Thin film drying device, thin film drying method and perovskite solar cell module

Abstract

The present invention belongs to the technical field of thin film drying equipment and relates to a thin film drying device, a thin film drying method, and a perovskite solar cell assembly. The thin film drying device includes: a blowing component that provides a first airflow in a first direction toward the liquid film to be dried, the air outlet direction of the blowing component and the plane where the liquid film to be dried are sandwiched to form an acute angle area; and an air supply device that provides solvent vapor; wherein, when the blowing component provides the first airflow in the first direction toward the liquid film to be dried, a drainage area is formed in the acute angle area, and the solvent vapor is covered by the drainage airflow in the drainage area to the surface of the liquid film to be dried. The thin film drying device and thin film drying method of the present invention can significantly accelerate the drying of the liquid film to be dried, and can also improve the crystallization quality during the drying process, taking into account the consistency of the crystal orientation of the film, thereby alleviating interface defects between the film and other materials.

Description

Technical Field

[0001] The present invention relates to the technical field of thin film drying equipment, and in particular to a thin film drying device, a thin film drying method and a perovskite solar cell assembly. Background Art

[0002] During the preparation of functional material thin films, the drying process of the wet film is crucial and directly impacts the properties of the dried film. Common drying methods include hot air drying, infrared drying, microwave drying, or vacuum drying. Different film drying methods can lead to different film properties, especially for functional material thin films that require a crystallization process during drying. For example, the drying of perovskite films requires rapid drying while also ensuring optimal crystal orientation and high crystal quality. For large-area perovskite films, uniformity over the entire drying area is also essential. For inorganic crystalline films, such as titanium dioxide (TiO2), the drying process involves solvent evaporation and chemical reactions, causing TiO2 molecules to aggregate and crystallize into a specific crystalline structure. This drying process also directly impacts the crystallization process. Therefore, achieving rapid film drying while maintaining optimal crystal consistency and high film quality remains a pressing technical challenge.

[0003] The drying of most functional material films relies on film drying equipment. Although existing drying equipment can achieve film drying to a certain extent, the drying speed and the quality of the dried films are poor, and it is impossible to achieve fast and efficient drying of the films. Some film drying equipment is also not suitable for drying large-area films (not limited to ultra-large sizes of 1m×2m).

[0004] CN219112105U discloses a solvent vapor-assisted air knife, comprising a main air knife, wherein the main air knife is provided with a gas outlet connected to the outside, through which the main air knife transports gas to the film, and further comprising an air supply device connected to the main air knife through a conduit, wherein the air supply device comprises a steam generating assembly for generating solvent vapor and a nitrogen transporting assembly for transporting nitrogen, and is capable of transporting nitrogen and solvent vapor to the main air knife, and in the main air knife, the gas can remain in a gaseous state in the process of reaching the surface of the film. The above-mentioned device is suitable for the preparation process of large-area perovskite solar cells. It can reduce the use of solvent vapor while achieving the effect of solvent annealing. At the same time, the corresponding device meets the requirements of controlling the amount of solvent gas charged, the time sequence of contact of different positions of the film layer with the solvent gas, and the direction control during vacuuming. However, the device disclosed in the above-mentioned technical solution still has the following defects: ① The air output of the main air knife is very large. Even if the corresponding proportion of solvent vapor is low, the total amount will be very large, and the effect of reducing the usage will not be achieved; ② The wind speed of the main air knife is very fast, resulting in the solvent vapor contained inside actually acting on the film to be dried for a very short time, and the solvent annealing effect is limited. It is difficult to achieve low-cost assembly of the device while ensuring a better drying effect.

[0005] Therefore, how to provide a simple and low-cost thin film drying device and thin film drying method that is suitable for drying most functional material films, especially suitable for improving the crystallization effect during the drying process of large-area functional material films to improve the film formation quality of the dried film, is a technical problem that needs to be solved urgently. Summary of the Invention

[0006] To address the above-mentioned technical problems, the present invention provides a thin film drying device, a thin film drying method, and a perovskite solar cell module. The thin film drying device provided by the present invention includes a blowing component and an air supply device, each of which is independently provided. The solvent vapor provided by the air supply device is driven by a drainage airflow in a drainage area (where the air outlet direction of the blowing component forms an acute angle with the plane of the liquid film to be dried). The solvent vapor is then applied to the surface of the liquid film to be dried and partially dissolves with the solvent in the liquid film to be dried. After being swept by the first airflow provided by the blowing component, the solvent vapor assists in the volatilization of the solvent in the liquid film to be dried, significantly accelerating the drying of the liquid film to be dried. Furthermore, the solvent vapor improves the crystallization quality during the drying process, while also ensuring the consistency of the crystal orientation of the film, thereby alleviating interface defects between the film and other materials.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a thin film drying device for drying a liquid film to be dried, the thin film drying device comprising:

[0009] a blowing component for providing a first air flow in a first direction toward the liquid film to be dried, wherein an air outlet direction of the blowing component and a plane where the liquid film to be dried are located form an acute angle region; and

[0010] a gas supply device, wherein the gas supply device provides solvent vapor;

[0011] When the blowing component provides the first airflow in the first direction toward the liquid film to be dried, a drainage area is formed in the acute angle region, and the solvent vapor is covered on the surface of the liquid film to be dried by the drainage airflow in the drainage area.

[0012] In the thin film drying device provided by the present invention, the blowing component and the air supply device are independently arranged and not connected, and each plays a corresponding role. The device is simple and has low assembly cost. It is suitable for drying most functional material films, and is particularly suitable for improving the crystallization quality of large-area functional material films, thereby improving the film formation quality of the dried film and alleviating interface defects between the film and other materials.

[0013] In a second aspect, the present invention further provides a thin film drying method, the thin film drying method comprising:

[0014] A blowing component is used to provide a first air flow in a first direction toward the liquid film to be dried, and a drainage area is formed in an acute angle region between the air outlet direction of the blowing component and the plane where the liquid film to be dried is located, wherein a drainage air flow exists in the drainage area;

[0015] The solvent vapor is provided by an air supply device, and the solvent vapor is covered on the surface of the liquid film to be dried through the drainage air flow.

[0016] In the present invention, the thin film drying method can be implemented by the thin film drying device described in the first aspect.

[0017] The air outlet direction of the blowing component of the present invention is inclined toward the liquid film to be dried, and a drainage area is formed in the acute angle area formed by the air outlet direction of the blowing component and the plane where the liquid film to be dried is located. The drainage airflow in the drainage area is used to drive the solvent vapor provided by the air supply device to cover the surface of the liquid film to be dried and partially dissolve with the solvent in the liquid film to be dried. After being blown by the first airflow provided by the blowing component, the solvent vapor can assist the solvent in the liquid film to be dried to volatilize, significantly accelerate the drying of the liquid film to be dried, accelerate the drying crystallization process, reduce the discontinuous volatilization caused by the delayed volatilization of the solvent inside the liquid film to be dried, reduce the stress and defects in the film, improve the phenomenon of untimely drying and partial blowing away of the liquid film to be dried due to excessive airflow velocity, and improve the yield rate. Among them, the present invention utilizes the anti-solvent characteristics, so that the solvent vapor covers the surface of the liquid film to be dried and is partially miscible with the solvent in the liquid film to be dried. The solvent vapor assists the volatilization of the solvent in the liquid film to be dried, and can extract the lower layer solvent in the liquid film to be dried to a certain extent, accelerate the growth of seed crystals in the lower layer of the film, form a bottom-up growth trend, improve the consistency of crystallization orientation, and thus improve the crystallization quality, and alleviate the interface defects between the film and other materials; in addition, the film drying method of the present invention utilizes the airflow movement law of the blowing component to cover the solvent vapor on the surface of the liquid film to be dried, with a fast covering speed, full coverage, and large coverage amount, and the covering method is passive, without the need for external force, so it will not disturb the airflow around the blowing component and will not have any negative impact on the drying process.

[0018] Furthermore, the present invention coats the surface of the liquid film to be dried with a film of solvent vapor. Compared to existing thin film drying methods that incorporate volatile solvents into the solvent system of the liquid film to be dried, this method avoids the problem of volatile solvents in the middle and bottom areas preferentially boiling and escaping during drying, which could lead to holes or other defects in the middle or bottom areas. Furthermore, the drainage airflow is ambient gas, not generated by an additional gas source. Therefore, neither the drainage airflow nor the solvent vapor affects the airflow out of the air outlet of the blowing component, and thus has no negative impact on the drying process.

[0019] As a preferred technical solution of the present invention, the solvent vapor is miscible with the solvent in the liquid film to be dried.

[0020] And / or, during the mutual dissolution of the solvent vapor and the solvent in the liquid film to be dried, the mutual dissolution ratio is 1% to 20%, for example, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18% or 20%.

[0021] It should be noted that the mutual solubility ratio of 1% to 20% specifically refers to that the mass of the solvent vapor accounts for 1% to 20% of the total mass of the solvent vapor and the solvent in the liquid film to be dried.

[0022] In the present invention, the mutual solubility ratio of the solvent vapor and the solvent in the liquid film to be dried is regulated to be 1% to 20%, which can ensure that when the first airflow directly blows the mixed liquid film to be dried, the film-forming effect during the drying process is better, that is, the volatilization rate of the solvent in the liquid film to be dried is accelerated, the bottom seed layer of the film is promoted to grow from bottom to top, and the crystallinity of the crystal is improved. If the mutual solubility ratio is too small, the mutual solubility penetration is insufficient, which is of little help in increasing the volatilization rate of the film solvent during drying; if the mutual solubility ratio is too large, the solvent vapor and the solvent in the liquid film to be dried are completely miscible or miscible too much, which is likely to cause an increase in holes and defects at the lower interface of the film during drying, which will have the same effect as directly adding an auxiliary solvent to the film to be dried; and it will also take away too much solvent in the mixed liquid film to be dried, resulting in premature volatilization and crystallization during drying, affecting the quality and uniformity of the crystal.

[0023] As a preferred technical solution of the present invention, in the air supply device, the outlet of the solvent vapor is located at a first horizontal distance from the air outlet of the blowing component and a second vertical distance from the liquid film to be dried, the first distance is 50mm~500mm, for example, 50mm, 100mm, 150mm, 200mm, 250mm, 300mm, 350mm, 400mm, 450mm or 500mm, etc., and the second distance is 10mm~200mm, for example, 10mm, 50mm, 80mm, 100mm, 120mm, 150mm, 180mm or 200mm, etc.

[0024] The present invention adjusts the first distance to 50mm~500mm and the second distance to 10mm~200mm, so that the released solvent vapor can be in the drainage area and can be driven by the drainage airflow, thereby achieving the effect of being able to move along the substrate surface and cover.

[0025] It should be noted that the present invention does not impose specific requirements and special limitations on the position of the air supply device itself. As long as the outlet of the solvent vapor provided by it is at the corresponding position, technical personnel in this field can adaptively select and adjust the position of the air supply device itself according to actual needs. For example, if the air supply device is far away from the blowing component and the film to be dried, the solvent vapor can be led into the drainage area through a pipeline to ensure that the outlet for releasing the solvent vapor into the environment is located in the drainage area.

[0026] As a preferred technical solution of the present invention, the particle diameter of the solvent vapor is greater than 0 and less than or equal to 10 μm, for example, 1 μm, 3 μm, 5 μm, 8 μm or 10 μm.

[0027] In the present invention, the particle diameter of the solvent vapor provided by the air supply device is controlled to be greater than 0 and less than or equal to 10 μm, thereby ensuring that the uniformity and crystal quality of the liquid film to be dried and the film after drying are not negatively impacted. This is because, when the solvent vapor droplets carried by the drained airflow land on (contact) the surface of the liquid film to be dried, an air film forms between the solvent vapor droplets and the film to be dried, causing the center of the liquid film to be dried to be repelled. Furthermore, the solvent vapor droplets may merge into the film to be dried multiple times. Therefore, if the solvent vapor droplets are large in size, the kinetic energy generated by their surface rupture and the potential energy generated by the droplets themselves during merging will exacerbate the repulsion of the center of the liquid film to be dried, resulting in a decrease in the film thickness at the center of the liquid film to be dried, forming a phenomenon similar to a coffee ring (manifested as a circular uneven film thickness, which takes a long time to reduce due to the self-leveling of the liquid film to be dried and the counteraction of forces such as the film tension or van der Waals forces). This, in turn, affects the uniformity and crystal quality of the film after drying.

[0028] It should be noted that the present invention does not make specific requirements and special limitations on the gas supply method of the gas supply device. Any method that can provide solvent vapor can be used, such as ultrasonic atomization, electrospraying, two-fluid atomization, self-volatilization (for example, the amount of volatile solvent can be adjusted and increased by increasing the volatile specific surface area, such as using a mesoporous structure, a filter structure or an ultrafine fiber structure, etc.), evaporation method (heating or friction, etc.) or inkjet method, etc.

[0029] And / or, the flow velocity of the solvent vapor is greater than 0 and less than or equal to 2 m / s, for example, 0.1 m / s, 0.3 m / s, 0.5 m / s, 0.8 m / s, 1 m / s, 1.2 m / s, 1.5 m / s, 1.8 m / s or 2 m / s.

[0030] And / or, the solvent vapor comprises a volatile solvent.

[0031] It should be noted that the present invention does not make specific requirements or special restrictions on the type of solvent in the solvent vapor provided by the gas supply device. As long as it is a volatile solvent, those skilled in the art can make adaptive selections and adjustments based on actual conditions. For example, it can be chlorobenzene, ethylene glycol monomethyl ether, ethanol or acetonitrile.

[0032] In the present invention, the solvent vapor provided by the gas supply device uses a volatile solvent, which can be easily converted into a solvent vapor state by utilizing its volatility and can quickly cover the surface of the liquid film to be dried.

[0033] As a preferred technical solution of the present invention, the acute angle between the air outlet direction of the blowing component and the plane where the liquid film to be dried is located to form an acute angle area is 15°~60°, for example, 15°, 20°, 25°, 30°, 35°, 40°, 45°, 50°, 55° or 60°, etc.

[0034] And / or, the blowing component provides a first wind flow, the flow rate of the first wind flow is 10m / s~200m / s, for example, 10m / s, 30m / s, 50m / s, 80m / s, 100m / s, 120m / s, 150m / s, 180m / s or 200m / s, etc.

[0035] And / or, the type of gas discharged from the air outlet of the blowing component includes high-pressure air or high-pressure nitrogen.

[0036] As a preferred technical solution of the present invention, the vertical distance between the air outlet of the blowing component and the liquid film to be dried is greater than 0 and less than or equal to 20 mm, for example, 1 mm, 3 mm, 5 mm, 8 mm, 10 mm, 12 mm, 15 mm, 18 mm or 20 mm, etc.

[0037] The present invention regulates the vertical distance between the air outlet and the substrate to be greater than 0 and less than or equal to 20 mm, and the acute angle between the air outlet direction and the plane where the substrate is located is 15°~60°, thereby ensuring that the subsequent coverage of the solvent vapor will follow a certain path and move along the surface of the film to be dried, thereby achieving the effect of full contact with the liquid film to be dried.

[0038] And / or, the width of the direct blowing airflow of the blowing component is 0.5mm~3mm, for example, 0.5mm, 0.8mm, 1mm, 1.2mm, 1.5mm, 1.8mm, 2mm, 2.2mm, 2.5mm, 2.8mm or 3mm, etc.

[0039] It should be noted that the present invention does not impose any specific requirements or special limitations on the specific equipment used for the blowing component, as long as it can achieve the function of blowing, for example, it can be an air knife.

[0040] As a preferred technical solution of the present invention, the concentration of the solvent vapor is greater than 0.38 mg / m 3 and is less than the saturated concentration of the solvent used in the solvent vapor in the air, for example, 0.4 mg / m 3 , 0.5mg / m 3 , 0.8mg / m 3 , 1mg / m 3 , 10mg / m 3 , 50mg / m 3 , 80mg / m 3or 100 mg / m 3 wait.

[0041] And / or, the coverage time of the solvent vapor on the surface of the liquid film to be dried is 2s to 90s, for example, 2s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s or 90s, etc.

[0042] It should be noted that, in the present invention, the coverage time of the solvent vapor on the surface of the liquid film to be dried refers to: taking point A on the film to be dried as an example, the time period from the time when the solvent vapor covers point A to the time when point A is directly blown by the first airflow for drying.

[0043] As a preferred technical solution of the present invention, the flow rate of the drainage airflow is greater than 0 and less than or equal to 20m / s, for example, 1m / s, 3m / s, 5m / s, 8m / s, 10m / s, 12m / s, 15m / s, 18m / s or 20m / s, etc.

[0044] And / or, the maximum linear length of the coverage area of ​​the solvent vapor is 1 cm to 50 cm, for example, 1 cm, 5 cm, 10 cm, 15 cm, 20 cm, 25 cm, 30 cm, 35 cm, 40 cm, 45 cm or 50 cm.

[0045] It should be noted that the maximum linear length of the coverage range of the solvent vapor in the present invention refers to the straight-line distance from the farthest edge of the coverage range of the solvent vapor to the drying position on the liquid film to be dried from the air outlet of the blowing component.

[0046] In the present invention, the maximum linear length of the coverage range of the solvent vapor is regulated to be 1 cm to 50 cm to avoid premature coverage of the vapor liquid film, which causes the mixed liquid film to be dried away from the blowing component to evaporate in advance, thereby resulting in uneven film thickness during drying and poor crystallization consistency of the film after drying.

[0047] And / or, the movement speed of the liquid film to be dried is 5 mm / s to 30 mm / s, for example, 5 mm / s, 10 mm / s, 15 mm / s, 20 mm / s, 25 mm / s or 30 mm / s, or the movement speed of the blowing component is 5 mm / s to 30 mm / s, for example, 5 mm / s, 10 mm / s, 15 mm / s, 20 mm / s, 25 mm / s or 30 mm / s, etc.

[0048] It should be noted that, during the drying process of the present invention, the liquid film to be dried can be fixed or movable. If the liquid film to be dried is fixed, the blowing component is movable; if the liquid film to be dried is movable, the blowing component is fixed. Those skilled in the art can make adaptive selections and adjustments based on actual conditions.

[0049] In a third aspect, the present invention further provides a perovskite solar cell assembly, comprising a perovskite light-absorbing layer, wherein the perovskite light-absorbing layer is dried using the thin film drying device described in the first aspect, or the thin film drying method described in the second aspect.

[0050] Compared with the prior art, the present invention has at least the following beneficial effects:

[0051] 1) In the thin film drying device provided by the present invention, the blowing component and the air supply device are independently arranged and not connected, and each performs a corresponding function. The device is simple and has low assembly cost. It is suitable for drying most functional material films, and is particularly suitable for improving the crystallization quality of large-area functional material films, thereby improving the film formation quality of the dried film and alleviating interface defects between the film and other materials.

[0052] 2) The thin film drying method of the present invention utilizes the airflow movement pattern of the blowing component to cover the solvent vapor on the surface of the liquid film to be dried. The covering speed is fast, the coverage area is full, and the coverage volume is large. Moreover, the covering method is passive and does not require external force. Therefore, it will not disturb the airflow around the blowing component and will not have any negative impact on the drying process. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 It is a schematic structural diagram of the thin film drying device provided in Example 1 of the present invention.

[0054] Figure 2 It is a side view of a physical model of the thin film drying device provided in Example 1 of the present invention.

[0055] Figure 3 Schematic diagram of the film drying method provided in Example 1 of the present invention.

[0056] Figure 4 It is a schematic structural diagram of a thin film drying device provided in Example 2 of the present invention.

[0057] Figure 5 This is a three-dimensional diagram of the thin film drying device provided in Example 3 of the present invention.

[0058] Figure 6 It is a structural schematic diagram of the thin film drying device provided in Comparative Example 1 of the present invention.

[0059] Figure 7Schematic diagram of the film drying method provided in Comparative Example 1 of the present invention.

[0060] Figure 8 This is a surface SEM image of the dried perovskite film provided in Example 1 of the present invention.

[0061] Figure 9 This is a surface SEM image of the dried perovskite film provided in Comparative Example 1 of the present invention.

[0062] Figure 10 3 is a comparison chart of XRD of the dried perovskite films provided in Example 1 of the present invention and Comparative Example 1.

[0063] Among them, 1-perovskite liquid film to be dried; 2-thermal evaporation device and supporting dispersion device; 21-solvent vapor outlet; 3-air knife; 4-drying perovskite film; 5-drainage airflow with acetonitrile solvent vapor; 6-drainage airflow; 7-first airflow. DETAILED DESCRIPTION

[0064] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0065] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0066] The specific embodiments of the present invention take the drying of perovskite liquid film as an example, but the film drying device and film drying method provided by the present invention are not limited to the drying of perovskite liquid film, but are also applicable to the drying of other functional liquid films.

[0067] Example 1

[0068] This embodiment provides a thin film drying device for drying perovskite liquid film, the structural diagram of which is shown in FIG. Figure 1 As shown, the side view of the physical model is as follows Figure 2 As shown, the film drying device includes an air knife 3 (fixed) and a heat evaporation device and a matching dispersion device 2, wherein Figure 2 In the side view of the physical model, the white area corresponding to the outlet position of the acetonitrile vapor is the area where the acetonitrile vapor is located.

[0069] The air knife 3 is inclined to the right with respect to the normal direction of the perovskite liquid film 1 to be dried as a reference, and is sandwiched with the plane where the perovskite liquid film to be dried to form an acute angle area, and the acute angle α is 45° (the angle between the first air flow 7 provided by the air knife 3 in the first direction toward the perovskite liquid film 1 to be dried and the plane where the perovskite liquid film 1 to be dried is also 45°), the vertical distance between the air outlet of the air knife 3 and the perovskite liquid film 1 to be dried is 10 mm, and the outlet 21 of the solvent vapor provided by the thermal evaporation device and the matching dispersion device 2 is located 300 mm horizontally from the air outlet of the air knife 3 and 50 mm vertically from the perovskite liquid film 1 to be dried, and the carrier of the perovskite liquid film 1 to be dried is a glass substrate.

[0070] This embodiment also provides a thin film drying method (the drying object is the perovskite liquid film to be dried). The thin film drying method is performed using the above-mentioned thin film drying device. The schematic diagram of the drying method is shown in FIG. Figure 3 As shown, the thin film drying method includes: coating a perovskite liquid film 1 to be dried (the perovskite material is MAPbI3, and the solvent is DMF:DMSO=10:1) on the surface of a glass substrate, turning on an air knife 3 to provide a first air flow 7 of high-pressure air at a speed of 45-55 m / s in a 45° direction (the angle between the first air flow and the plane where the perovskite liquid film to be dried is 45°), forming a drainage zone in the acute angle region between the outlet direction of the air knife and the plane where the perovskite liquid film to be dried is located, and a drainage air flow 6 with a flow rate of 0.8-1.2 m / s exists inside the drainage zone (due to the acetonitrile solvent vapor being carried, Figure 3 The drainage airflow 6 is not shown).

[0071] Turn on the thermal evaporation device and the supporting dispersion device 2, and provide acetonitrile solvent vapor with a flow rate of 0.8~1.2m / s, the particle diameter of the acetonitrile solvent vapor is 0.05~0.2μm, and the concentration is 36~40g / m 3 The drainage air flow 5 carrying acetonitrile solvent vapor is covered on the surface of the perovskite liquid film to be dried. While covering, the acetonitrile solvent vapor is also partially miscible with the DMF and DMSO solvents in the perovskite liquid film to be dried, and the miscibility ratio is 8-12%, thereby forming a perovskite mixed liquid film to be dried. The coverage time of the acetonitrile solvent vapor on the surface of the liquid film to be dried is 10 seconds, and the maximum linear length of the coverage range of the acetonitrile solvent vapor is 20 cm.

[0072] The glass substrate is moved from right to left at a speed of 20 mm / s. The surface of the dried perovskite mixed liquid film is blown by a first air flow of high-pressure air with a flow rate of 45-55 m / s. The acetonitrile solvent vapor evaporates and drives the DMF and DMSO solvents to evaporate, thereby obtaining a dry perovskite film 4.

[0073] Among them, regarding the thermal evaporation device and the matching dispersion device, the thermal evaporation device is used to prepare acetonitrile solvent into acetonitrile solvent vapor in steam form, obtaining droplet particles with a diameter of 0.05~0.2μm, and then a micro fan is used to blow the acetonitrile solvent vapor to move in a specified direction. A dispersion plate is set on the blowing direction path, which is a multi-layer mesh structure with adjustable size to control the distribution uniformity and flow rate of the acetonitrile solvent vapor.

[0074] Example 2

[0075] This embodiment provides a thin film drying device for drying perovskite liquid film, the structural diagram of which is shown in FIG. Figure 4 As shown, the film drying device includes an air knife 3 (fixed) and a heat evaporation device and a matching dispersion device 2.

[0076] The air knife 3 is inclined to the left with respect to the normal direction of the perovskite liquid film 1 to be dried, and is sandwiched with the plane where the perovskite liquid film 1 to be dried is located to form an acute angle area, and the acute angle α is 60° (the angle between the first airflow provided by the air knife 3 in the first direction toward the perovskite liquid film 1 to be dried and the plane where the perovskite liquid film 1 to be dried is also 60°), the vertical distance between the air outlet of the air knife 3 and the perovskite liquid film 1 to be dried is 10 mm, and the outlet 21 of the solvent vapor provided by the thermal evaporation device and the matching dispersion device 2 is located 300 mm horizontally from the air outlet of the air knife 3 and 50 mm vertically from the perovskite liquid film 1 to be dried, and the carrier of the perovskite liquid film 1 to be dried is a glass substrate.

[0077] This embodiment also provides a thin film drying method (the drying object is a perovskite liquid film to be dried), which is performed using the above-mentioned thin film drying device. The thin film drying method includes: coating the perovskite liquid film to be dried (the perovskite material is MAPbI3, and the solvent is DMF:DMSO=10:1) on the surface of a glass substrate, turning on the air knife to provide a first airflow of high-pressure air at a speed of 45~55m / s in a 60° direction (the angle between the first airflow and the plane where the liquid film to be dried is 60°), forming a drainage zone in the acute angle area between the air outlet direction of the air knife and the plane where the perovskite liquid film to be dried is located, and a drainage airflow with a flow rate of 0.3~0.6m / s exists inside the drainage zone.

[0078] Turn on the thermal evaporation device and the supporting dispersion device to provide acetonitrile solvent vapor with a flow rate of 0.8~1.2m / s, the particle diameter of acetonitrile solvent vapor is 0.05~0.2μm, and the concentration is 54~60g / m 3The drainage air flow carrying acetonitrile solvent vapor is covered on the surface of the perovskite liquid film to be dried. While covering, the acetonitrile solvent vapor is also partially miscible with the DMF and DMSO solvents in the perovskite liquid film to be dried, and the miscibility ratio is 16~20%, forming a perovskite mixed liquid film to be dried. Among them, the coverage time of the acetonitrile solvent vapor on the surface of the liquid film to be dried is 25s, and the maximum linear length of the coverage range of the acetonitrile solvent vapor is 50cm.

[0079] The glass substrate is moved from left to right at a speed of 20 mm / s. The surface of the dried perovskite mixed liquid film is blown by the first air flow high-pressure air with a flow rate of 45-55 m / s. The acetonitrile solvent vapor evaporates and drives the DMF and DMSO solvents to evaporate, thereby obtaining a dry perovskite film.

[0080] Among them, regarding the thermal evaporation device and the matching dispersion device, the thermal evaporation device is used to prepare acetonitrile solvent into acetonitrile solvent vapor in steam form, obtaining droplet particles with a diameter of 0.05~0.2μm, and then a micro fan is used to blow the acetonitrile solvent vapor to move in a specified direction. A dispersion plate is set on the blowing direction path, which is a multi-layer mesh structure with adjustable size to control the distribution uniformity and flow rate of the acetonitrile solvent vapor.

[0081] Example 3

[0082] This embodiment provides a thin film drying device for drying a perovskite liquid film. The three-dimensional diagram of the thin film drying device is as follows: Figure 5 As shown, the difference from Example 1 is that the glass substrate remains stationary, the wind knife 3 is located in a movable track and is movable, and the other devices remain unchanged from Example 1.

[0083] This embodiment also provides a thin film drying method (the drying object is a perovskite liquid film to be dried). The difference between the thin film drying method and Example 1 is that the air knife is moved from left to right at a speed of 20 mm / s. Since the position of the air knife is changing, the position of the acetonitrile solvent vapor outlet is adaptively changed (the position relative to the air knife remains unchanged). The surface of the perovskite mixed liquid film to be dried is blown by a first air flow of high-pressure air with a flow rate of 45 to 55 m / s. The acetonitrile solvent vapor evaporates and drives the DMF and DMSO solvents to evaporate, thereby obtaining a dry perovskite film. The remaining drying methods and parameters are consistent with Example 1.

[0084] Example 4

[0085] This embodiment provides a thin film drying device for drying a perovskite liquid film. The difference between the thin film drying device and Example 1 is that the glass substrate remains stationary, the wind knife 3 is located in a movable track and is movable, and the remaining devices remain unchanged from Example 1.

[0086] This embodiment also provides a thin film drying method (the drying object is a perovskite liquid film to be dried). The difference between the thin film drying method and Example 1 is that the air knife is moved from right to left at a speed of 20 mm / s. Since the position of the air knife is changing, the position of the acetonitrile solvent vapor outlet is adaptively changed (the position relative to the air knife remains unchanged). The surface of the perovskite mixed liquid film to be dried is blown by a first air flow of high-pressure air with a flow rate of 45 to 55 m / s. The acetonitrile solvent vapor evaporates and drives the DMF and DMSO solvents to evaporate, thereby obtaining a dried perovskite film. The remaining drying methods and parameters are consistent with Example 1.

[0087] Comparative Example 1

[0088] This comparative example provides a thin film drying device for drying perovskite liquid film, the structural diagram of which is shown in FIG. Figure 6 As shown, the only difference from Example 1 is that the thermal evaporation device and the matching dispersion device 2 are omitted, and the rest of the device remains consistent with Example 1.

[0089] This comparative example also provides a thin film drying method (the drying object is the perovskite liquid film to be dried). The thin film drying method is carried out using the above-mentioned thin film drying device. The schematic diagram of the drying process is shown in FIG. Figure 7 As shown, the thin film drying method includes: coating the perovskite liquid film 1 to be dried (the perovskite material is MAPbI3, and the solvent is DMF:DMSO=10:1) on the surface of the glass substrate, turning on the air knife 3 to provide a first air flow 7 of high-pressure air at a speed of 45~55m / s (the angle between the first air flow and the plane where the perovskite liquid film to be dried is 45°), and forming a drainage area in the acute angle area between the air outlet direction of the air knife 3 and the plane where the perovskite liquid film to be dried 1 is located. There is a drainage air flow 6 with a flow rate of 0.8~1.2m / s inside the drainage area.

[0090] The glass substrate is moved from right to left at a speed of 20 mm / s, and the surface of the dried perovskite liquid film is blown by the first air flow high-pressure air with a flow rate of 45-55 m / s, and the DMF and DMSO solvents are evaporated to obtain a dry perovskite film.

[0091] Figure 3 FIG1 shows a schematic diagram of a thin film drying method provided in Example 1 of the present invention. Figure 7A schematic diagram of the thin film drying method provided in Comparative Example 1 of the present invention is shown. As can be seen from the figure, the distance between the position where the wind knife is directly facing the air outlet direction and the critical position of the perovskite liquid film to be dried and the dried perovskite film is defined as W1 (Example 1) and W2 (Comparative Example 1), respectively. It can be observed that W2>W1 and the fluctuation of the width of W2 is larger. In the area of ​​W2, there are also semi-wet film and semi-dry situations. That is, in Comparative Example 1, the transition time from the perovskite liquid film to be dried to the dry perovskite film is longer, the volatilization consistency of the solvent inside the perovskite liquid film to be dried will become worse, and the position of the completely dried perovskite film will fluctuate more, which in turn leads to poor crystallization consistency of the perovskite film and a significant decrease in crystallization quality.

[0092] Figure 8 The surface SEM image of the dried perovskite film provided in Example 1 of the present invention is shown. As can be seen from the image, the surface grains of the dried perovskite film are relatively large, there are no abnormal crystal grains, and the film quality is high.

[0093] Figure 9 The surface SEM image of the dried perovskite film provided in Comparative Example 1 of the present invention is shown. It can be seen from the figure that the grains on the surface of the dried perovskite film are smaller and there are other types of crystal grains, such as PbI2 crystals.

[0094] Figure 10 The XRD comparison diagrams of the dried perovskite films provided by Example 1 of the present invention and Comparative Example 1 are shown. It can be seen from the figure that the characteristic diffraction peak intensity value of Comparative Example 1 is smaller than that of Example 1, indicating that the crystallization of the dried perovskite film of Comparative Example 1 is worse than that of Example 1, and there is an additional obvious diffraction peak near 2θ of 12.6° in Comparative Example 1, which is a peak of abnormal crystallization.

[0095] The devices provided in Examples 2, 3 and 4 are used to dry the perovskite liquid film. The resulting dried perovskite film can also achieve the effect presented in Example 1, that is, the surface grains of the dried perovskite film are large, there are no abnormal crystal grains, the dried perovskite film is well crystallized, and the film quality is high.

[0096] In summary, the film drying device provided by the present invention includes a blowing component and an air supply device, which are independently arranged. The blowing component and the air supply device are driven by the drainage airflow in the drainage area (the air outlet direction of the blowing component and the plane where the liquid film to be dried are located to form an acute angle area) to drive the solvent vapor provided by the air supply device to cover the surface of the liquid film to be dried and partially dissolve with the solvent in the liquid film to be dried. After being blown by the first airflow provided by the blowing component, the solvent vapor can assist in the volatilization of the solvent in the liquid film to be dried, which can significantly accelerate the drying of the liquid film to be dried, and at the same time improve the crystallization quality during the drying process, taking into account the consistency of the crystal orientation of the film, thereby alleviating the interface defects between the film and other materials.

[0097] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A thin film drying device for drying a liquid film to be dried, characterized in that: The thin film drying device comprises: a blowing component for providing a first air flow in a first direction toward the liquid film to be dried, wherein an air outlet direction of the blowing component and a plane where the liquid film to be dried are located form an acute angle region; and a gas supply device, wherein the gas supply device provides solvent vapor; When the blowing component provides the first air flow toward the liquid film to be dried in the first direction, a drainage area is formed in the acute angle area, and the solvent vapor is passively covered to the surface of the liquid film to be dried by the drainage air flow in the drainage area. The solvent vapor assists the volatilization of the solvent in the liquid film to be dried, and the crystal orientation of the resulting dried film is consistent.

2. The thin film drying device according to claim 1, characterized in that: The solvent vapor is miscible with the solvent in the liquid film to be dried; And / or, during the mutual dissolution process between the solvent vapor and the solvent in the liquid film to be dried, the mutual dissolution ratio is 1% to 20%.

3. The thin film drying device according to claim 1, characterized in that: In the air supply device, the outlet of the solvent vapor is located at a first horizontal distance from the air outlet of the blowing component and a second vertical distance from the liquid film to be dried, the first distance is 50mm~500mm, and the second distance is 10mm~200mm.

4. The thin film drying device according to claim 1, characterized in that: The particle diameter of the solvent vapor is greater than 0 and less than or equal to 10 μm; and / or, the flow velocity of the solvent vapor is greater than 0 and less than or equal to 2 m / s; And / or, the solvent vapor comprises a volatile solvent.

5. The thin film drying device according to claim 1, characterized in that: The acute angle formed by the air outlet direction of the blowing component and the plane where the liquid film to be dried is 15° to 60°; And / or, the blowing component provides a first air flow, and the flow rate of the first air flow is 10m / s~200m / s.

6. The thin film drying device according to claim 1, characterized in that: The vertical distance between the air outlet of the blowing component and the liquid film to be dried is greater than 0 and less than or equal to 20 mm; And / or, the width of the direct blowing airflow of the blowing component is 0.5mm~3mm.

7. The thin film drying device according to claim 1, characterized in that: The concentration of the solvent vapor is>0.38mg / m 3 and is less than the saturated concentration of the solvent used in the solvent vapor in the air; And / or, the coverage time of the solvent vapor on the surface of the liquid film to be dried is 2s to 90s.

8. The thin film drying device according to claim 1, characterized in that: The flow rate of the drainage airflow is greater than 0 and less than or equal to 20 m / s; and / or, the maximum linear length of the coverage area of ​​the solvent vapor is 1 cm to 50 cm; And / or, the movement speed of the liquid film to be dried is 5 mm / s to 30 mm / s, or the movement speed of the blowing component is 5 mm / s to 30 mm / s.

9. A film drying method, characterized in that: The film drying method comprises: A blowing component is used to provide a first air flow in a first direction toward the liquid film to be dried, and a drainage area is formed in an acute angle region between the air outlet direction of the blowing component and the plane where the liquid film to be dried is located, wherein a drainage air flow exists in the drainage area; Solvent vapor is provided by an air supply device and passively covered on the surface of the liquid film to be dried through the drainage airflow. The solvent vapor assists in volatilization of the solvent in the liquid film to be dried, and the crystal orientation of the obtained dried film is consistent.

10. The thin film drying method according to claim 9, characterized in that: The solvent vapor is miscible with the solvent in the liquid film to be dried; And / or, during the mutual dissolution process between the solvent vapor and the solvent in the liquid film to be dried, the mutual dissolution ratio is 1% to 20%.

11. The thin film drying method according to claim 9, characterized in that: In the air supply device, the outlet of the solvent vapor is located at a first horizontal distance from the air outlet of the blowing component and a second vertical distance from the liquid film to be dried, the first distance is 50mm~500mm, and the second distance is 10mm~200mm.

12. The thin film drying method according to claim 9, characterized in that: The particle diameter of the solvent vapor is greater than 0 and less than or equal to 10 μm; and / or, the flow velocity of the solvent vapor is greater than 0 and less than or equal to 2 m / s; And / or, the solvent vapor comprises a volatile solvent.

13. The thin film drying method according to claim 9, characterized in that: The acute angle formed by the air outlet direction of the blowing component and the plane where the liquid film to be dried is 15° to 60°; And / or, the blowing component provides a first air flow, and the flow rate of the first air flow is 10m / s~200m / s.

14. The thin film drying method according to claim 9, characterized in that: The vertical distance between the air outlet of the blowing component and the liquid film to be dried is greater than 0 and less than or equal to 20 mm; And / or, the width of the direct blowing airflow of the blowing component is 0.5mm~3mm.

15. The thin film drying method according to claim 9, characterized in that: The concentration of the solvent vapor is>0.38mg / m 3 and is less than the saturated concentration of the solvent used in the solvent vapor in the air; And / or, the coverage time of the solvent vapor on the surface of the liquid film to be dried is 2s to 90s.

16. The thin film drying method according to claim 9, characterized in that: The flow rate of the drainage airflow is greater than 0 and less than or equal to 20 m / s; and / or, the maximum linear length of the coverage area of ​​the solvent vapor is 1 cm to 50 cm; And / or, the movement speed of the liquid film to be dried is 5 mm / s to 30 mm / s, or the movement speed of the blowing component is 5 mm / s to 30 mm / s.

17. A perovskite solar cell module, characterized in that: The perovskite solar cell assembly includes a perovskite light-absorbing layer, and the perovskite light-absorbing layer is dried using the thin film drying device according to any one of claims 1 to 8, or the thin film drying method according to any one of claims 9 to 16.

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