuum deposition chamber, and a plurality of gas outlets are provided on the gas transmission plate. The gas transmission plate is located above the vapor distribution chamber, and the top end of the gas transmission plate is connected to a process gas pipeline, and a second valve is provided on the process gas pipeline. Thus, the local air pressure in the vacuum deposition chamber can be adjusted.

[0015] In some embodiments of the present invention, a plurality of the gas transmission plates are included, and the plurality of gas transmission plates are arranged along the length direction of the vapor distribution chamber. Thus, the local air pressure in the vacuum deposition chamber can be adjusted.

[0016] In some embodiments of the present invention, a gas flow controller is provided on the process gas pipeline. Thereby, the gas flow rate in the process gas pipeline can be controlled.

[0017] In some embodiments of the present invention, a spoiler tube group is provided in the steam distribution cavity. The spoiler tube group is arranged along the length direction of the steam distribution cavity. The spoiler tube group includes at least two spoiler tubes arranged at intervals from the inside to the outside. The spoiler tubes are arranged in a cylindrical tube shape. Openings and heating tubes are provided on the side walls of the spoiler tubes. The openings of adjacent two spoiler tubes are arranged staggeredly. The spoiler tube located in the innermost is communicated with the steam inlet. Thereby, the steam in the steam distribution cavity can be distributed more evenly.

[0018] In some embodiments of the present invention, the central axes of multiple spoiler tubes coincide. Thereby, the steam in the steam distribution cavity can be distributed more evenly.

[0019] In some embodiments of the present invention, the spoiler tube group includes three spoiler tubes. Thereby, the steam in the steam distribution cavity can be distributed more evenly.

[0020] In some embodiments of the present invention, the opening of the spoiler tube located in the outermost layer faces the steam distribution outlet.

[0021] In some embodiments of the present invention, an adjustable baffle is provided at the opening of the spoiler tube located in the outermost layer. Thereby, the uniformity of steam distribution can be improved.

[0022] In some embodiments of the present invention, the feeding device includes a storage tank, a material pushing cavity and a feeding cavity. The lower end opening of the storage tank is communicated with the top end of one side of the material pushing cavity. A material pusher is provided in the material pushing cavity; the upper end of the feeding cavity is communicated with the other side of the material pushing cavity. A first gate valve is provided between the feeding cavity and the material pushing cavity. The lower end of the feeding cavity is communicated with the heating evaporation cavity. A second gate valve is provided between the feeding cavity and the heating evaporation cavity. A weighing device is provided above the second gate valve. A second vacuum pump and a second carrier gas pipeline are connected to the feeding cavity. Thereby, continuous addition or replacement of raw materials can be realized.

[0023] In some embodiments of the present invention, a first vacuum gauge is installed in the feeding cavity. Thereby, the vacuum degree in the feeding cavity can be monitored.

[0024] In some embodiments of the present invention, an observation window is provided on the side wall of the feeding cavity. Thereby, the internal environment of the feeding cavity can be observed.

[0025] In some embodiments of the present invention, the heating and evaporation chamber includes an upper chamber B and a lower chamber A, the upper chamber B and the lower chamber A are detachable, the crucible is placed in the lower chamber A, and a first heating element is installed on the inner side wall of the lower chamber A. Thus, it is convenient to repair or clean the crucible and related accessories.

[0026] In some embodiments of the present invention, a heat reflection plate and a water cooling plate are sequentially arranged between the first heating element and the chamber wall of the lower chamber A from inside to outside. Thus, the temperature of the crucible can be adjusted.

[0027] In some embodiments of the present invention, the first heating element is a three-section heating element. Thus, the temperatures of different upper, middle, and lower sections of the crucible can be adjusted separately.

[0028] In some embodiments of the present invention, a second vacuum gauge is installed in the heating and evaporation chamber. Thus, the vacuum degree of the heating and evaporation chamber can be monitored.

[0029] In some embodiments of the present invention, a second heating element is installed outside the vapor delivery pipeline. Thus, the vapor delivery pipeline can be heated to prevent vapor condensation.

[0030] In some embodiments of the present invention, an atmosphere sensor is installed in the vacuum deposition chamber. Thus, the vapor atmosphere can be monitored.

[0031] In the second aspect of the present invention, the present invention provides a method for preparing a perovskite absorption layer by using the above-mentioned perovskite layer gas-phase transport deposition device with a continuous feeding function. According to the embodiments of the present invention, the method includes:

[0032] (1) Place the substrate in the vacuum deposition chamber, supply inorganic raw materials into the crucible through the feeding device, heat the crucible to evaporate the inorganic raw materials, and deposit the inorganic raw material vapor on the substrate through the heating and evaporation chamber and then through the vapor distribution outlet to form an inorganic skeleton layer;

[0033] (2) Supply organic raw materials into the crucible through the feeding device, heat the crucible to evaporate the organic raw materials, and deposit the organic raw material vapor on the inorganic skeleton layer through the heating and evaporation chamber and then through the vapor distribution outlet to form an organic precursor layer;

[0034] (3) Heat and anneal the substrate material obtained in step (2) to obtain a perovskite absorption layer.

[0035] Thus, by using the above device and this method, the raw materials can be heated into vapor separately and then transported to the vacuum deposition chamber for deposition, thereby avoiding the blockage of the vapor distribution chamber. At the same time, on the premise of not breaking the vacuum during the vacuum deposition process, the transformation and addition of raw materials and the maintenance of the equipment can be realized, saving time and labor costs, and having high production efficiency.

[0036] In addition, the method according to the above embodiments of the present invention may further have the following technical features:

[0037] In some embodiments of the present invention, in step (1), the vacuum degree of the vacuum deposition chamber is 10 -1 Pa to 10 Pa.

[0038] In some embodiments of the present invention, in step (1), the temperature of the crucible is 80 °C to 1000 °C.

[0039] In some embodiments of the present invention, in step (1), the thickness of the inorganic skeleton layer is 100 nm to 600 nm.

[0040] In some embodiments of the present invention, in step (1), the inorganic raw material includes at least one of lead iodide, lead chloride, and lead bromide.

[0041] In some embodiments of the present invention, in step (1), the inorganic raw material further includes at least one of cesium iodide, cesium chloride, and cesium bromide.

[0042] In some embodiments of the present invention, in step (2), the vacuum degree of the vacuum deposition chamber is 10 -1 Pa to 10 Pa.

[0043] In some embodiments of the present invention, in step (2), the temperature of the crucible is 60 °C to 300 °C.

[0044] In some embodiments of the present invention, in step (2), the thickness of the organic precursor layer is 100 nm to 600 nm.

[0045] In some embodiments of the present invention, in step (2), the organic raw material includes at least one of methylammonium iodide, formamidinium iodide, methylammonium bromide, formamidinium bromide, methylammonium chloride, and formamidinium chloride.

[0046] In a third aspect of the present invention, the present invention provides a perovskite solar cell. According to the embodiments of the present invention, the perovskite solar cell sequentially includes a top electrode, a first charge transport layer, a perovskite absorption layer, a second charge transport layer, and a bottom electrode, and the perovskite absorption layer is prepared by the above equipment or the above method. Thus, the perovskite solar cell has a high production efficiency.

[0047] The additional aspects and advantages of the present invention will be partially given in the following description, partially become apparent from the following description, or be understood through the practice of the present invention. Description of the Drawings

[0048] 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, wherein:

[0049] Figure 1 is a schematic structural diagram of a perovskite layer vapor transport deposition device with a continuous feeding function according to an embodiment of the present invention;

[0050] Figure 2 is a side view of a longitudinal section of a vapor distribution chamber according to an embodiment of the present invention;

[0051] Figure 3 is a schematic structural diagram of an evaporation device and a feeding device according to an embodiment of the present invention;

[0052] Figure 4 is a schematic structural diagram of a crucible according to an embodiment of the present invention. Detailed Embodiments

[0053] 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 limiting the present invention.

[0054] In one aspect of the present invention, the present invention provides a perovskite layer vapor transport deposition device with a continuous feeding function. According to an embodiment of the present invention, referring to Figure 1 , the device includes a vacuum deposition device 100, an evaporation device 200, and a feeding device 220. By separately arranging the vacuum deposition device 100 and the evaporation device 200, the solid or powder raw material is heated and evaporated into vapor in the evaporation device 200, and then transported into the vacuum deposition device 100 for deposition. At the same time, the feeding device 220 can continuously supply raw materials to the evaporation device 200 or change the raw materials. Thereby, the blockage of the vapor distribution chamber 120 is avoided, and on the premise of not breaking the vacuum during the vacuum deposition process, the transformation and addition of raw materials and the maintenance of the device can be realized, saving time and labor costs and having high production efficiency.

[0055] According to an embodiment of the present invention, referring to Figure 1 , the vacuum deposition device 100 includes a vacuum deposition chamber 110 and a vapor distribution chamber 120. The substrate 140 is arranged in the vacuum deposition chamber 110, the vapor distribution chamber 120 is arranged in the vacuum deposition chamber 110, a vapor distribution outlet 121 is provided on the lower side surface of the vapor distribution chamber 120, the substrate 140 is located below the vapor distribution outlet 121, and a vapor inlet 122 is provided in the vapor distribution chamber 120. The evaporation device 200 heats and evaporates the solid or powder raw material into a raw material gas, the raw material gas enters the vapor distribution chamber 120 from the vapor inlet 122, and finally is deposited on the substrate 140 through the vapor distribution outlet 121. Thereby, the blockage of the vapor distribution chamber 120 is avoided.

[0056] According to an embodiment of the present invention, referring toFigure 1 , the evaporation device 200 includes a heating evaporation chamber 210, a crucible 211 is arranged in the heating evaporation chamber 210, a vapor outlet 212 is arranged at the upper end of the heating evaporation chamber 210, a vapor transmission pipeline 230 is connected between the vapor inlet 122 and the vapor outlet 212, and a first valve 231 is arranged on the vapor transmission pipeline 230; the heating evaporation chamber 210 is connected with a first vacuum pump 213 and a first carrier gas pipeline 214, and a first carrier gas valve 215 is arranged on the first carrier gas pipeline 214; the feeding device 220 is arranged at the upper end of the heating evaporation chamber 210 and is communicated with the heating evaporation chamber 210. First, the raw material is fed into the crucible 211 in the heating evaporation chamber 210 through the feeding device 220. Then, by controlling the first carrier gas valve 215, the flow rate and size of the carrier gas in the first carrier gas pipeline 214 are adjusted, the first vacuum pump 213 is started, after the air in the heating evaporation chamber 210 is discharged, the first carrier gas valve 215 is closed, and the first vacuum pump 213 starts to pump vacuum to make the heating evaporation chamber 210 reach a predetermined vacuum degree. The crucible 211 starts to heat the raw material to evaporate the raw material into gas. At this time, the first valve 231 on the vapor transmission pipeline 230 is opened simultaneously, and the raw material vapor enters the vapor distribution chamber 120 through the vapor outlet 212, the vapor transmission pipeline 230 and the vapor inlet 122 in sequence, and is finally deposited on the substrate 140 through the vapor distribution outlet 121. Thus, the solid or powder raw material is first evaporated into gas in the evaporation device 200, and then the raw material gas is transported to the vacuum deposition device 100 through the vapor transmission pipeline 230 for deposition, thereby avoiding the blockage of the vapor distribution chamber 120. At the same time, if it is necessary to change the type of raw material or add materials and perform maintenance on equipment such as the evaporation device 200, only the first valve 231 on the vapor transmission pipeline 230 needs to be closed, and the vacuum deposition device 100 can operate normally, so as not to affect the normal deposition of the substrate 140 and ensure the production efficiency. It should be noted that the carrier gas is an inert gas such as helium, nitrogen, argon, etc.

[0057] Specifically, during the first process, the vacuum degree of the vacuum deposition chamber 110 is pumped to a low pressure state of 5×10 -4 pa or below, the first vacuum pump 213 is started to pump vacuum for the heating evaporation chamber 210. After the vacuum reaches 10×10 -1 pa, the first carrier gas valve 215 is opened, and the first carrier gas pipeline 214 fills the heating evaporation chamber 210 with the carrier gas until it reaches kPa. The first vacuum pump 213 is started again, and this is repeated three times to replace the air in the heating evaporation chamber 210 with an inert gas to protect the components in the heating evaporation chamber 210 and maintain the vacuum degree at 10×10 -1 pa, and the crucible 211 is started to be heated.

[0058] Thus, the device avoids clogging of the vapor distribution chamber 120, and realizes the transformation, addition of raw materials and maintenance of the device without breaking the vacuum during the vacuum deposition process, saving time and labor costs, and having high production efficiency.

[0059] According to an embodiment of the present invention, referring to Figure 1 , an air delivery plate 130 is provided in the vacuum deposition chamber 110. A plurality of gas outlets (not shown) are provided on the air delivery plate 130. The air delivery plate 130 is located above the vapor distribution chamber 120. The top end of the air delivery plate 130 is connected to a process gas pipeline 131, and a second valve 132 is provided on the process gas pipeline 131. Since the vacuum deposition process has air pressure requirements for the vacuum deposition chamber 110, by providing the air delivery plate 130 in the vacuum deposition chamber 110, some inert gases are sent into the vacuum deposition chamber 110 from the air delivery plate 130 through the process gas pipeline 131, and the gas flow rate of the air delivery plate 130 at different positions in the vacuum deposition chamber 110 can be adjusted to control the local air pressure at different positions in the vacuum deposition chamber 110. Thus, the present application provides an air delivery plate 130 in the vacuum deposition chamber 110, which can adjust the local air pressure in the vacuum deposition chamber. Further, a plurality of air delivery plates 130 are included. The upper end of each air delivery plate 130 is connected to the process gas pipeline 131, and a gas flow controller 133 is respectively installed on the process gas pipeline 131 connected to each air delivery plate 130, so as to respectively adjust the gas flow rate of the corresponding air delivery plate 130 through the independent gas flow controller 133. Preferably, 3 air delivery plates 130 are included, which are respectively located in the front, middle and rear sections of the vacuum deposition chamber 110. It should be noted that according to specific process requirements, the process gas pipeline 131 can transport corresponding reaction gases to react with the raw material gas output from the vapor distribution chamber 120. Further, an atmosphere sensor 150 is installed in the vacuum deposition chamber 110. Thus, the vapor atmosphere can be monitored, and when the conditions allowed by the process are reached, the substrate 140 can be transported and deposited on the substrate 140.

[0060] According to an embodiment of the present invention, referring to Figure 1 and Figure 2, a spoiler tube group 123 is provided in the vapor distribution chamber 120. The spoiler tube group 123 is arranged along the length direction of the vapor distribution chamber 120. The spoiler tube group 123 includes at least two spoiler tubes 124 arranged at intervals from the inside to the outside. The spoiler tubes 124 are arranged in a cylindrical tube body. An opening 125 and a heating tube 126 are provided on the side wall of the spoiler tube 124. The openings 125 of two adjacent spoiler tubes 124 are arranged staggeredly. The spoiler tube 124 located on the innermost side is communicated with the vapor inlet 122. A spoiler tube group 123 is provided in the vapor distribution chamber 120. The raw material vapor input from the vapor inlet 122 first enters the innermost spoiler tube 124, and then enters the adjacent spoiler tube 124 from the opening 125 of the innermost spoiler tube 124, and so on until the gas enters the outermost spoiler tube 124, and then enters the vapor distribution chamber 120 from the opening 125 of the outermost spoiler tube 124, and finally is output through the vapor distribution outlet 121 of the vapor distribution chamber 120 and deposited on the substrate 140. Thus, in this application, by providing the spoiler tube group 123 in the vapor distribution chamber 120, the vapor in the vapor distribution chamber 120 can be distributed more evenly, thereby improving the uniformity of the deposited film layer. Further, the central axes of the plurality of spoiler tubes 124 coincide. Preferably, the spoiler tube group includes 3 spoiler tubes; preferably, the opening directions of two adjacent spoiler tubes 125 are opposite. Those skilled in the art can understand that for the heating temperature of the heating tube 126, those skilled in the art can select according to the properties of the material. Generally, the heating temperature of the heating tube 126 should be higher than the evaporation temperature of the raw material, so as to prevent the condensation of the raw material vapor.

[0061] According to an embodiment of the present invention, the opening 125 of the outermost spoiler tube 124 faces the vapor distribution outlet 121. Thus, the vapor in the vapor distribution chamber can be distributed more evenly. Further, due to the different diffusivities of different materials, the dispersion amounts at different positions of the opening 125 of the outermost spoiler tube 124 will be different. Therefore, an adjustable baffle 127 can be provided at the opening 125 of the outermost spoiler tube 124 to correct the gas dispersion amount at the opening 125. Thus, the uniformity of the vapor distribution at the opening 125 of the outer spoiler tube 124 can be improved. It should be noted that for the number of the baffles 127 and the length of the baffles 127 along the axis direction of the spoiler tube 124, those skilled in the art can select according to the specific raw material properties or process conditions, which will not be elaborated here.

[0062] According to an embodiment of the present invention, refer to Figure 3, the feeding device 220 includes a storage tank 221, a material pushing chamber 222, and a feeding chamber 223. The lower end of the storage tank 221 is open and connected to the top of one side of the material pushing chamber 222. A material pusher 2221 is provided in the material pushing chamber 222; the upper end of the feeding chamber 223 is connected to the other side of the material pushing chamber 222. A first gate valve 224 is provided between the feeding chamber 223 and the material pushing chamber 222. The lower end of the feeding chamber 223 is connected to the heating and evaporation chamber 210. A second gate valve 225 is provided between the feeding chamber 223 and the heating and evaporation chamber 210. A weighing device 226 is provided above the second gate valve 225. A second vacuum pump 2231 and a second carrier gas pipeline 2232 are connected to the feeding chamber 223. The solid raw material is placed in the storage tank 221. The lower end of the storage tank 221 is open and connected to the top of one side of the material pushing chamber 222. The material pusher 2221 in the material pushing chamber 222 rotates, driving the raw material to move to the other end of the material pushing chamber 222, and the other end of the material pushing chamber 222 is connected to the upper end of the feeding chamber 223. Then the raw material falls into the feeding chamber 223. A second gate valve 225 is provided between the feeding chamber 223 and the heating and evaporation chamber 210. A weighing device 226 is provided above the second gate valve 225. When the raw material enters the feeding chamber 223, it first falls on the weighing device 226. The weighing device 226 feeds back the weight of the raw material to the material pusher 2221. After reaching the specified weight, the material pusher 2221 stops pushing. At this time, the second gate valve 225 opens, and the weighing device 226 tilts to put the raw material into the crucible 211 in the heating and evaporation chamber 210. Thus, by adopting this feeding device 220 in this application, continuous addition or replacement of the raw material can be realized. Specifically, after the raw material falls on the weighing device 226, the first gate valve 224 is closed, and the second carrier gas pipeline 2232 is connected to the carrier gas pipeline, so that the carrier gas can be sent into the feeding chamber 223. At the same time, the second vacuum pump 2231 evacuates the air, removing the air in the feeding chamber 223 and making the feeding chamber 223 reach the required vacuum degree. On the one hand, the vacuum degrees of the feeding chamber 223 and the heating and evaporation chamber 210 are balanced, and the vapor atmosphere in the heating and evaporation chamber 210 is avoided from fluctuating to the greatest extent. On the other hand, air is prevented from entering the heating and evaporation chamber 210, causing oxidation of the raw material and the heating wire, etc. Further, the carrier gas is an inert gas such as helium, nitrogen, argon, etc.

[0063] Specifically, open the first gate valve 224, start the material pusher 2221 for feeding, and at the same time the weighing device 226 weighs in real time. After reaching the required weight, the material pusher 2221 stops feeding, close the first gate valve 224, start the second vacuum pump 2231 to evacuate to 0 Pa, close the second vacuum pump 2231 and the valves of its vacuum pipeline, open the second carrier gas pipeline 2232, inflate to kPa, and then start the second vacuum pump 2231 to evacuate again. Repeat three times to replace the air in the feeding chamber 223 with an inert gas and maintain the vacuum degree at 10×10 -1Open the second gate valve 225, and the weigher 226 can be tilted to pour the material into the crucible 211. Rotate 120° each time for pouring to ensure uniform distribution of the material in the crucible 211. Close the second gate valve 225. After the temperature of the crucible 211 stabilizes, open the first valve 231 on the steam delivery pipe 230, and at the same time, the first carrier gas pipe 214 can be opened to maintain a stable input of the carrier gas. When the material in the crucible 211 is nearly exhausted, repeatedly open the second carrier gas pipe 2232 to restore the pressure to atmospheric pressure. Use the material pusher 2221 to feed the material. When the required amount is reached, stop feeding, close the first gate valve 224, and use the two-stage vacuum pump 2231 and the carrier gas in the second carrier gas pipe 2232 to exchange the gas, replacing the gas in the feeding chamber 223 with an inert gas, and controlling the vacuum degree in the feeding chamber 223 to be the same as that in the heating and evaporation chamber 210. Open the second gate valve 225, and the weigher 226 starts to feed the material.

[0064] According to an embodiment of the present invention, refer to Figure 3 , a first vacuum gauge 227 is installed in the feeding chamber 223 to monitor the vacuum degree in the feeding chamber 223; an observation window 228 is provided on the side wall of the feeding chamber 223. The observation window 228 is a double-layer glass. The outer glass can isolate the internal and external environments of the pipeline, and the inner glass is a replaceable glass that can be replaced after being soiled. By installing the observation window 228, the internal environment of the feeding chamber 223 can be observed; above the first gate valve 224, a pipeline baffle 229 is installed at the lower end of the pushing chamber 222 to better feed the raw materials pushed down by the material pusher 2221 into the center of the weigher 226; the weigher 226 can be tilted at multiple angles, thus avoiding the accumulation of raw materials at the same position in the crucible 211. At the same time, the weigher 226 can feed back data to the material pusher 2221 to adjust the rotation speed and feeding amount of the material pusher 2221; the pipes of the two-stage vacuum pump 2231 and the second carrier gas pipe 2232 are thin pipes to prevent the materials on the weigher 226 from being lifted by the air flow.

[0065] According to an embodiment of the present invention, refer to Figure 3, the heating evaporation chamber 210 includes an upper chamber B 215 and a lower chamber A 216. The upper chamber B 215 and the lower chamber A 216 are detachably connected. The crucible 211 is placed in the lower chamber A 216, and a first heating element 217 is installed on the inner side wall of the lower chamber A 216. Since the upper chamber B 215 and the lower chamber A 216 are detachable, the lower chamber A 216 can be detached from the heating evaporation chamber 210. The crucible 211 is placed in the lower chamber A 216. If maintenance or cleaning of the crucible 211 is required, it is very convenient to take out the crucible 211 from the lower chamber A 216. When in use for heating, the first heating element 217 is installed on the inner side wall of the lower chamber A 216, and the crucible 211 can be heated. Thus, by adopting the heating evaporation chamber 210 of the present application, it is convenient to repair or clean the crucible and related parts. Further, a second vacuum gauge (not shown) is installed in the heating evaporation chamber 210. Thus, the vacuum degree of the heating evaporation chamber can be monitored. It should be noted that the first heating element 217 is a conventional heating element in the art. For example, a whole piece of heating sheet, or 2 segments, 3 segments, 4 segments of heating sheets, etc., or a heating wire is used as the first heating element 217. As long as the heating function can be achieved, those skilled in the art can select the specific type of the first heating element 217 according to the actual situation. Preferably, the first heating element 217 is a three-section heating element. Thus, the temperatures of different upper, middle, and lower sections of the crucible 211 can be adjusted respectively.

[0066] According to an embodiment of the present invention, referring to Figure 4 , a heat reflection plate 218 and a water cooling plate 219 are sequentially arranged between the first heating element 217 and the cavity wall of the lower chamber A 216 from inside to outside. Thus, the temperature of the crucible 211 can be adjusted. According to an embodiment of the present invention, referring to Figure 3 , a second heating element 232 is installed outside the vapor delivery pipe 230. Thus, the vapor delivery pipe 230 can be heated to prevent vapor condensation.

[0067] In the second aspect of the present invention, the present invention provides a method for preparing a perovskite absorption layer by using the above-mentioned perovskite layer vapor transport deposition device with a continuous feeding function. According to an embodiment of the present invention, the method includes:

[0068] S100: Form an inorganic skeleton layer on the substrate

[0069] In this step, the substrate is placed in the vacuum deposition chamber. The inorganic raw material is supplied to the crucible through the feeding device. The crucible is heated to evaporate the inorganic raw material. The inorganic raw material vapor passes through the heating evaporation chamber and is deposited on the substrate through the vapor distribution outlet to form an inorganic skeleton layer.

[0070] According to an embodiment of the present invention, the vacuum degree of the vacuum deposition chamber is 10 -110 Pa to 10 Pa; the temperature of the crucible is 80°C to 1000°C; the thickness of the inorganic framework layer is 100 nm to 600 nm. Further, the inorganic raw material includes at least one of lead iodide, lead chloride, and lead bromide, and the inorganic raw material further includes at least one of cesium iodide, cesium chloride, and cesium bromide.

[0071] S200: Form an organic precursor layer on the inorganic framework layer

[0072] In this step, the organic raw material is supplied into the crucible through a feeding device, the crucible is heated to evaporate the organic raw material, and the organic raw material vapor is deposited on the inorganic framework layer through the heating evaporation chamber and then through the vapor distribution outlet to form an organic precursor layer.

[0073] According to an embodiment of the present invention, the degree of vacuum in the vacuum deposition chamber is 10 -1 Pa to 10 Pa; the temperature of the crucible is 60°C to 300°C; the thickness of the organic precursor layer is 100 nm to 600 nm. Further, the organic raw material includes at least one of methylammonium iodide, formamidinium iodide, methylammonium bromide, formamidinium bromide, methylammonium chloride, and formamidinium chloride.

[0074] S300: Anneal the substrate material obtained in S200

[0075] In this step, the substrate material obtained in S200 is heated and annealed to obtain a perovskite absorption layer. Those skilled in the art can understand that the annealing conditions are conventional processes in the art, and those skilled in the art can select specific annealing conditions according to actual situations.

[0076] Thus, by using the above equipment and method, the raw materials can be heated into vapor separately and then transported to the vacuum deposition chamber for deposition, thereby avoiding the blockage of the vapor distribution chamber. At the same time, on the premise of not breaking the vacuum during the vacuum deposition process, the transformation and addition of raw materials and the maintenance of the equipment can be realized, saving time and labor costs, and having high production efficiency. It should be noted that the features and advantages described for the above perovskite layer gas-phase transport deposition equipment with continuous feeding function also apply to this method, and will not be elaborated here.

[0077] In the third aspect of the present invention, the present invention proposes a perovskite solar cell. According to an embodiment of the present invention, the perovskite solar cell sequentially includes an upper electrode, a first charge transport layer, a perovskite absorption layer, a second charge transport layer, and a lower electrode, and the above perovskite absorption layer is prepared by using the above equipment or the above method. Thus, the perovskite solar cell has high production efficiency. It should be noted that the features and advantages described for the above equipment and method also apply to this perovskite solar cell, and will not be elaborated here.

[0078] The present invention will be described below 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.

[0079] Embodiment 1

[0080] (1)Prepare a first charge transport layer on a conductive glass substrate or a textured substrate.

[0081] The first charge transport layer is prepared by vacuum evaporation on a tin-doped indium oxide (ITO) conductive glass substrate, and the thickness of the first charge transport layer is 20 nm.

[0082] Conductive glasses include tin-doped indium oxide (ITO) conductive glass, fluorine-doped tin oxide (FTO) conductive glass, etc. Textured substrates include crystalline silicon textured substrates of perovskite-silicon tandem solar cells and other textured substrates. The first charge transport layer includes cuprous thiocyanate (CuSCN), cuprous iodide (CuI), cuprous oxide (CuO), nickel oxide (NiO), vanadium pentoxide (V2O5), molybdenum trioxide (MoO3), Spiro-OMeTAD, P3HT, PTAA, PEDOT:PSS, titanium dioxide (TiO2), tin dioxide (SnO2), fullerene (C 60 ), zinc oxide (ZnO), PCBM, etc. The preparation methods of the first charge transport layer include evaporation method, sputtering method, chemical bath deposition method, precursor solution spin coating method, precursor solution blade coating method, Slot-die method, etc. The optimal thickness range of the first charge transport layer is 0.1 nm - 50 nm.

[0083] (2)Prepare the perovskite absorption layer by a two-step method.

[0084] The vacuum degree of the vacuum deposition chamber is 2 Pa, the carrier gas is nitrogen, and the flow rate is maintained at 500 sccm. After waiting for the atmosphere in the vacuum deposition chamber to stabilize, the substrate obtained in step (1) enters the vacuum deposition chamber. Deposit an inorganic framework layer on the first charge transport layer substrate. The raw material of the inorganic framework layer is Cs-doped PbI2. Heat the crucible and control the temperature at 500 °C. The thickness of the deposited inorganic framework layer is 200 nm.

[0085] The vacuum degree of the vacuum deposition chamber is 2 Pa, the carrier gas is nitrogen, and the flow rate is maintained at 500 sccm. Continue to deposit an organic precursor on the inorganic framework layer. The organic precursor is formamidinium iodide (FAI). Heat the crucible and control the temperature at 200 °C. The thickness range of the formed organic precursor layer is 400 nm.

[0086] When the organic precursor is deposited, the substrate enters the temperature control box of the substrate heating and annealing equipment through a conveyor belt. Under the heating effect of the temperature control box, the organic precursor reacts with the inorganic precursor to form a perovskite film layer.

[0087] Reaction mechanism: PbI2 + FAI → FAPbI3

[0088] The first inorganic framework layer can also be prepared using the device of the present application, and then the second organic precursor is prepared using the solution method. Finally, using the annealing process, under the heating effect of the temperature control box, a chemical reaction occurs between the organic precursor and the inorganic precursor, thereby forming a perovskite film layer.

[0089] (3)Prepare the second charge transport layer.

[0090] Using the vacuum evaporation method, the second charge transport layer is prepared on the above-mentioned perovskite film layer. The second charge transport layer is nickel oxide (NiO); the thickness of the second charge transport layer is 20 nm.

[0091] The second charge transport layer includes cuprous thiocyanate (CuSCN), cuprous iodide (CuI), cuprous oxide (CuO), nickel oxide (NiO), vanadium pentoxide (V2O5), molybdenum trioxide (MoO3), Spiro-OMeTAD, P3HT, PTAA, PEDOT:PSS, titanium dioxide (TiO2), tin dioxide (SnO2), fullerene (C 60 ), zinc oxide (ZnO), PCBM, etc. The preparation methods of the second charge transport layer include evaporation method, sputtering method, spin coating method of precursor solution or doctor blade coating method of precursor solution, and Slot-die method, etc. The optimal thickness range of the second charge transport layer is 5 nm - 50 nm.

[0092] (4)Prepare the back electrode to form a perovskite solar cell.

[0093] Using the vacuum evaporation method, the back electrode is prepared on the above-mentioned second charge transport layer. The back electrode is a Cu electrode with a thickness of 60 nm.

[0094] The back electrode includes metal back electrodes such as silver electrode (Ag), copper electrode (Cu), gold electrode (Au), aluminum electrode (Al), molybdenum electrode (Mo), chromium electrode (Cr), etc. The back electrode also includes transparent back electrodes such as indium tin oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide, etc. The optimal thickness range of the metal back electrode is 40 nm - 100 nm. The preparation methods of the metal back electrode include evaporation method and sputtering method, etc. The optimal thickness range of the transparent back electrode is 50 nm - 100 nm. The preparation methods of the transparent back electrode include sputtering method, etc.

[0095] In the description of this specification, the descriptions referring to terms such as "one embodiment", "some embodiments", "examples", "specific examples", 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.

[0096] 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 layer gas-phase transport deposition device with a continuous feeding function, characterized in that, Comprising: A vacuum deposition device, the vacuum deposition device comprising: A vacuum deposition chamber, a substrate being disposed in the vacuum deposition chamber; A vapor distribution chamber, the vapor distribution chamber being disposed in the vacuum deposition chamber, a vapor distribution outlet being provided on the lower side surface of the vapor distribution chamber, the substrate being located below the vapor distribution outlet, and a vapor inlet being provided in the vapor distribution chamber; An evaporation device, the evaporation device comprising a heating evaporation chamber, a crucible being disposed in the heating evaporation chamber, a vapor outlet being provided at the upper end of the heating evaporation chamber, a vapor transport pipeline being connected between the vapor inlet and the vapor outlet, and a first valve being provided on the vapor transport pipeline; the heating evaporation chamber is connected to a first vacuum pump and a first carrier gas pipeline, and a first carrier gas valve is provided on the first carrier gas pipeline; A feeding device, the feeding device being disposed at the upper end of the heating evaporation chamber and communicating with the heating evaporation chamber; A turbulator tube group is provided in the vapor distribution chamber, the turbulator tube group is arranged along the length direction of the vapor distribution chamber, the turbulator tube group comprises at least two turbulator tubes arranged at intervals from the inside to the outside, the turbulator tubes are arranged in a cylindrical tube shape, openings are provided on the side walls of the turbulator tubes, the openings of adjacent two turbulator tubes are arranged staggeredly, the turbulator tube located at the innermost side is communicated with the vapor inlet, and the openings of the turbulator tubes located at the outermost layer face the vapor distribution outlet.

2. The device according to claim 1, characterized in that, Comprising at least one of the following features: (T2.1) An air delivery plate is provided in the vacuum deposition chamber, a plurality of gas outlets are provided on the air delivery plate, the air delivery plate is located above the vapor distribution chamber, the top end of the air delivery plate is connected to a process gas pipeline, and a second valve is provided on the process gas pipeline; (T2.2) A plurality of the air delivery plates are included, and the plurality of air delivery plates are arranged along the length direction of the vapor distribution chamber; (T2.3) A gas flow controller is provided on the process gas pipeline; (T2.4) An atmosphere sensor is installed in the vacuum deposition chamber.

3. The device according to claim 1 or 2, characterized in that, Comprising at least one of the following features: (T3.1) A heating tube is further provided on the side wall of the turbulator tube; (T3.2) The central axes of the plurality of turbulator tubes coincide.

4. The device according to claim 1, characterized in that, An adjustable baffle is provided at the opening of the turbulator tube located at the outermost layer.

5. The device according to claim 1, characterized in that The feeding device comprises: A storage tank; A material pushing chamber, the lower end opening of the storage tank is communicated with the top end of one side of the material pushing chamber, and a material pusher is provided in the material pushing chamber; A feeding chamber, the upper end of the feeding chamber is communicated with the other side of the material pushing chamber, a first gate valve is provided between the feeding chamber and the material pushing chamber, the lower end of the feeding chamber is communicated with the heating evaporation chamber, a second gate valve is provided between the feeding chamber and the heating evaporation chamber, a weighing device is provided above the second gate valve, and a second vacuum pump and a second carrier gas pipeline are connected to the feeding chamber.

6. The device according to claim 5, characterized in that, A first vacuum gauge is installed in the feeding chamber.

7. The device according to claim 1, characterized in that, Comprising at least one of the following features: (T7.1) The heating evaporation chamber comprises an upper chamber B and a lower chamber A, the upper chamber B and the lower chamber A are detachable, the crucible is placed in the lower chamber A, and a first heating element is installed on the inner side wall of the lower chamber A; A heat reflection plate and a water-cooled plate are sequentially arranged between the first heating element and the chamber wall of the lower chamber A from inside to outside; A second vacuum gauge is installed in the heating and evaporation chamber; A second heating element is installed outside the vapor delivery pipeline.

8. A method for preparing a perovskite absorption layer by using the perovskite layer gas-phase transport deposition device with a continuous feeding function according to any one of claims 1-7, characterized in that, It includes: (1) Place the substrate in the vacuum deposition chamber, supply inorganic raw materials to the crucible through the feeding device, heat the crucible to evaporate the inorganic raw materials, and deposit the inorganic raw material vapor on the substrate through the heating and evaporation chamber and the vapor distribution outlet to form an inorganic skeleton layer; (2) Supply organic raw materials to the crucible through the feeding device, heat the crucible to evaporate the organic raw materials, and deposit the organic raw material vapor on the inorganic skeleton layer through the heating and evaporation chamber and the vapor distribution outlet to form an organic precursor layer; (3) Heat and anneal the substrate material obtained in step (2) to obtain a perovskite absorption layer.

9. The method according to claim 8, wherein It includes at least one of the following features: (T9.1) In step (1), the vacuum degree of the vacuum deposition chamber is 10 -1 Pa to 10 Pa; (T9.2) In step (1), the temperature of the crucible is 80°C to 1000°C; (T9.3) In step (1), the thickness of the inorganic skeleton layer is 100 nm to 600 nm; (T9.4) In step (2), the vacuum degree of the vacuum deposition chamber is 10 -1 Pa to 10 Pa; (T9.5) In step (2), the temperature of the crucible is 60°C to 300°C; (T9.6) In step (2), the thickness of the organic precursor layer is 100 nm to 600 nm.

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