Rapid annealing equipment and rapid annealing process for large-area perovskite thin film

Abstract

The invention provides rapid annealing equipment for a large-area perovskite thin film and a rapid annealing process of the large-area perovskite thin film. The rapid annealing equipment comprises a shell, a rapid drying area, a constant-temperature drying area and a cooling area are sequentially arranged in the shell, a substrate inlet and a substrate outlet are formed in the shell, the substrate inlet is located in the rapid drying area, and the substrate outlet is located in the cooling area; a first heating piece and an air knife are arranged in the upper space of the quick drying area from top to bottom, and a second heating piece is arranged in the upper space of the constant-temperature drying area; and the conveying mechanism is used for conveying a perovskite substrate to be subjected to film formation to sequentially pass through the lower spaces of the quick drying area, the constant-temperature drying area and the cooling area. The rapid annealing equipment not only can carry out the steps of rapid heating seed crystal generation, grain growth, cooling and the like to realize multifunctional integration, efficiency improvement and cost reduction of the equipment, but also is compatible with preparation of a large-area perovskite thin film, and has a good industrial prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of solar cells and relates to the technical field of perovskite thin films, and in particular to a rapid annealing device for a large-area perovskite thin film and a rapid annealing process thereof. Background Art

[0002] After 50 years of development, solar photovoltaic modules are divided into the first generation of crystalline silicon solar cells, the second generation of semiconductor compound thin film cells and the third generation of perovskite solar cells. The technological iteration of solar cells is one of the important ways to reduce the cost of electricity, but with the continuous deepening of the industrialization process of perovskites, improving efficiency and reducing costs will become the main direction of the sustainable development of perovskites. The crystallization quality of perovskite materials plays a vital role in the efficiency and stability of modules. Therefore, improving the crystallization quality of large-area perovskite films is conducive to the sustainable development of the perovskite industry.

[0003] The existing large-area perovskite film preparation process is mainly achieved by slit coating + vacuum drying + post-annealing. The perovskite wet film after slit coating is crystallized by vacuum drying to obtain a semi-dry perovskite intermediate phase, and the intermediate phase is then annealed to obtain the final perovskite film. However, since the intermediate phase after vacuum drying is a complex of perovskite and a non-volatile solvent, post-annealing has higher requirements for the heating rate. The slower heating rate will increase the residual time of the non-volatile solvent, resulting in poor crystallization quality of the perovskite film. Existing annealing equipment often uses upper and lower hot plates and minimizes the distance between the upper and lower hot plates to ensure transmission, but since the heat transfer method is thermal radiation, the conduction efficiency is low, so it cannot meet the heating rate requirements. When using an infrared lamp with a faster heating rate for heating, since the lamp is a point light source, the infrared light is conducted in a fan-shaped form. There is a junction at the junction of the infrared lamp tube, resulting in heat superposition, which ultimately leads to the existence of a light and dark boundary on the perovskite film, affecting the performance of the perovskite component.

[0004] Therefore, exploring a technology that can effectively increase the heating rate of annealing equipment is crucial to improving the perovskite precursor window, perovskite film crystallization quality, battery efficiency, battery stability, and improving efficiency and reducing costs. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide a rapid annealing device and a rapid annealing process for a large-area perovskite film. The present invention can quickly transfer heat to the substrate surface by adding a rapid drying zone, and using the cooperation of the first heating element and the wind knife in the rapid drying zone, and quickly increase the heating rate of the substrate surface, thereby reducing the residence time of the residual solvent in the perovskite intermediate phase, significantly improving the crystallization quality of the perovskite film, and ultimately improving the efficiency and stability of the battery; and the addition of the rapid drying zone can increase the optimization window of the perovskite precursor liquid system, and quickly introduce the small-size perovskite precursor liquid system into the preparation of a large-area perovskite film. Therefore, the rapid annealing equipment can not only perform the steps of rapid temperature increase seed crystal generation, grain growth and cooling, realize the multifunctional integration of the equipment, improve efficiency and reduce costs, but also be compatible with the preparation of large-area perovskite films, and have good industrial prospects.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a rapid annealing device for a large-area perovskite film, the rapid annealing device comprising:

[0008] A shell, wherein a quick drying zone, a constant temperature drying zone and a cooling zone are sequentially arranged in the shell, and a substrate inlet and a substrate outlet are provided on the shell, wherein the substrate inlet is located in the quick drying zone, and the substrate outlet is located in the cooling zone; a first heating element and an air knife are arranged in the upper space of the quick drying zone from top to bottom, and a second heating element is arranged in the upper space of the constant temperature drying zone.

[0009] A conveying mechanism is used to transport the perovskite film-forming substrate to pass through the rapid drying zone, the constant temperature drying zone and the lower space of the cooling zone in sequence.

[0010] The present invention can quickly transfer heat to the substrate surface by adding a quick drying zone, and using the cooperation of the first heating element and the wind knife in the quick drying zone, and quickly increase the heating rate of the substrate surface, thereby reducing the residence time of the residual solvent in the perovskite intermediate phase, significantly improving the crystallization quality of the perovskite film, and ultimately improving the efficiency and stability of the battery; and the addition of the quick drying zone can increase the optimization window of the perovskite precursor liquid system, and quickly introduce the small-size perovskite precursor liquid system into the preparation of a large-area perovskite film. Therefore, the rapid annealing equipment can not only perform the steps of rapid temperature increase seed crystal generation, grain growth and cooling, realize the multifunctional integration of the equipment, improve efficiency and reduce costs, and is compatible with the preparation of large-area perovskite films, and has good industrial prospects.

[0011] Preferably, the first heating element and the second heating element each independently include any one of a hot air heating element, a hot plate heating element, an electric heating tube heating element or an infrared lamp tube heating element, or a combination of at least two of them.

[0012] Preferably, the temperature control range of the first heating element and the second heating element is independently 100-200°C, for example, it can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, etc.

[0013] Preferably, the air outlet temperature of the air knife is 50-200°C, for example, it can be 50°C, 100°C, 150°C or 200°C.

[0014] Preferably, the wind knife has an air inlet and an air outlet, the air inlet is close to the first heating element, the air outlet is close to the perovskite film-forming substrate, and the hot air flow blown out of the air outlet directly acts on the surface of the perovskite film-forming substrate.

[0015] Preferably, the vertical distance between the air outlet of the wind knife and the perovskite film-forming substrate passing through the rapid drying zone is 3-10 cm, for example, it can be 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm or 10 cm.

[0016] Preferably, the air knife pressure of the air knife is 0.05-0.5 MPa, for example, it can be 0.05 MPa, 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa or 0.5 MPa.

[0017] Preferably, a plurality of wind knives arranged in parallel are provided in the upper space of the rapid drying zone, and the wind knives are parallel to each other and are also parallel to the surface of the first heating element.

[0018] Preferably, the number of the wind knives is 1-10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, etc.

[0019] Preferably, the interval width between adjacent wind knives is 5-50 cm, for example, it may be 5 cm, 8 cm, 10 cm, 12 cm, 15 cm, 20 cm, 30 cm, 40 cm or 50 cm.

[0020] Preferably, the conveying mechanism includes a carrier and a transmission track, the carrier is connected to the transmission track via a transmission roller, and the carrier carries the perovskite film-forming substrate to pass through the rapid drying zone, the constant temperature drying zone and the lower space of the cooling zone in sequence.

[0021] Preferably, the transmission speed of the carrier in the rapid drying zone is denoted as V1, and V1 is 0.1-1 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min, 0.9 m / min or 1 m / min.

[0022] Preferably, the transmission speed of the carrier in the constant temperature drying zone is denoted as V2, and V2 is 0.1-1 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min, 0.9 m / min or 1 m / min.

[0023] Preferably, V1 is greater than V2.

[0024] Preferably, the transmission speed of the carrier in the cooling zone is denoted as V3, where V3=V2.

[0025] It should be noted that the transmission speeds of the rapid drying zone, the constant temperature drying zone and the cooling zone are adjustable separately.

[0026] Preferably, a third heating element is provided on the carrier, and the third heating element is located below the perovskite film-forming substrate and is used for heating the perovskite film-forming substrate.

[0027] Preferably, the third heating element comprises any one of a hot air heating element, a hot plate heating element, an electric heating tube heating element or an infrared lamp tube heating element, or a combination of at least two of them.

[0028] Preferably, the temperature control range of the third heating element is 100-180°C, for example, it may be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C.

[0029] Preferably, the vertical distance between the lower surface of the second heating element and the perovskite film-forming substrate passing through the constant temperature drying zone is 1-10 cm, for example, it can be 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm or 10 cm, etc.

[0030] Preferably, the cooling zone is provided with a cooling element, which is located in the upper space of the cooling zone and is used to cool the perovskite film-forming substrate passing through the cooling zone. Preferably, the temperature control range of the cooling zone is 20-50°C, for example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C.

[0031] Preferably, the cooling element comprises a cooling fan.

[0032] Preferably, a perforated steel plate is provided below the cooling zone to discharge the hot air blown downward by the cooling fan to an exhaust member for collection.

[0033] Preferably, the exhaust member comprises an exhaust fan.

[0034] In a second aspect, the present invention provides a rapid annealing process for a large-area perovskite film, wherein the rapid annealing process is performed in the rapid annealing device as described in the first aspect, and comprises the following steps:

[0035] The perovskite film-forming substrate coated with the perovskite precursor film is placed on a carrier, enters the substrate inlet through the carrier, and then passes through the rapid drying zone, constant temperature drying zone and lower space of the cooling zone of the rapid annealing equipment in sequence, and then passes through the substrate outlet to obtain a large-area perovskite film.

[0036] Preferably, the coating method of the perovskite precursor film comprises the following steps:

[0037] The perovskite precursor solution is coated on a perovskite film-forming substrate, and then dried and crystallized to obtain a perovskite precursor film.

[0038] Preferably, the chemical formula of the perovskite precursor solution is Cs x (FA y MA 1-y ) 1-x Pb(I z Br 1-z )3, wherein x≤1, for example, it can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, y≤1, for example, it can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, and z≤1, for example, it can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, etc.

[0039] Preferably, the concentration of the perovskite precursor solution is 0.2-1.5 mol / L, for example, 0.2 mol / L, 0.5 mol / L, 1 mol / L or 1.5 mol / L.

[0040] Preferably, the solvent of the perovskite precursor solution is a polyvalent solvent.

[0041] Preferably, the polysolvent includes a volatile solvent and a less volatile solvent.

[0042] Preferably, the volatile solvent includes any one or a combination of at least two of DMF (N,N-dimethylformamide), 2-Me (2-methoxyethanol), EOH (ethanol), THF (tetrahydrofuran), DMAC (N,N-dimethylacetamide), ACN (acetonitrile) or γ-GBL (γ-butyrolactone).

[0043] Preferably, the low-volatile solvent includes any one of DMSO (dimethyl sulfoxide), NMP (N-methyl-2-pyrrolidine) or DMI (dimethyl-2-imidazolidinone) or a combination of at least two thereof.

[0044] Preferably, the coating method includes a slot coating method.

[0045] Preferably, the specific parameters of the slot coating method include:

[0046] The slit coating rate is 10-60 mm / s, for example, it can be 10 mm / s, 20 mm / s, 30 mm / s, 40 mm / s, 50 mm / s or 60 mm / s, etc. The vertical distance between the slit coating head and the perovskite film-forming substrate is 50-200 μm, for example, it can be 50 μm, 100 μm, 150 μm or 200 μm, etc. The injection speed is 80-300 μL / s, for example, it can be 80 μL / s, 100 μL / s, 150 μL / s, 200 μL / s, 250 μL / s, or 300 μL / s, etc.

[0047] Preferably, the drying and crystallization method comprises vacuum drying.

[0048] Preferably, the vacuum drying time is 10-100 s, for example, it can be 10 s, 30 s, 50 s, 70 s, 90 s or 100 s.

[0049] Preferably, in the vacuum drying equipment for performing the vacuum drying, the cavity pressure is 0.1-100 Pa, for example, it may be 0.1 Pa, 1 Pa, 10 Pa, 30 Pa, 50 Pa, 70 Pa or 90 Pa.

[0050] Preferably, the rapid drying time of the perovskite film-forming substrate in the rapid drying zone is 1-10 min, for example, it can be 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min, etc.

[0051] Preferably, the constant temperature drying time of the perovskite film-forming substrate in the constant temperature drying zone is 10-30 min, for example, 10 min, 15 min, 20 min, 25 min or 30 min.

[0052] For example, the present invention does not specifically limit the area of ​​the large-area perovskite film, for example, it can be 300×400 mm, 1200×600 mm or 2400 mm×1200 mm.

[0053] In a third aspect, the present invention provides a perovskite solar cell, comprising a stacked TCO glass, a first carrier transport layer, a perovskite film, a second carrier transport layer and an electrode, wherein a rapid annealing process for preparing the perovskite film adopts the rapid annealing process described in the second aspect.

[0054] Preferably, the first carrier transport layer and the second carrier transport layer transport charges of opposite electrical properties.

[0055] Preferably, the first carrier transport layer is an electron transport layer, and the second carrier transport layer is a hole transport layer.

[0056] Preferably, the electron transport layer comprises a tin dioxide layer, a C 60 Any one of the layers or PCBM layers or a combination of at least two.

[0057] Preferably, the hole transport layer includes any one of a nickel oxide layer, a PEDOT:PSS layer, a PTAA layer or a Spiro-OMeTAD layer, or a combination of at least two thereof.

[0058] Preferably, the electrode is a metal electrode, and illustratively, it can be any one of an Ag electrode, an Au electrode or a Cu electrode.

[0059] However, it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0060] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] (1) The present invention adds a rapid drying zone and uses the cooperation of the first heating element and the air knife in the rapid drying zone to quickly transfer heat to the substrate surface, quickly increase the heating rate of the substrate surface, thereby reducing the residence time of the residual solvent in the perovskite intermediate phase, significantly improving the crystallization quality of the perovskite film, and ultimately improving the efficiency and stability of the battery; secondly, the uniformity requirement of the perovskite intermediate phase to the air knife is low, and it is simple and easy to process with low cost; and the addition of the rapid drying zone can increase the optimization window of the perovskite precursor solution system, and quickly introduce the small-size perovskite precursor solution system into the preparation of a large-area perovskite film.

[0063] (2) The rapid annealing equipment and rapid annealing process provided by the present invention are both automated, and can not only perform the steps of rapid heating seed crystal generation, grain growth and cooling, realize the multifunctional integration of the equipment, improve efficiency and reduce costs, but also are compatible with the preparation of large-area perovskite films. It is only necessary to widen the size of the equipment body, transmission mechanism, wind knife and other components to achieve compatibility. The uniformity of the film can meet the requirements, and it has a good industrial prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 A side view of the rapid annealing equipment provided by the present invention.

[0065] Figure 2 A top view of the rapid annealing equipment provided by the present invention.

[0066] Figure 3 Front view of the rapid annealing equipment provided by the present invention

[0067] Figure 4 This is a comparison diagram of the XRD curves of the large-area perovskite film provided in Example 1 of the present invention and Comparative Example 1.

[0068] Figure 5 This is a SEM image of the large-area perovskite film provided in Example 1 of the present invention.

[0069] Figure 6 This is a SEM image of the large-area perovskite film provided in Comparative Example 1 of the present invention.

[0070] Figure 7 This is a comparison chart of changes in annealing heating rate in the rapid annealing process provided in Example 1 of the present invention and Comparative Example 1.

[0071] Among them, 1-quick drying area; 2-constant temperature drying area; 3-cooling area; 4-first heating element; 5-wind knife; 6-second heating element; 7-carrier; 8-transmission track; 9-third heating element; 10-cooling element. DETAILED DESCRIPTION

[0072] It should be understood that, in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", etc., indicating the orientation or positional relationship are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention. In addition, the terms "first", "second", etc. are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first", "second", etc. may explicitly or implicitly include one or more of the features. In the description of the present invention, unless otherwise specified, "multiple" means two or more.

[0073] It should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "disposed", "connected", and "connected" 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 by specific circumstances.

[0074] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0075] In a specific embodiment, the present invention provides a rapid annealing device for a large-area perovskite film, the side view, top view and front view of which are as follows: Figure 1 , Figure 2 and Figure 3 As shown, the rapid annealing equipment comprises:

[0076] A shell, wherein a quick drying zone 1, a constant temperature drying zone 2 and a cooling zone 3 are sequentially arranged in the shell, and a substrate inlet and a substrate outlet are provided on the shell, wherein the substrate inlet is located in the quick drying zone 1, and the substrate outlet is located in the cooling zone 3; in the upper space of the quick drying zone 1, a first heating element 4 and a wind knife 5 are arranged from top to bottom, and in the upper space of the constant temperature drying zone 2, a second heating element 6 is arranged.

[0077] The conveying mechanism is used to transport the perovskite film-forming substrate to pass through the lower space of the rapid drying zone 1, the constant temperature drying zone 2 and the cooling zone 3 in sequence.

[0078] The present invention can quickly transfer heat to the substrate surface by adding a quick drying zone 1, and using the cooperation of the first heating element 4 and the wind knife 5 in the quick drying zone 1, and quickly increase the heating rate of the substrate surface, thereby reducing the residence time of the residual solvent in the perovskite intermediate phase, significantly improving the crystallization quality of the perovskite film, and ultimately improving the efficiency and stability of the battery; and the addition of the quick drying zone 1 can increase the optimization window of the perovskite precursor liquid system, and quickly introduce the small-size perovskite precursor liquid system into the preparation of a large-area perovskite film. Therefore, the rapid annealing equipment can not only perform the steps of rapid temperature increase seed crystal generation, grain growth and cooling, realize the multifunctional integration of the equipment, improve efficiency and reduce costs, and is compatible with the preparation of large-area perovskite films, and has good industrial prospects.

[0079] Furthermore, the first heating element 4 and the second heating element 6 independently include any one of a hot air heating element, a hot plate heating element, an electric heating tube heating element or an infrared lamp tube heating element, or a combination of at least two of them.

[0080] Furthermore, the temperature control range of the first heating element 4 and the second heating element 6 is independently 100-200°C, for example, it can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C, etc.

[0081] Furthermore, the air outlet temperature of the air knife 5 is 50-200°C, for example, it can be 50°C, 100°C, 150°C or 200°C.

[0082] In the present invention, the air outlet temperature of the wind knife 5 is kept consistent with the temperature of the first heating element 4. The same temperature enables the perovskite film to crystallize at the same temperature, thereby ensuring the film quality.

[0083] Furthermore, the wind knife 5 has an air inlet and an air outlet, the air inlet is close to the first heating element 4, the air outlet is close to the perovskite film-forming substrate, and the hot air flow blown out of the air outlet directly acts on the surface of the perovskite film-forming substrate.

[0084] In the present invention, the design of the above-mentioned wind knife 5 can quickly transfer heat to the surface of the perovskite film-forming substrate, quickly increase the surface heating rate of the perovskite film-forming substrate, reduce the residence time of the residual solvent in the perovskite intermediate phase, improve the perovskite crystallization performance and ultimately improve the device efficiency.

[0085] Furthermore, the vertical distance between the air outlet of the wind knife 5 and the perovskite film-forming substrate passing through the rapid drying zone 1 is 3-10 cm, for example, it can be 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm or 10 cm.

[0086] In the present invention, the wind knife 5 at a suitable position helps to ensure temperature uniformity and prevent temperature non-uniformity from causing different perovskite crystal orientations in different regions.

[0087] Furthermore, the air knife pressure of the air knife 5 is 0.05-0.5 MPa, for example, it can be 0.05 MPa, 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa or 0.5 MPa.

[0088] In the present invention, the wind knife 5 with appropriate wind knife pressure helps to ensure the heating rate of the perovskite film. Too much pressure will lead to uneven amplification of the wind knife itself, resulting in different crystal orientations in different regions. Too low pressure will make the film heating rate fail to meet the requirements.

[0089] Furthermore, a plurality of wind knives 5 arranged in parallel are provided in the upper space of the rapid drying zone 1 , and the wind knives 5 are parallel to each other and are also parallel to the surface of the first heating element 4 .

[0090] In the present invention, multiple wind knives 5 arranged in parallel are provided to help ensure the heating rate of the perovskite. A single wind knife requires a slower speed and cannot meet the production rhythm required. By increasing the number of wind knives, the mass production rhythm requirements can be met.

[0091] Furthermore, the number of the wind knives 5 is 1-10, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, etc.

[0092] Furthermore, the interval width between adjacent wind knives 5 is 5-50 cm, for example, it can be 5 cm, 8 cm, 10 cm, 12 cm, 15 cm, 20 cm, 30 cm, 40 cm or 50 cm.

[0093] In the present invention, the air knives 5 with suitable spacing width are helpful to meet the temperature increase requirements under a faster production cycle, and the suitable width can effectively discharge the volatile organic gas.

[0094] Furthermore, the conveying mechanism includes a carrier 7 and a transmission track 8, and the carrier 7 is connected to the transmission track through a transmission roller. The carrier 7 carries the perovskite film-forming substrate to pass through the lower space of the rapid drying zone 1, the constant temperature drying zone 2 and the cooling zone 3 in sequence.

[0095] Furthermore, the transmission speed of the carrier 7 in the rapid drying zone 1 is denoted as V1, and V1 is 0.1-1 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min, 0.9 m / min or 1 m / min.

[0096] Furthermore, the transmission speed of the carrier 7 in the constant temperature drying zone 2 is denoted as V2, and V2 is 0.1-1 m / min, for example, it can be 0.1 m / min, 0.3 m / min, 0.5 m / min, 0.7 m / min, 0.9 m / min or 1 m / min.

[0097] Furthermore, V1 is greater than V2.

[0098] In the present invention, V1 is limited to be greater than V2, so as to reduce the exposure time of the film in the air before the perovskite crystallization, thereby improving the film quality. The longer the residence time, the more susceptible the film is to the influence of the air, which affects the crystallization of the film.

[0099] Furthermore, the transmission speed of the carrier 7 in the cooling zone 3 is recorded as V3, and V3=V2.

[0100] Furthermore, a third heating element 9 is disposed on the carrier 7 , and the third heating element 9 is located below the perovskite film-forming substrate, and is used for heating the perovskite film-forming substrate.

[0101] In the present invention, the heat convection radiation of the wind knife 5 + the first heating element 4 and the third heating element 9 arranged up and down are different from the traditional hot air convection, which can quickly transfer heat to the surface of the substrate, quickly increase the heating rate of the substrate surface, reduce the residence time of the residual solvent in the intermediate phase, improve the crystallization performance of the perovskite and ultimately improve the device efficiency.

[0102] Furthermore, the third heating element 9 includes any one of a hot air heating element, a hot plate heating element, an electric heating tube heating element or an infrared lamp tube heating element, or a combination of at least two of them.

[0103] Further, the temperature control range of the third heating element 9 is 100-180°C, for example, it can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C.

[0104] Furthermore, the vertical distance between the lower surface of the second heating element 6 and the perovskite film-forming substrate passing through the constant temperature drying zone 2 is 1-10 cm, for example, it can be 1 cm, 2 cm, 3 cm, 4 cm, 5 cm, 6 cm, 7 cm, 8 cm, 9 cm or 10 cm, etc.

[0105] Furthermore, the cooling zone 3 is provided with a cooling element 10 , and the cooling element 10 is located in the upper space of the cooling zone 3 , and is used to cool the perovskite film-forming substrate passing through the cooling zone 3 .

[0106] Furthermore, the temperature control interval of the cooling zone 3 is 20-50°C, for example, it can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C.

[0107] Furthermore, the cooling element 10 includes a cooling fan.

[0108] Furthermore, a perforated steel plate is provided below the cooling zone to discharge the hot air blown downward by the cooling fan to an exhaust member for collection.

[0109] Furthermore, the exhaust member includes an exhaust fan.

[0110] In another specific embodiment, the present invention provides a rapid annealing process for a large-area perovskite film, wherein the rapid annealing process is performed in the rapid annealing device as described above, and comprises the following steps:

[0111] The perovskite film-forming substrate coated with the perovskite precursor film is placed on a carrier, enters the substrate inlet through the carrier, and then passes through the rapid drying zone, constant temperature drying zone and lower space of the cooling zone of the rapid annealing equipment in sequence, and then passes through the substrate outlet to obtain a large-area perovskite film.

[0112] Example 1

[0113] This embodiment provides a rapid annealing process for a large-area perovskite film, and the rapid annealing process includes the following steps:

[0114] (1) The perovskite precursor solution is coated on the perovskite film-forming substrate by a slit coating method, and then placed in a vacuum drying device for vacuum drying and crystallization to obtain a perovskite precursor film.

[0115] The chemical formula of the perovskite precursor solution is (Cs 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 )3, the concentration is 1.2 mol / L, and the solvents include DMF, ACN, DMSO and DMI in a volume ratio of 4:2:1:1; the specific parameters of the slit coating method include: the slit coating rate is 20 mm / s, the vertical distance between the slit coating head and the perovskite film-forming substrate is 200 μm, and the injection speed is 220 μL / s; the vacuum drying time is 10 s, and the chamber pressure during vacuum drying crystallization is 100 Pa.

[0116] (2) The perovskite film-forming substrate coated with the perovskite precursor film is placed on a carrier, enters the substrate inlet of the rapid annealing equipment through the carrier, and then passes through the lower space of the rapid drying zone at a transmission speed of 0.5 m / min for 5 min, and then passes through the lower space of the constant temperature drying zone at a transmission speed of 0.2 m / min for 18 min, and then passes through the lower space of the cooling zone at a transmission speed of 0.2 m / min, and then passes through the substrate outlet to obtain a large-area perovskite film with an area of ​​1200×600 mm and a thickness of 3.2 mm.

[0117] Among them, the first heating element in the rapid drying zone is an electric heating tube heating element, and the heating temperature is 150°C; the third heating element is an electric heating tube heating element, and the heating temperature is 150°C; the number of wind knives is 5, the wind knife pressure is 0.3MPa, the air outlet temperature of the wind knife is 150°C, the vertical distance between the air outlet of the wind knife and the perovskite film-forming substrate passing through the rapid drying zone is 10cm, and the interval width between adjacent wind knives is 20cm; the second heating element in the constant temperature drying zone is an electric heating tube heating element, and the heating temperature is 150°C; the vertical distance between the lower surface of the second heating element and the perovskite film-forming substrate passing through the constant temperature drying zone is 2cm; the cooling element in the cooling zone is a cooling fan, and the cooling temperature is 20°C.

[0118] Example 2

[0119] This embodiment provides a rapid annealing process for a large-area perovskite film, and the rapid annealing process includes the following steps:

[0120] (1) The perovskite precursor solution is coated on the perovskite film-forming substrate by a slit coating method, and then placed in a vacuum drying device for vacuum drying and crystallization to obtain a perovskite precursor film.

[0121] The chemical formula of the perovskite precursor solution is (Cs 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 )3, the concentration is 0.5 mol / L, and the solvent includes DMF, ACN, DMSO and DMI in a volume ratio of 4:2:1:1; the specific parameters of the slit coating method include: the slit coating rate is 10 mm / s, the vertical distance between the slit coating head and the perovskite film-forming substrate is 100 μm, and the injection speed is 80 μL / s; the vacuum drying time is 50 s, and the chamber pressure during vacuum drying crystallization is 100 Pa.

[0122] (2) The perovskite film-forming substrate coated with the perovskite precursor film is placed on a carrier, enters the substrate inlet of the rapid annealing equipment through the carrier, and then passes through the lower space of the rapid drying zone at a transmission speed of 0.25 m / min for 10 min, and then passes through the lower space of the constant temperature drying zone at a transmission speed of 0.12 m / min for 30 min, and then passes through the lower space of the cooling zone at a transmission speed of 0.12 m / min, and then passes through the substrate outlet to obtain a large-area perovskite film with an area of ​​1200 mm×600 mm and a thickness of 3.2 mm.

[0123] Among them, the first heating element in the rapid drying zone is an electric heating tube heating element, and the heating temperature is 180°C; the third heating element is an electric heating tube heating element, and the heating temperature is 180°C; the number of wind knives is 5, the wind knife pressure is 0.5MPa, the air outlet temperature of the wind knife is 180°C, the vertical distance between the air outlet of the wind knife and the perovskite film-forming substrate passing through the rapid drying zone is 5cm, and the interval width between adjacent wind knives is 10cm; the second heating element in the constant temperature drying zone is an electric heating tube heating element, and the heating temperature is 180°C; the vertical distance between the lower surface of the second heating element and the perovskite film-forming substrate passing through the constant temperature drying zone is 2cm; the cooling element in the cooling zone is a cooling fan, and the cooling temperature is 20°C.

[0124] Example 3

[0125] This embodiment provides a rapid annealing process for a large-area perovskite film, and the rapid annealing process includes the following steps:

[0126] (1) The perovskite precursor solution is coated on the perovskite film-forming substrate by a slit coating method, and then placed in a vacuum drying device for vacuum drying and crystallization to obtain a perovskite precursor film.

[0127] The chemical formula of the perovskite precursor solution is (Cs 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 )3, the concentration is 1.5 mol / L, and the solvent includes DMF, ACN, DMSO and DMI in a volume ratio of 4:2:1:1; the specific parameters of the slit coating method include: the slit coating rate is 60 mm / s, the vertical distance between the slit coating head and the perovskite film-forming substrate is 50 μm, and the injection speed is 300 μL / s; the vacuum drying time is 100 s, and the chamber pressure during vacuum drying crystallization is 100 Pa.

[0128] (2) The perovskite film-forming substrate coated with the perovskite precursor film is placed on a carrier, enters the substrate inlet of the rapid annealing equipment through the carrier, and then passes through the lower space of the rapid drying zone at a transmission speed of 1 m / min for 2.5 min, and then passes through the lower space of the constant temperature drying zone at a transmission speed of 0.2 m / min for 10 min, and then passes through the lower space of the cooling zone at a transmission speed of 0.2 m / min, and then passes through the substrate outlet to obtain a large-area perovskite film with an area of ​​1200×600 mm and a thickness of 3.2 mm.

[0129] Among them, the first heating element in the rapid drying zone is an electric heating tube heating element, and the heating temperature is 100°C; the third heating element is an electric heating tube heating element, and the heating temperature is 100°C; the number of wind knives is 5, the wind knife pressure is 0.05MPa, the air outlet temperature of the wind knife is 100°C, the vertical distance between the air outlet of the wind knife and the perovskite film-forming substrate passing through the rapid drying zone is 3cm, and the interval width between adjacent wind knives is 5cm; the second heating element in the constant temperature drying zone is an electric heating tube heating element, and the heating temperature is 100°C; the vertical distance between the lower surface of the second heating element and the perovskite film-forming substrate passing through the constant temperature drying zone is 2cm; the cooling element in the cooling zone is a cooling fan, the exhaust element is an exhaust fan, and the cooling temperature is 20°C.

[0130] Example 4

[0131] The difference between this embodiment and embodiment 1 is that the temperature of the electric heating tube heating element is adjusted so that the air outlet temperature of the air knife is 40°C.

[0132] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0133] Example 5

[0134] The difference between this embodiment and embodiment 1 is that the temperature of the electric heating tube heating element is adjusted so that the air outlet temperature of the air knife is 220°C.

[0135] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0136] Example 6

[0137] The difference between this embodiment and embodiment 1 is that the vertical distance between the air outlet of the air knife and the perovskite film-forming substrate passing through the rapid drying zone is 2 cm.

[0138] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0139] Example 7

[0140] The difference between this embodiment and embodiment 1 is that the vertical distance between the air outlet of the air knife and the perovskite film-forming substrate passing through the rapid drying zone is 12 cm.

[0141] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0142] Example 8

[0143] The difference between this embodiment and embodiment 1 is that the air knife pressure of the air knife is 0.02 MPa.

[0144] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0145] Example 9

[0146] The difference between this embodiment and embodiment 1 is that the air knife pressure of the air knife is 0.6 MPa.

[0147] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0148] Example 10

[0149] The difference between this embodiment and embodiment 1 is that the transmission speed of the carrier through the rapid drying zone is 0.2 m / min, which is the same as the transmission speed through the constant temperature drying zone.

[0150] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0151] Comparative Example 1

[0152] The difference between this comparative example and Example 1 is that no air knife is provided.

[0153] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0154] Figure 4 A comparison of the XRD curves of the large-area perovskite films provided by Example 1 and Comparative Example 1 is shown. It can be seen from the figure that the peak intensity of the main peak (13.8°) of the perovskite in Example 1 is significantly higher than that in Comparative Example 1, indicating that the crystal orientation under the experimental conditions is better and the perovskite crystallization quality is high.

[0155] Figure 5 and Figure 6 The SEM images of the large-area perovskite films provided by Example 1 and Comparative Example 1 are respectively shown. By comparison, it can be seen that the grains of Example 1 are larger, and there is no obvious secondary crystal phase on the surface of the film, while the perovskite grains in Comparative Example 1 are smaller and there are more secondary crystal phases. The above analysis is consistent with the XRD curve, proving that the crystal orientation of the perovskite is obviously due to the comparative example.

[0156] Figure 7 A comparison chart of the annealing heating rates in the rapid annealing processes provided in Example 1 and Comparative Example 1 is shown. By comparison, it can be seen that the surface temperature of the perovskite film in Example 1 rises quickly, which is beneficial to reducing the exposure time of the perovskite film at low temperatures, accelerating the volatilization of residual solvents in the film, and improving the crystallization quality of the perovskite film. This phenomenon is consistent with the SEM and XRD data.

[0157] Comparative Example 2

[0158] The difference between this comparative example and Example 1 is that no quick drying zone is provided.

[0159] The rest of the device structure, rapid annealing process and parameters remain the same as those in Example 1.

[0160] Application Example 1

[0161] This application example provides a perovskite solar cell, which comprises a stacked ITO glass, an electron transport layer, a large-area perovskite film, a hole transport layer and an electrode; wherein the electron transport layer is C 60 layer, the hole transport layer is nickel oxide layer, and the electrode is Cu.

[0162] This application example also provides a method for preparing the above-mentioned perovskite solar cell, comprising the following steps:

[0163] (1) The electron transport layer was prepared on the ITO glass by vacuum coating method.

[0164] (2) A large-area perovskite film is prepared on the electron transport layer by using the rapid annealing process described in Example 1.

[0165] (3) The hole transport layer is prepared on a large area perovskite film by thermal evaporation.

[0166] (4) The electrode is prepared on the hole transport layer by thermal evaporation.

[0167] Application Example 2-10

[0168] The difference between Application Example 2-10 and Application Example 1 is that the large-area perovskite film in Application Example 2-10 is obtained by the rapid annealing process described in Example 2-10.

[0169] The rest of the preparation methods and parameters were the same as those in Application Example 1.

[0170] Application Comparative Example 1-2

[0171] The difference between Application Comparative Examples 1-2 and Application Example 1 is that the large-area perovskite films in Application Comparative Examples 1-2 are obtained by the rapid annealing process described in Comparative Examples 1-2.

[0172] The rest of the preparation methods and parameters were the same as those in Application Example 1.

[0173] Performance Testing

[0174] 1. The thickness distribution of the large-area perovskite films provided in the above embodiments and comparative examples is measured using a step profiler.

[0175] The measurement results are shown in Table 1.

[0176] Table 1

[0177]

[0178]

[0179] 2. Conduct photoelectric performance tests on the perovskite solar cells provided in the above application examples and comparative application examples.

[0180] The test conditions are: testing under AM1.5 simulated sunlight, the irradiance provided by the solar simulator is 100mW·cm -2 , photoelectric conversion efficiency = (open circuit voltage × short circuit current × fill factor) / (cell area × illumination amplitude) × 100%. .

[0181] The test results are shown in Table 2.

[0182] Table 2

[0183]

[0184]

[0185] analyze:

[0186] It can be seen from Tables 1 and 2 that the present invention, by adding a rapid drying zone and utilizing the cooperation of the first heating element and the air knife in the rapid drying zone, can quickly transfer heat to the substrate surface and quickly increase the heating rate of the substrate surface, thereby reducing the residence time of the residual solvent in the perovskite intermediate phase, significantly improving the crystallization quality of the perovskite film, and ultimately improving the efficiency and stability of the battery.

[0187] By comparing Example 1 (Application Example 1) with Example 4-5 (Application Example 4-5), it can be seen that if the air outlet temperature of the wind knife is too low, the crystallization quality of the perovskite film will be poor and the battery efficiency will be too low; if the air outlet temperature of the wind knife is too high, the crystallization quality of the perovskite film will be higher and the battery efficiency will be improved.

[0188] By comparing Example 1 (Application Example 1) with Example 6-7 (Application Examples 6-7), it can be seen that if the vertical distance between the air outlet of the wind knife and the perovskite film-forming substrate passing through the rapid drying zone is too low, the heating rate of the perovskite film will be too fast and the battery efficiency will decrease; if the vertical distance between the air outlet of the wind knife and the perovskite film-forming substrate passing through the rapid drying zone is too high, the heating rate of the perovskite film will be too slow and the battery efficiency will be low.

[0189] By comparing Example 1 (Application Example 1) with Example 8-9 (Application Examples 8-9), it can be seen that if the wind knife pressure of the wind knife is too low, the crystallization quality of the perovskite film will deteriorate and the battery efficiency will decrease; if the wind knife pressure of the wind knife is too high, the crystallization quality of the perovskite film will deteriorate and the battery efficiency will decrease.

[0190] By comparing Example 1 (Application Example 1) with Example 10 (Application Example 10), it can be seen that if the transmission speed of the carrier through the rapid drying zone is the same as the transmission speed through the constant temperature drying zone, the crystallization quality of the perovskite film will deteriorate and the battery efficiency will decrease.

[0191] By comparing Example 1 (Application Example 1) with Comparative Example 1 (Application Comparative Example 1), it can be seen that if no wind knife is provided, the surface heating rate of the perovskite film is slow, which is not conducive to improving the perovskite crystallization quality, and ultimately leads to poor perovskite crystallization quality, affecting device performance.

[0192] By comparing Example 1 (Application Example 1) with Comparative Example 2 (Application Comparative Example 2), it can be seen that if a rapid drying zone is not set, the surface heating rate of the perovskite film is slow, which is not conducive to improving the perovskite crystallization quality, and ultimately leads to poor perovskite crystallization quality, affecting device performance.

[0193] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope 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 shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A rapid annealing device for large-area perovskite films, characterized in that: The rapid annealing equipment comprises: A shell, wherein a quick drying zone, a constant temperature drying zone and a cooling zone are sequentially arranged in the shell, and a substrate inlet and a substrate outlet are provided on the shell, wherein the substrate inlet is located in the quick drying zone, and the substrate outlet is located in the cooling zone; a first heating element and an air knife are arranged in the upper space of the quick drying zone from top to bottom, and a second heating element is arranged in the upper space of the constant temperature drying zone; A conveying mechanism is used to transport the perovskite film-forming substrate to pass through the rapid drying zone, the constant temperature drying zone and the lower space of the cooling zone in sequence.

2. The rapid annealing equipment according to claim 1, characterized in that: The first heating element and the second heating element each independently include any one of a hot air heating element, a hot plate heating element, an electric heating tube heating element or an infrared lamp tube heating element, or a combination of at least two thereof; Preferably, the temperature control ranges of the first heating element and the second heating element are independently 100-200°C.

3. The rapid annealing equipment according to claim 1 or 2, characterized in that: The air outlet temperature of the air knife is 50-200°C; Preferably, the air knife has an air inlet and an air outlet, the air inlet is close to the first heating element, the air outlet is close to the perovskite film-forming substrate, and the hot air flow blown out of the air outlet directly acts on the surface of the perovskite film-forming substrate; Preferably, the vertical distance between the air outlet of the air knife and the perovskite film-forming substrate passing through the rapid drying zone is 3-10 cm; Preferably, the air knife pressure of the air knife is 0.05-0.5 MPa.

4. The rapid annealing equipment according to any one of claims 1 to 3, characterized in that: In the upper space of the rapid drying zone, a plurality of wind knives are arranged in parallel, and the wind knives are parallel to each other and are arranged parallel to the surface of the first heating element; Preferably, the number of the wind knives is 1-10; Preferably, the interval width between adjacent wind knives is 5-50 cm.

5. The rapid annealing equipment according to any one of claims 1 to 4, characterized in that: The conveying mechanism includes a carrier and a transmission track, wherein the carrier is connected to the transmission track via a transmission roller, and the carrier carries the perovskite film-forming substrate to pass through the lower space of the rapid drying zone, the constant temperature drying zone and the cooling zone in sequence; Preferably, the transmission speed of the carrier in the rapid drying zone is denoted as V1, and V1 is 0.1-1 m / min; Preferably, the transmission speed of the carrier in the constant temperature drying zone is denoted as V2, and V2 is 0.1-1 m / min; Preferably, V1 is greater than V2; Preferably, the transmission speed of the carrier in the cooling zone is denoted as V3, where V3=V2.

6. The rapid annealing equipment according to claim 5, characterized in that: A third heating element is disposed on the carrier, and the third heating element is located below the perovskite film-forming substrate and is used to heat the perovskite film-forming substrate; Preferably, the third heating element comprises any one of a hot air heating element, a hot plate heating element, an electric heating tube heating element or an infrared lamp heating element, or a combination of at least two thereof; Preferably, the temperature control range of the third heating element is 100-180°C.

7. The rapid annealing equipment according to any one of claims 1 to 6, characterized in that: The vertical distance between the lower surface of the second heating element and the perovskite film-forming substrate passing through the constant temperature drying zone is 1-10 cm; Preferably, the cooling zone is provided with a cooling element, and the cooling element is located in the upper space of the cooling zone, and is used to cool the perovskite film-forming substrate passing through the cooling zone; Preferably, the temperature control range of the cooling zone is 20-50°C; Preferably, the cooling element comprises a cooling fan.

8. A rapid annealing process for large-area perovskite films, characterized in that: The rapid annealing process is carried out in a rapid annealing device as claimed in any one of claims 1 to 7, comprising the following steps: The perovskite film-forming substrate coated with the perovskite precursor film is placed on a carrier, enters the substrate inlet through the carrier, and then passes through the rapid drying zone, constant temperature drying zone and lower space of the cooling zone of the rapid annealing equipment in sequence, and then passes through the substrate outlet to obtain a large-area perovskite film.

9. The rapid annealing process according to claim 8, characterized in that: The coating method of the perovskite precursor film comprises the following steps: The perovskite precursor solution is coated on a perovskite film-forming substrate, and then dried and crystallized to obtain a perovskite precursor film; Preferably, the chemical formula of the perovskite precursor solution is Cs x (FA y MA 1-y ) 1-x Pb(I z Br 1-z )3, where x≤1, y≤1, z≤1; Preferably, the concentration of the perovskite precursor solution is 0.2-1.5 mol / L; Preferably, the coating method includes a slot coating method; Preferably, the specific parameters of the slot coating method include: The slit coating rate is 10-60 mm / s, the vertical distance between the slit coating head and the perovskite film substrate is 50-200 μm, and the injection speed is 80-300 μL / s; Preferably, the drying and crystallization method comprises vacuum drying; Preferably, the vacuum drying time is 10-100s; Preferably, in the vacuum drying equipment for performing the vacuum drying, the cavity pressure is 0.1-100Pa.

10. The rapid annealing process according to claim 8 or 9, characterized in that: The rapid drying time of the perovskite film-forming substrate in the rapid drying zone is 1-10 minutes; Preferably, the constant temperature drying time of the perovskite film-forming substrate in the constant temperature drying zone is 10-30 minutes.

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