Thin film and nucleation crystallization method and nucleation crystallization device thereof

Abstract

The invention discloses a thin film and a nucleation crystallization method and a nucleation crystallization device thereof, and relates to the technical field of photovoltaics. The nucleation crystallization device comprises a treatment cabin with a vacuum chamber, vacuum equipment and a blowing mechanism, a bearing base is arranged in the vacuum chamber, the vacuum equipment is communicated with the vacuum chamber, the vacuum equipment is used for vacuumizing the vacuum chamber, and the blowing mechanism is communicated with the vacuum chamber; the bearing base is used for bearing a base body coated with a liquid film, the blowing mechanism is used for blowing air to the surface of the liquid film, the connecting position of the blowing mechanism and the vacuum cavity is a first connecting position, and the bearing base is located between the first connecting position and the vacuum device. The nucleation and crystallization device can improve the nucleation and crystallization quality of a large-area thin film, so that a high-quality thin film can be obtained after annealing.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic technology, and in particular to a thin film and a nucleation crystallization method and a nucleation crystallization device thereof. Background Art

[0002] Perovskite solar cells are solar cells that use perovskite-type organic metal halide semiconductors as light-absorbing materials. They belong to the third generation of solar cells and are also called new concept solar cells. As an emerging field in thin-film solar cell technology, they have the characteristics of high efficiency potential, low cost, and a wide range of application scenarios. They have become the research focus of the global photovoltaic field.

[0003] Among them, the quality of nucleation and crystallization of perovskite film as the core part of perovskite solar cells is crucial to the photoelectric performance of the battery, which will directly affect the generation and transmission of electrons and holes, and then affect the conversion efficiency, stability and service life of the battery. The existing nucleation and crystallization methods of perovskite film mainly include the following three: the first is the anti-solvent method, but the timing of dripping, the amount of anti-solvent and the selection of anti-solvent type in this method will seriously affect the film properties, so this method is limited to the preparation of small-area perovskite film; the second is the blowing method, but when this method is used for nucleation and crystallization, in order to make the liquid film dry quickly to form an intermediate phase of small grains, a large flow of gas is required to blow the surface of the liquid film. However, the large flow of blowing will lead to uneven film formation, and the large flow of blowing still has the problem that the solvent is difficult to effectively remove and needs to be used in conjunction with a large amount of highly volatile solvent as a coordination solvent; the third is the vacuum method, but this method also has the problems of unstable film quality and uneven device efficiency, and this method may also produce holes, insufficient density, fine grains and unstable efficiency. Therefore, how to provide a new nucleation and crystallization method for perovskite films to solve the above problems is a technical challenge that needs to be solved urgently. Summary of the invention

[0004] The object of the present invention is to provide a thin film and a nucleation crystallization method and a nucleation crystallization device, which can improve the nucleation crystallization quality of a large-area thin film, thereby facilitating the acquisition of a high-quality thin film after annealing.

[0005] The embodiment of the present invention is achieved as follows:

[0006] In one aspect of the present invention, a nucleation crystallization device is provided, which includes a processing cabin with a vacuum chamber, a vacuum device and a blowing mechanism; a supporting base is provided in the vacuum chamber, the vacuum device is connected to the vacuum chamber, and the vacuum device is used to evacuate the vacuum chamber, and the blowing mechanism is connected to the vacuum chamber; the supporting base is used to support a substrate coated with a liquid film, the blowing mechanism is used to blow air on the surface of the liquid film, the connection between the blowing mechanism and the vacuum chamber is a first connection, and the supporting base is located between the first connection and the vacuum device. The nucleation crystallization device can improve the nucleation crystallization quality of large-area thin films, thereby facilitating the acquisition of high-quality thin films after annealing.

[0007] Optionally, the nucleation crystallization device further comprises a temperature measuring element disposed in the vacuum chamber, and the temperature measuring element is used to measure the temperature of the supporting base.

[0008] Optionally, a cooling channel is provided in the supporting base, a cooling port is provided on the processing chamber, and the cooling channel is connected to the cooling port through a cooling pipe.

[0009] Optionally, the nucleation crystallization device further comprises a lifting mechanism, which is located at the bottom of the supporting base, and the lifting mechanism can drive the substrate to move along a first direction through the supporting base, and the first direction is the arrangement direction of the substrate and the supporting base.

[0010] Optionally, the lifting mechanism includes a main body and a plurality of lifting members fixedly arranged on the main body, the main body is located on the side of the bearing base away from the base; the main body is driven to drive the plurality of lifting members to move along the first direction, and the lifting members can pass through the bearing base to drive the base away from the bearing base.

[0011] Optionally, the nucleation crystallization device further comprises a vacuum gauge, and the vacuum gauge is used to measure the vacuum degree in the vacuum chamber.

[0012] Optionally, the blowing mechanism includes a first pipeline, a second pipeline connected to the first pipeline, a first gas pipeline and a second gas pipeline connected in parallel between the first pipeline and the second pipeline, a source bottle connected to the first gas pipeline, a first valve arranged on the first pipeline, a second valve arranged on the first gas pipeline, and a third valve arranged on the second gas pipeline; the outlet of the second pipeline is connected to the vacuum chamber.

[0013] Optionally, the blowing mechanism further includes a third pipeline and a fourth valve arranged on the third pipeline, and one end of the third pipeline is connected to the first pipeline, and the other end of the third pipeline is connected to the second pipeline.

[0014] Optionally, the first gas pipeline and the second gas pipeline are respectively provided with a gas flow meter; and / or, the second pipeline is also provided with a gas mixing tank, which is used to mix the gas transmitted from the first gas pipeline and the second gas pipeline to the second pipeline.

[0015] Optionally, the nucleation crystallization device also includes an air uniforming plate arranged on the processing chamber, and the air uniforming plate is used to uniformize the gas blown out by the blowing mechanism; and / or, the nucleation crystallization device also includes an air distribution plate arranged on the processing chamber, and the air distribution plate is provided with multiple evenly distributed air outlets, and the multiple air outlets are all connected to the air outlet of the blowing mechanism.

[0016] Another aspect of the present invention provides a thin film nucleation crystallization method, which adopts the above-mentioned nucleation crystallization device, and the nucleation crystallization method includes: placing a substrate coated with a liquid film in a vacuum chamber; using a vacuum device to evacuate the vacuum chamber to evaporate part of the solvent in the liquid film; filling the vacuum chamber with gas through a blowing mechanism, and evenly blowing the surface of the liquid film with the gas to form intermediate phase crystals in the liquid film; closing the vacuum device to break the vacuum chamber, and taking out the substrate.

[0017] Optionally, gas is filled into the vacuum chamber through a blowing mechanism, and the surface of the liquid film is evenly blown by the gas to form intermediate phase crystals in the liquid film, including: a first volume of gas is filled into the vacuum chamber through the blowing mechanism, and the surface of the liquid film is evenly blown by the gas; a second volume of gas is filled into the vacuum chamber through the blowing mechanism, and the surface of the liquid film is evenly blown by the gas, and the second volume is greater than the first volume.

[0018] Another aspect of the present invention provides a thin film, which is prepared by the above-mentioned thin film nucleation crystallization method.

[0019] The beneficial effects of the present invention include:

[0020] The nucleation crystallization device provided by the present application includes a processing cabin with a vacuum chamber, a vacuum device and a blowing mechanism; a supporting base is provided in the vacuum chamber, the vacuum device is connected to the vacuum chamber, and the vacuum device is used to evacuate the vacuum chamber, and the blowing mechanism is connected to the vacuum chamber; the supporting base is used to support the substrate coated with a liquid film, the blowing mechanism is used to blow air to the surface of the liquid film, the connection between the blowing mechanism and the vacuum chamber is a first connection, and the supporting base is located between the first connection and the vacuum device. The present application can evacuate the vacuum chamber by setting a vacuum device, and can purge the surface of the liquid film in the vacuum chamber by setting a blowing mechanism. In this way, the nucleation crystallization device provided by the present application can realize the combination of the blowing method and the vacuum method. In this way, the vacuum blowing method can be used to dry and crystallize the liquid film, and uniform and dense intermediate phase grains can be formed. The present application can realize the combination of vacuum method and blowing method through the setting of vacuum equipment and blowing mechanism, so that it can not only realize the drying and crystallization of large-area thin films, but also improve the nucleation and crystallization quality of thin films, and improve the quality problems of uneven film formation, holes, and insufficient density in the prior art. In this way, the quality of the thin film dried and crystallized by the nucleation crystallization device provided by the present application can be improved after annealing. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0022] Figure 1 A schematic diagram of the structure of a nucleation crystallization device provided in an embodiment of the present invention;

[0023] Figure 2 A schematic diagram of the structure of the blowing mechanism provided by an embodiment of the present invention;

[0024] Figure 3 One of the schematic flow charts of the nucleation and crystallization method of the perovskite film provided in an embodiment of the present invention;

[0025] Figure 4 A second schematic flow chart of the nucleation and crystallization method of a perovskite film provided in an embodiment of the present invention;

[0026] Figure 5 A distribution diagram of the surface solvent concentration of the perovskite film after vacuuming provided by an embodiment of the present invention;

[0027] Figure 6 A distribution diagram of the surface solvent concentration of the perovskite film provided in an embodiment of the present invention after being blown for 0.5 seconds by a blowing mechanism;

[0028] Figure 7 A distribution diagram of the surface solvent concentration of the perovskite film provided in an embodiment of the present invention after being blown for 1 second by a blowing mechanism.

[0029] Icons: 10-processing chamber; 11-vacuum chamber; 12-hatch cover; 20-support base; 30-vacuum equipment; 40-blowing mechanism; 41-first pipeline; 42-second pipeline; 431-first gas pipeline; 432-second gas pipeline; 44-source bottle; 451-first valve; 452-second valve; 453-third valve; 454-fourth valve; 46-third pipeline; 47-gas flow meter; 48-mixing tank; 50-temperature measuring element; 60-cooling port; 70-lifting mechanism; 71-main body; 72-lifting piece; 80-vacuum gauge; 91-gas uniform plate; 92-gas distribution plate. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Generally, the components of the embodiments of the present invention described and shown in the drawings here can be arranged and designed in various different configurations.

[0031] Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] It should be noted that similar reference numerals and letters denote similar items in the following drawings, and therefore, once an item is defined in one drawing, further definition and explanation thereof is not required in subsequent drawings.

[0033] In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inside", "outside", etc. indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, or the positions or positional relationships in which the product of the invention is usually placed when in use. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific position, be constructed and operated in a specific position, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", "third", etc. are only used to distinguish the description, and cannot be understood as indicating or implying relative importance.

[0034] In addition, the terms "horizontal", "vertical" and the like do not mean that the components are required to be absolutely horizontal or suspended, but can be slightly tilted. For example, "horizontal" only means that its direction is more horizontal than "vertical", and does not mean that the structure must be completely horizontal, but can be slightly tilted.

[0035] In the description of the present invention, it is also necessary to explain that, unless otherwise clearly specified and limited, the terms "set", "install", "connect", and "connect" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0036] Please refer to Figure 1 and Figure 2 The present embodiment provides a nucleation crystallization device, which includes a processing chamber 10 having a vacuum chamber 11, a vacuum device 30 and a blowing mechanism 40; a supporting base 20 is provided in the vacuum chamber 11, the vacuum device 30 is connected to the vacuum chamber 11, the vacuum device 30 is used to evacuate the vacuum chamber 11, and the blowing mechanism 40 is connected to the vacuum chamber 11; the supporting base 20 is used to support a substrate coated with a liquid film, the blowing mechanism 40 is used to blow air on the surface of the liquid film, and the blowing mechanism 40 is located on the side of the supporting base 20 away from the vacuum device 30. The nucleation crystallization device can improve the nucleation crystallization quality of a large-area thin film, thereby facilitating the acquisition of a high-quality thin film after annealing.

[0037] It should be noted that the nucleation crystallization device provided in the present application includes a processing chamber 10, a vacuum device 30 and a blowing mechanism 40. A supporting base 20 is provided in the vacuum chamber 11 of the processing chamber 10.

[0038] The processing chamber 10 includes a chamber body and a chamber cover 12 covering the chamber body. After the chamber cover 12 is covered on the chamber body, the chamber in the chamber body and the chamber cover 12 can form a vacuum chamber 11 together. Figure 1 shown.

[0039] The supporting base 20 is located in the vacuum chamber 11, and the supporting base 20 is fixed relative to the processing chamber 10. Specifically, the present application does not limit the fixing method of the supporting base 20 in the vacuum chamber 11, which can be by relatively fixing the peripheral side wall of the supporting base 20 and the inner wall of the vacuum chamber 11, or by relatively fixing the bottom of the supporting base 20 and the bottom wall of the vacuum chamber 11. As long as the fixing method does not hinder the vacuuming of the vacuum chamber 11 and the flow of the blowing mechanism 40 in the vacuum chamber 11, the specific fixing method is not limited in the present application, and those skilled in the art can determine it by themselves.

[0040] It should be noted that the support base 20 is used to support a substrate coated with a liquid film. Therefore, in order to facilitate the crystallization of the liquid film, the support base 20 of the present application should be arranged horizontally as much as possible. The above-mentioned liquid film can be a perovskite liquid film, and the following description will be made taking the liquid film as a perovskite liquid film as an example.

[0041] The vacuum device 30 is connected to the vacuum chamber 11 and is used to evacuate the vacuum chamber 11 of the processing chamber 10. In this embodiment, optionally, as Figure 1 As shown, the connection between the vacuum device 30 and the vacuum chamber 11 is located at the bottom of the vacuum chamber 11 .

[0042] The blowing mechanism 40 is in communication with the vacuum chamber 11 and is used for blowing air onto the surface of the liquid film in the vacuum chamber 11 , so that the liquid film is dried quickly to form an intermediate phase of fine grains.

[0043] In this embodiment, the connection between the blowing mechanism 40 and the vacuum chamber 11 is located on the side of the supporting base 20 away from the vacuum device 30 (corresponding to Figure 1 In the middle, it is directly above the supporting base 20), so when the blowing mechanism 40 is used to blow air on the surface of the liquid film, the blowing mechanism 40 can make the blowing of the surface of the liquid film relatively more uniform.

[0044] The present application sets up a blowing mechanism 40 and a vacuum device 30, so that when the liquid film is dried and crystallized, the vacuum chamber 11 can be evacuated by the vacuum device 30 first, thereby drying the liquid film to remove part of the solvent therein, and then the blowing mechanism 40 is opened while maintaining the vacuum evacuation state to blow the surface of the liquid film, so as to obtain a dried and crystallized thin film.

[0045] In addition, it should be noted that the connection between the vacuum device 30 and the vacuum chamber 11 of the present application is located at the middle position of the bottom of the vacuum chamber 11, and the connection between the blowing mechanism 40 and the vacuum chamber 11 is located above the supporting base 20. On the one hand, the blowing mechanism 40 can effectively purge the surface of the liquid film, and compared with setting the connection between the blowing mechanism 40 and the vacuum chamber 11 on one side of the supporting base 20, the connection between the blowing mechanism 40 and the vacuum chamber 11 of the present application is set directly above the supporting base 20, which can make the blowing effect of the blowing mechanism 40 on the liquid film better and more uniform; on the other hand, the connection between the vacuum device 30 and the vacuum chamber 11 of the present application is set at the bottom of the vacuum chamber 11, which can facilitate vacuuming, and the purge uniformity of the blowing mechanism 40 will not be affected during the vacuuming; secondly, the solvent volatiles generated by the purge mechanism after the purge mechanism purges the surface of the liquid film can be drawn out of the vacuum chamber 11 under the action of the vacuum device 30.

[0046] In summary, the nucleation crystallization device provided by the present application includes a processing chamber 10 having a vacuum chamber 11, a vacuum device 30 and a blowing mechanism 40; a supporting base 20 is provided in the vacuum chamber 11, the vacuum device 30 is connected to the vacuum chamber 11, the vacuum device 30 is used to evacuate the vacuum chamber 11, and the blowing mechanism 40 is connected to the vacuum chamber 11; the supporting base 20 is used to support the substrate coated with the liquid film, the blowing mechanism 40 is used to blow air to the surface of the liquid film, the connection between the blowing mechanism 40 and the vacuum chamber 11 is the first connection, and the supporting base 20 is located between the first connection and the vacuum device 30. The present application can evacuate the vacuum chamber 11 by setting the vacuum device 30, and can purge the surface of the liquid film in the vacuum chamber 11 by setting the blowing mechanism 40. The nucleation crystallization device provided by the present application can realize the combination of the blowing method and the vacuum method, so that the vacuum blowing method can be used to dry and crystallize the liquid film, and uniform and dense intermediate phase grains can be formed. The present application can realize the combination of vacuum method and blowing method by setting up vacuum equipment 30 and blowing mechanism 40, which can not only realize the drying and crystallization of large-area thin films, but also improve the nucleation and crystallization quality of thin films, and improve the quality problems of uneven film formation, holes, and insufficient density in the prior art. In this way, the quality of the thin film dried and crystallized by the nucleation crystallization device provided by the present application can be improved after annealing.

[0047] Of course, it should be noted that the above-mentioned nucleation crystallization device provided by the present application can be used for the preparation of films of various sizes, as well as the drying process of multiple perovskite crystalline silicon stacked cells of various sizes. The present application does not limit the application scenario of the device, and those skilled in the art can determine it by themselves. Since the larger the size of the film to be formed, the more obvious the difference in film quality, therefore, when the above-mentioned nucleation crystallization device provided by the present application is applied to the scenario of the preparation of large-size films, the more obvious the effect is, and the larger the size of the film, the more prominent the advantages of the nucleation crystallization device of the present application.

[0048] Since the liquid film is relatively sensitive to temperature during the nucleation and crystallization process, in this embodiment, the nucleation and crystallization apparatus further includes a temperature measuring element 50 disposed in the vacuum chamber 11 , and the temperature measuring element 50 is used to measure the temperature in the vacuum chamber 11 .

[0049] For example, the temperature measuring element 50 may be a thermocouple or other temperature sensor. The present application does not limit the specific form of the temperature measuring element 50. As long as the temperature measuring element 50 can measure the temperature in the vacuum chamber 11, it is convenient for the user to monitor the temperature in the vacuum chamber 11 when processing the liquid film using the nucleation crystallization device.

[0050] In order to facilitate the control of the process temperature when the liquid film is subjected to the nucleation crystallization treatment, optionally, a cooling channel is provided in the above-mentioned support base 20, and a cooling port 60 is provided on the processing chamber 10, and the cooling channel is connected to the cooling port 60 through a cooling pipe. Cooling water can be injected into the cooling channel of the support base 20 through the cooling port 60, so as to control the temperature of the support base 20, and then appropriately regulate the working temperature of the liquid film.

[0051] In this embodiment, the cooling channels are evenly distributed in the support base 20. Specifically, the arrangement of the cooling channels in the support base 20 is not limited in this application, and those skilled in the art can determine it according to actual conditions, as long as the temperature of the support base 20 can be evenly controlled.

[0052] Please continue to refer to Figure 1 Optionally, the nucleation crystallization device further includes a lifting mechanism 70, which is located at the bottom of the supporting base 20, and the lifting mechanism 70 can pass through the supporting base 20 to drive the substrate to move along a first direction, and the first direction is the arrangement direction of the substrate and the supporting base 20.

[0053] By setting the lifting mechanism 70, when the liquid film nucleation and crystallization are completed, the vacuum chamber 11 is broken. At this time, the substrate set on the supporting base 20 can be driven upward by the lifting mechanism 70, so as to be separated from the supporting base 20, so that the user can take out the substrate.

[0054] Specifically, the present application does not impose any limitation on the structural form of the lifting mechanism 70 , as long as it can drive the base on the supporting base 20 to move up and down.

[0055] For example, Figure 1 As shown, the lifting mechanism 70 may include a main body 71 and a plurality of lifting members 72 fixedly arranged on the main body 71, and the main body 71 is located on the side of the supporting base 20 away from the base; the main body 71 is driven to drive the plurality of lifting members 72 to move along the first direction, and the lifting members 72 can pass through the supporting base 20 to drive the base away from the supporting base 20.

[0056] The plurality of lifting members 72 are respectively fixedly connected to the body 71, and the plurality of lifting members 72 are evenly distributed on one side of the body 71 close to the hatch cover 12, and the heights of the plurality of lifting members 72 are equal. When the base needs to be lifted, the body 71 is driven to drive the lifting members 72 to move toward the direction close to the base.

[0057] In addition, in this embodiment, in order to achieve real-time monitoring of the vacuum degree in the vacuum chamber 11 , the nucleation crystallization device optionally further includes a vacuum gauge 80 , and the vacuum gauge 80 is used to measure the vacuum degree in the vacuum chamber 11 .

[0058] Reference Figure 1 and Figure 2 Optionally, the blowing mechanism 40 includes a first pipeline 41, a second pipeline 42 connected to the first pipeline 41, a first gas pipeline 431 and a second gas pipeline 432 connected in parallel between the first pipeline 41 and the second pipeline 42, a source bottle 44 connected to the first gas pipeline 431, a first valve 451 provided on the first pipeline 41, a second valve 452 provided on the first gas pipeline 431, and a third valve 453 provided on the second gas pipeline 432; the outlet of the second pipeline 42 is connected to the vacuum chamber 11.

[0059] It should be noted that the blowing mechanism 40 includes a first pipe 41 and a second pipe 42 connected to the first pipe 41. The end of the second pipe 42 away from the first pipe 41 is used to communicate with the vacuum chamber 11. Gas can be input into the vacuum chamber 11 through the second pipe 42 to purge the surface of the liquid film in the vacuum chamber 11.

[0060] The first gas pipeline 431 and the second gas pipeline 432 are connected between the first pipeline 41 and the second pipeline 42, and the source bottle 44 is connected to the first gas pipeline 431. It should be noted that methylamine can be stored in the source bottle 44. When gas is input into the first pipeline 41, the gas coming out of the first pipeline 41 can be divided into two paths, one path passes through the source bottle 44 provided on the first gas pipeline 431, so that the gas carrying methylamine is input into the second pipeline 42, and the other path passes through the second gas pipeline 432 and is input into the second pipeline 42. After the two paths of gas are mixed in the second pipeline 42, they can enter the vacuum chamber 11 from the second pipeline 42 to purge the surface of the liquid film.

[0061] Optionally, the blowing mechanism 40 further includes a third pipe 46 and a fourth valve 454 disposed on the third pipe 46 , and one end of the third pipe 46 is connected to the first pipe 41 , and the other end of the third pipe 46 is connected to the second pipe 42 .

[0062] In this way, part of the gas in the first pipe 41 can also enter the third pipe 46 and enter the vacuum chamber 11 from the second pipe 42 .

[0063] It should be noted that, in the present application, by setting up the third pipeline 46, when the liquid film needs to be dried, nucleated and crystallized, the first valve 451, the second valve 452 and the third valve 453 can be opened, and the fourth valve 454 can be closed, so that the mixed gas can enter the vacuum chamber 11 to purge the surface of the liquid film in the vacuum chamber 11; and when the nucleation and crystallization of the liquid film is completed and the vacuum chamber 11 needs to be broken, the vacuum equipment 30 can be closed, the second valve 452 and the third valve 453 can be closed, and the first valve 451 and the fourth valve 454 can be opened, so that the gas can enter the vacuum chamber 11.

[0064] In order to facilitate the regulation of the gas flow of the first gas pipeline 431 and the second gas pipeline 432 , optionally, a gas flow meter 47 is further provided on the first gas pipeline 431 and the second gas pipeline 432 , respectively.

[0065] In addition, in order to enable the gases in the first gas pipeline 431 and the second gas pipeline 432 to be evenly mixed in the second pipeline 42, in this embodiment, a mixing tank 48 is also provided on the second pipeline 42, and the mixing tank 48 is used to mix the gases transmitted from the first gas pipeline 431 and the second gas pipeline 432 to the second pipeline 42.

[0066] Also, for example, the first valve 451 can be a hand valve, and the second valve 452, the third valve 453 and the fourth valve 454 can be pneumatic diaphragm valves. In addition, a needle valve can be added to the third pipeline 46, and the needle valve can be located between the fourth valve 454 and the first pipeline 41.

[0067] In order to make the mixed gas entering the vacuum chamber 11 from the air blowing mechanism 40 more uniform, optionally, the nucleation crystallization device also includes an air homogenizing plate 91 arranged on the processing chamber 10, and the air homogenizing plate 91 is used to homogenize the gas blown out by the air blowing mechanism 40.

[0068] It should be noted that the present application does not limit the specific structure of the gas homogenizing plate 91 , and those skilled in the art can determine it as needed, as long as the mixed gas can be mixed evenly.

[0069] The nucleation crystallization device provided in the present application also includes an air distribution plate 92 arranged on the processing chamber 10 , and the air distribution plate 92 is provided with a plurality of evenly distributed air outlets, and the plurality of air outlets are all connected to the air blowing port of the air blowing mechanism 40 .

[0070] By setting the air distribution plate 92, the present application can discharge air through multiple evenly arranged air outlets to evenly blow the surface of the liquid film. In this way, the blowing uniformity of the blowing mechanism 40 can be improved, which is beneficial to the uniformity of nucleation and crystallization of the liquid film.

[0071] While adopting the vacuum method, the present application also adds an air distribution plate 92 on the top of the vacuum chamber 11. While controlling the vacuum degree, a trace amount of airflow is introduced and the airflow is evenly guided by the gas spray plate to remove the saturated solvent vapor on the surface of the liquid film, thereby accelerating the liquid film to enter a supersaturated state and nucleate and crystallize.

[0072] The trace gas flow provided by the blowing mechanism 40 is generally an inert gas, such as nitrogen. In addition to the inert gas path, the device is also equipped with a heating source bottle 44 storing methylamine on the first gas pipeline 431, and the inert gas can be used as a carrier gas to carry methylamine into the vacuum chamber 11, thereby promoting crystal growth, or carrying materials that can form a coordination passivation effect on the surface of the liquid film into the cavity, such as methylamine.

[0073] In addition, in this embodiment, in order to prevent the substrate from shifting on the supporting base 20, a vacuum adsorption hole may be provided on the supporting base 20, and the substrate may be vacuum adsorbed on the supporting base 20, thereby ensuring that the substrate and the supporting base 20 are in close fit and ensuring the temperature uniformity of the large-area liquid film, thereby ensuring the uniformity of the film formation quality.

[0074] Please refer to Figure 3 and Figure 4 In another aspect of the present invention, a thin film nucleation crystallization method is provided. The thin film nucleation crystallization method adopts the above-mentioned nucleation crystallization device. The nucleation crystallization method comprises the following steps:

[0075] S100 , placing the substrate coated with the liquid film in a vacuum chamber 11 .

[0076] Specifically, in this embodiment, the hatch 12 of the processing chamber 10 is first opened, and then the substrate coated with the liquid film is placed on the supporting base 20 of the vacuum chamber 11 , and then the hatch 12 is fixed to the chamber body to close the processing chamber 10 .

[0077] S200 , using the vacuum equipment 30 to evacuate the vacuum chamber 11 to evaporate part of the solvent in the liquid film.

[0078] At this time, the solvent on the surface of the liquid film evaporates rapidly and reaches a solid-liquid conversion equilibrium on the surface of the liquid film.

[0079] S300 , filling the vacuum chamber 11 with gas through the blowing mechanism 40 , and evenly blowing the surface of the liquid film with the gas, so that mesophase crystals are formed in the liquid film.

[0080] It should be noted that the present application can accelerate the volatilization of the solvent through gas purging, which is beneficial to the nucleation and crystallization of the liquid film.

[0081] In addition, the gas may be dry air, nitrogen, a mixture of nitrogen and other gases (for example, the other gas may be methylamine or chlorine, etc.), or a gas carrying a small amount of small molecule substances (for example, the small molecule substances may be methylamine chloride or urea, etc.). The application does not limit the specific type of gas used for purging, and those skilled in the art may select any of the above-mentioned multiple gas forms according to actual needs.

[0082] When the above-mentioned mixed gas or the gas carrying a small amount of small molecular substances is used to sweep the surface of the liquid film, the speed of nucleation and crystallization can be further accelerated.

[0083] Optionally, the above step S300, in which gas is filled into the vacuum chamber 11 by the blowing mechanism 40 and the surface of the liquid film is evenly swept by the gas to form mesophase crystals in the liquid film, may specifically include the following steps:

[0084] S310 , a first volume of gas is filled into the vacuum chamber 11 through the blowing mechanism 40 , and the surface of the liquid film is evenly purged with the gas to form intermediate phase crystal nuclei in the liquid film.

[0085] S320, a second volume of gas is filled into the vacuum chamber 11 through the blowing mechanism 40, and the surface of the liquid film is evenly swept by the gas to form intermediate phase crystals in the liquid film, and the second volume is larger than the first volume.

[0086] That is, the above step S300 can be divided into several small steps to be performed one by one. Exemplarily, it can be performed in two steps. Among them, the first step (i.e., step S310) uses a small flow rate to purge the surface of the liquid film to produce solvent volatiles, and the chamber is pumped out by the above vacuum equipment 30 (such as a vacuum pump). As the concentration of the solvent gas on the surface decreases, the solvent in the liquid film continues to evaporate, and a uniform intermediate phase crystal nucleus is formed in the liquid film.

[0087] For example, in step S310, the gas mass flow meter at the first gas pipeline 431 can be set to 10 sccm, the mass flow meter at the second gas pipeline 432 can be set to 50 sccm, the ventilation time is 30 s, and the cavity pressure is 1 Pa. In addition, in order to form uniform crystal nuclei throughout the liquid film, it is necessary to ensure that the solvent gas solubility at the interface between the liquid phase and the gas phase is uniform, so it is necessary to ensure that the gas flow rate blowing across the surface of the liquid film is uniform.

[0088] Step S320 increases the gas flow rate relative to step S310, further reducing the solvent concentration at the interface between the liquid film and the gas, allowing the solvent to evaporate quickly and the mesophase nuclei to grow quickly, ultimately forming dense, uniform and appropriately sized mesophase crystals.

[0089] Exemplarily, in step S310, the gas mass flow meter at the first gas pipeline 431 can be set between 10 sccm and 100 sccm, the gas mass flow meter at the second gas pipeline 432 can be set between 50 sccm and 200 sccm, the ventilation time can be set between 30s and 50s, and the cavity pressure can be set between 50pa and 200pa.

[0090] In step S320, the gas mass flow meter at the first gas pipeline 431 can be set between 20sccm and 200sccm, the gas mass flow meter at the second gas pipeline 432 can be set between 100sccm and 1000sccm, the ventilation time can be set between 20s and 60s, and the cavity pressure can be set between 50pa and 200pa. Of course, the flow rate, time, and pressure of the gas introduced in the above steps S310 and S320 are only examples and should not be regarded as limitations on the present application. If a larger area of ​​liquid film needs to be processed, the required gas flow rate, time, and pressure control need to be adjusted accordingly.

[0091] It should be noted that the present application divides step S300 into two steps, S310 and S320, for illustrative purposes only. In other embodiments, the above step S300 can be divided into more steps for execution according to different process recipes, but it should be noted that the gas mass flow rate, ventilation time and chamber pressure of any two steps should be different in at least one.

[0092] For example, the process may be performed in multiple steps, and the gas volume of any step should be greater than the gas volume of the previous step.

[0093] Please refer to Figure 5 , Figure 5 When the thin film nucleation crystallization method provided by the present application is used, the concentration distribution diagram of the surface solvent of the perovskite film after performing step S200 shows that its concentration distribution is relatively uniform, but its concentration value is relatively high; Figure 6 The surface solvent concentration distribution diagram of the perovskite film after the blowing mechanism 40 is used to blow air for 0.5S. At this time, its concentration distribution is relatively uniform, and its overall concentration value is relatively Figure 5 has been lowered; Figure 7 FIG. 4 is a surface solvent concentration distribution diagram of the perovskite film after the blowing mechanism 40 is used to blow air for 1 second. It can be seen that at this time, the concentration distribution of the surface solvent of the perovskite film is already very uniform, and its concentration value is already very low overall ( Figure 7 The relative surface solvent concentration of the perovskite film Figure 6 The surface solvent concentration of the perovskite film is lower), which shows that the drying effect is very significant at this time, and the nucleation and crystallization effect of the perovskite film is better.

[0094] S400 , closing the vacuum device 30 to break the vacuum in the vacuum chamber 11 , and taking out the substrate.

[0095] That is, after the liquid film nucleation and crystallization are completed, the vacuum chamber 11 is de-vacuumed and the substrate with the thin film is taken out.

[0096] The vacuum breaking can be achieved by closing the vacuum device 30 , closing the second valve 452 and the third valve 453 , and opening the first valve 451 and the fourth valve 454 .

[0097] Another aspect of the present invention provides a thin film, which is prepared by the above-mentioned thin film nucleation crystallization method. Since the specific steps and technical effects of the above-mentioned thin film nucleation crystallization method have been described in detail above, this application will not repeat them here.

[0098] The above description is only an optional embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

[0099] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A nucleation crystallization device, characterized in that: It comprises a processing cabin with a vacuum chamber, a vacuum device and a blowing mechanism; a bearing base is provided in the vacuum chamber, the vacuum device is communicated with the vacuum chamber, and the vacuum device is used to evacuate the vacuum chamber, and the blowing mechanism is communicated with the vacuum chamber; The supporting base is used to support a substrate coated with a liquid film, the blowing mechanism is used to blow air to the surface of the liquid film, the connection between the blowing mechanism and the vacuum chamber is a first connection, and the supporting base is located between the first connection and the vacuum equipment.

2. The nucleation crystallization device according to claim 1, characterized in that: The nucleation crystallization device further comprises a temperature measuring element disposed in the vacuum chamber, and the temperature measuring element is used to measure the temperature of the supporting base.

3. The nucleation crystallization device according to claim 1 or 2, characterized in that: A cooling channel is provided in the bearing base, a cooling port is provided on the processing chamber, and the cooling channel is communicated with the cooling port through a cooling pipe.

4. The nucleation crystallization device according to claim 1, characterized in that: The nucleation crystallization device also includes a lifting mechanism, which is located at the bottom of the supporting base, and the lifting mechanism can pass through the supporting base to drive the substrate to move along a first direction, and the first direction is the arrangement direction of the substrate and the supporting base.

5. The nucleation crystallization device according to claim 4, characterized in that: The lifting mechanism comprises a main body and a plurality of lifting members fixedly arranged on the main body, wherein the main body is located on a side of the bearing base away from the base; The main body is driven to drive the plurality of lifting members to move along a first direction, and the lifting members can pass through the bearing base to drive the base body away from the bearing base.

6. The nucleation crystallization device according to claim 1, characterized in that: The nucleation crystallization device further comprises a vacuum gauge, and the vacuum gauge is used to measure the vacuum degree in the vacuum chamber.

7. The nucleation crystallization device according to claim 1, characterized in that: The blowing mechanism includes a first pipeline, a second pipeline connected to the first pipeline, a first gas pipeline and a second gas pipeline connected in parallel between the first pipeline and the second pipeline, a source bottle connected to the first gas pipeline, a first valve arranged on the first pipeline, a second valve arranged on the first gas pipeline, and a third valve arranged on the second gas pipeline; the outlet of the second pipeline is connected to the vacuum chamber.

8. The nucleation crystallization device according to claim 7, characterized in that: The blowing mechanism further includes a third pipeline and a fourth valve arranged on the third pipeline. One end of the third pipeline is connected to the first pipeline, and the other end of the third pipeline is connected to the second pipeline.

9. The nucleation crystallization device according to claim 7 or 8, characterized in that: The first gas pipeline and the second gas pipeline are also provided with a gas flow meter respectively; and / or, the second pipeline is also provided with a gas mixing tank, and the gas mixing tank is used to mix the gas transmitted from the first gas pipeline and the second gas pipeline to the second pipeline.

10. The nucleation crystallization device according to claim 1, characterized in that: The nucleation crystallization device also includes an air uniforming plate arranged on the processing chamber, and the air uniforming plate is used to uniformize the gas blown out by the blowing mechanism; and / or, the nucleation crystallization device also includes an air distribution plate arranged on the processing chamber, and the air distribution plate is provided with a plurality of evenly distributed air outlets, and the plurality of air outlets are all connected to the air outlet of the blowing mechanism.

11. A method for nucleation crystallization of a thin film, characterized in that: The film nucleation crystallization method adopts the nucleation crystallization device according to any one of claims 1 to 10, and the nucleation crystallization method comprises: placing the substrate coated with the liquid film in a vacuum chamber; Using a vacuum device to evacuate the vacuum chamber to evaporate part of the solvent in the liquid film; Filling the vacuum chamber with gas through a blowing mechanism, and evenly sweeping the surface of the liquid film with the gas, so as to form mesophase crystals in the liquid film; The vacuum device is closed to break the vacuum chamber, and the substrate is taken out.

12. The thin film nucleation crystallization method according to claim 11, characterized in that: The step of filling the vacuum chamber with gas through the blowing mechanism and evenly sweeping the surface of the liquid film with the gas to form mesophase crystals in the liquid film includes: Filling a first volume of gas into the vacuum chamber through the blowing mechanism, and evenly blowing the surface of the liquid film through the gas; The second volume of the gas is filled into the vacuum chamber by the blowing mechanism, and the surface of the liquid film is evenly purged by the gas, and the second volume is greater than the first volume.

13. A film, characterized in that: The film is prepared by the nucleation crystallization method of claim 11 or 12.

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