Macro-quantity high-yield perovskite thin film gas extraction crystallizer

Abstract

The utility model relates to solar cell equipment technical field, concretely is a kind of macro high yield perovskite thin film air extraction crystallizer, including horizontal vacuum narrow cavity structure, substrate connection system, vacuum air extraction system, active air intake system and crystallization control system;Horizontal vacuum narrow cavity structure is slit type (height≤100mm), top plate is equipped with the airflow pumping structure containing bar-shaped air extraction / air intake, rectifier unit and uniform flow dispersion transition surface (equivalent curvature radius≥5mm), substrate connection system contains flexible thimble support and vacuum adsorption positioning unit, vacuum air extraction system can realize 50-5000L / s pumping speed and 0.1-1000Pa vacuum degree regulation, crystallization control system controls temperature atmosphere, the utility model macro high yield perovskite thin film air extraction crystallizer, can form stable two-dimensional laminar flow, improve film uniformity, reduce defect, make large-area thin film maintain high density and crystallinity, improve component photoelectric conversion efficiency and production yield, satisfy commercialization demand.

Description

Technical Field

[0001] This utility model relates to the field of solar cell equipment technology, specifically a high-yield perovskite thin-film pump crystallizer. Background Technology

[0002] Perovskite solar cells boast excellent photoelectric performance and promising commercial prospects. Their large-scale manufacturing requires high-yield production on large-area (≥0.1 m²) substrates. One key aspect is the rapid solvent removal after wet coating and the controllable crystallization. Currently, the photoelectric conversion efficiency of small-area perovskite cells has exceeded 27%, while the efficiency of large-area modules is typically less than 22%, and the photoelectric conversion efficiency of commercial square meter-scale modules is even lower than 20%. The main reason for this gap is the significantly increased difficulty in crystallization control during film scaling, making it difficult to maintain the film uniformity and defect density at the levels required for high efficiency. In the large-area thin film preparation process, traditional crystallization methods mostly rely on flash evaporation, thermal annealing, and solvent atmosphere-assisted crystallization. Among them, the pressure fluctuations and local shearing effects generated by flash evaporation can easily trigger boiling and turbulence in the film, forming pinholes, streaks, and uneven white areas. Moreover, it is limited by the cavity geometry, the position of the vent, and improper pumping speed, which can produce obvious spatial non-uniformity. Thermal annealing relies on the thermal field to drive the gradual evaporation of solvent, which has a long process time and poor control over the crystallization process, making it difficult to achieve high-yield production. Although solvent atmosphere-assisted crystallization can improve the film quality to a certain extent, it has stringent requirements for atmosphere control and is difficult to combine with high-throughput preparation. Existing technologies cannot simultaneously achieve rapid solvent removal and precise control of crystallization kinetics under conditions of large-scale, large-area, and high-yield production.

[0003] Although the vacuum crystallization method (CN107894741B, CN116685184A, CN105702871B) can avoid the shortcomings of traditional methods to some extent, existing vacuum crystallization schemes still have several deficiencies when facing large-scale, large-area, and high-yield fabrication: First, the cavity structure is unreasonable. Most devices have large or irregular cavity volumes, leading to uneven flow field distribution, easy generation of local turbulence, and difficulty in forming a stable laminar vacuum effect; Second, the substrate bearing and positioning are unstable. Large-area substrates are prone to... Warping or drifting can affect the uniformity of the film layer, while rigid fixation needs to take into account issues such as substrate connection movement, vacuum sealing, flexible contact, and anti-drift; thirdly, the gas extraction control is crude, and the pumping speed and background vacuum are often adjusted in a single stage, which cannot match the solvent evaporation requirements of different crystallization stages; fourthly, the lack of temperature field control and adjustable atmosphere environment results in limited crystallization kinetics regulation capabilities, making it difficult to achieve uniform grain growth and defect control. Therefore, in view of the above situation, there is an urgent need to develop a high-yield perovskite thin film gas extraction crystallizer to overcome the shortcomings in current practical applications. Utility Model Content

[0004] The purpose of this invention is to provide a high-yield perovskite thin-film pump crystallizer to solve the problems mentioned in the background art.

[0005] To achieve the above objectives, this utility model provides the following technical solution:

[0006] A high-yield perovskite thin film vacuum crystallizer, which has a horizontal vacuum cavity structure, a substrate connection system, a vacuum pumping system, an active air intake system, and a crystallization control system.

[0007] The horizontal vacuum cavity structure includes a top plate and a bottom plate, and the horizontal vacuum cavity structure is formed by the top plate and the bottom plate through a dynamic seal;

[0008] The top plate contains an airflow extraction structure consisting of strip-shaped air extraction ports and strip-shaped air inlets, as well as a rectification unit; each air inlet is equipped with a rectification unit, and a uniform flow dispersion transition surface is provided near the inner wall of the cavity along the airflow path;

[0009] The substrate connection system is located inside the horizontal vacuum cavity structure. The vacuum pumping system is connected to the strip-shaped pumping port through a pipeline. The active air intake system is connected to the strip-shaped air intake port through a pipeline. The crystallization control system works in conjunction with the horizontal vacuum cavity structure.

[0010] As a further embodiment of this utility model: the horizontal vacuum cavity structure is a slit structure, the inner cavity length L and width W are ≤ 1.5 times the maximum outer contour feature size of the single or multiple substrates to be processed, and the height H is ≤ 100mm.

[0011] As a further embodiment of this utility model: the airflow extraction structure includes a strip-shaped air extraction port and a strip-shaped air inlet, the strip-shaped air extraction port and the strip-shaped air inlet being opened through the top plate.

[0012] As a further embodiment of this utility model: the airflow extraction structure includes a strip-shaped air inlet and strip-shaped air extraction ports directly adjacent to its two sides, the strip-shaped air extraction ports and the strip-shaped air inlet being opened through the top plate.

[0013] As a further embodiment of this utility model: the airflow extraction structure includes no less than a number of strip-shaped airflow ports, including at least a number of strip-shaped air extraction ports and a number of strip-shaped air inlets. The number of strip-shaped air extraction ports and strip-shaped air inlets may be equal or unequal. The strip-shaped air extraction ports and strip-shaped air inlets are opened through the top plate.

[0014] As a further embodiment of this utility model: in the airflow extraction structure, the strip-shaped air extraction port and the strip-shaped air inlet are arranged in a linear array, a circumferential multi-ring array, or a spatial superposition of the two.

[0015] The linear array refers to the strip airflow inlets arranged at equal or non-equal intervals, while the circumferential multi-ring array refers to the strip airflow inlets distributed along concentric circles or spirals.

[0016] As a further embodiment of this utility model: the uniform flow dispersion transition surface is a transition structure surface, which is a continuous curved surface, a chamfered structure, or a combination of multiple plane segments and their components, and its equivalent radius of curvature R is not less than 5mm;

[0017] The uniform flow dispersion transition surface is located near the inner wall of the cavity at the strip-shaped air extraction port and the strip-shaped air inlet.

[0018] As a further embodiment of this utility model: the rectifier unit is a structure disposed in the area adjacent to the airflow extraction structure, and is a combination of one or more structures, the shape of which is a planar, curved, or a combination thereof;

[0019] The rectifier unit is fixedly installed below the strip-shaped air extraction port and the strip-shaped air inlet.

[0020] As a further embodiment of this utility model: the substrate connection system includes a pin support unit and a vacuum adsorption positioning unit.

[0021] As a further embodiment of this utility model: the support end of the ejector pin support unit is provided with a flexible buffer layer, the flexible buffer layer is located at the support end of the ejector pin support unit, and the material of the flexible buffer layer is selected from one or more of silicone, polyurethane, fluororubber, and composite polymer elastic materials.

[0022] As a further embodiment of this utility model: the vacuum pumping system includes: a pumping speed control unit, comprising a regulating valve and a variable frequency vacuum pump group;

[0023] The regulating valve is located near the strip-shaped air intake port and is used to achieve continuous pumping speed regulation within the range of 50L / s to 5000L / s.

[0024] The background vacuum control unit includes a pressure control module; the pressure control module is connected to the vacuum pipeline of the horizontal vacuum cavity structure and is used to realize continuous control of the background vacuum level in the cavity within the range of 0.1P to 1000P.

[0025] The collaborative control unit is signal-connected to the pumping speed control unit and the background vacuum control unit.

[0026] As a further embodiment of this utility model: the active air intake system is connected to the strip-shaped air intake through a pipeline, and includes an active air intake device and an air intake control module;

[0027] The active air intake device is a clean air source, a nitrogen source, or a combination of a solvent vapor and a chemically reactive gas vapor generator. The air intake control module is at least one mass flow controller, and each mass flow controller corresponds to a strip-shaped air intake.

[0028] The intake control module can independently control one or more intake ports, enabling continuous adjustment of gas mass flow rate within the range of 0.1L / min to 100L / min;

[0029] The air intake control module is connected to the strip-shaped air intake via a polytetrafluoroethylene (PTFE) pipe or a stainless steel pipe using a quick-connect fitting and a compression fitting.

[0030] As a further embodiment of this utility model: the crystallization control system includes a multi-zone temperature control module and an atmosphere adjustment module;

[0031] The atmosphere conditioning module is connected to the horizontal vacuum cavity structure via a pipeline. The pipeline is equipped with a solenoid valve, and the atmosphere conditioning module is configured to introduce one or more of the following gases into the cavity: dry air, air with ≤60%RH humidity, inert gas, solvent vapor with ≤20% volume fraction, and chemically reactive gas.

[0032] Compared with the prior art, the beneficial effects of this utility model are:

[0033] This invention relates to a high-yield perovskite thin film pump crystallizer, which employs a narrow cavity structure to form a near-two-dimensional laminar flow pump channel. This significantly reduces local pressure fluctuations and turbulence interference, avoids pinholes, streaks, boiling over, and white area defects that are easily generated in the flash evaporation method, and effectively improves the uniformity of the film layer.

[0034] By employing a dual mechanism of flexible pin support and vacuum adsorption positioning, the flatness and stability of large-area substrates are ensured during the evacuation and heating process, effectively reducing the risk of substrate warping, drifting and stress cracking, and solving the problem of substrate load-bearing positioning.

[0035] By combining a multi-zone temperature control and atmosphere conditioning system, the temperature field and atmosphere composition can be synergistically adjusted during the evacuation process, achieving precise control of crystallization thermo-dynamics, promoting uniform growth of perovskite grains, and improving crystal quality.

[0036] By optimizing the structure and control methods described above, film defects and crystallization inhomogeneity can be reduced, enabling the prepared perovskite thin film to maintain high density and high crystallinity even under large-area conditions. This, in turn, improves the photoelectric conversion efficiency and production yield of the module, meeting the commercialization needs of large-area perovskite solar cell modules. Attached Figure Description

[0037] Figure 1This is a schematic diagram of the overall structure of the high-yield perovskite thin-film pump crystallizer of this utility model.

[0038] Figure 2 This is a schematic diagram of the horizontal vacuum cavity structure of this utility model.

[0039] In the diagram: 1-Horizontal vacuum cavity structure, 1.1-Top plate, 1.2-Bottom plate, 1.1.1-Airflow extraction structure, 1.1.1a-Strip-shaped extraction port, 1.1.1b-Strip-shaped inlet port, 1.1.2-Rectifying unit, 1.1.3-Inner wall of the cavity, 1.1.4-Uniform flow dispersion transition surface, 2-Substrate connection system, 2.1-Ejector pin support unit, 2.2-Vacuum adsorption positioning unit, 2.1.1-Flexible buffer layer, 3-Vacuum extraction system, 3.1-Pumping speed control unit, 3.1.1-Regulating valve, 3.1.2-Variable frequency vacuum pump group, 3.2-Base vacuum control unit, 3.2.1-Pressure control module, 3.3-Cooperative control unit, 4-Active air intake system, 4.1-Active air intake device, 4.2-Air intake control module, 5-Crystallization control system, 5.1-Multi-zone temperature control module, 5.2-Atmosphere conditioning module. Detailed Implementation

[0040] The technical solutions of the present utility model will be clearly and completely described below with reference to the accompanying drawings of the embodiments. Obviously, the described embodiments are only some embodiments of the present utility model, and not all embodiments. Based on the embodiments of the present utility model, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present utility model.

[0041] The specific implementation of this utility model will be described in detail below with reference to specific embodiments.

[0042] It should be noted that the horizontal structure of the present invention refers to the main extension direction of the key functional component (vacuum cavity) of the main body of the equipment being basically parallel to the horizontal plane, and its installation posture allows for an inclination angle within ±60° (i.e., oblique horizontal). Within this angle range, the liquid film on the substrate surface can maintain stable spreading and is less affected by gravity disturbance, and it still falls within the horizontal category of the present invention.

[0043] The maximum outer contour feature size refers to the feature size of the rectangle enclosing the substrate or substrate group; airflow ports not only refer to multiple physically independent airflow ports, but also include multiple effective airflow units formed by physical separation, structural partitioning, or functional zoning of the same continuous airflow channel, such as... Figure 1 and 2 As shown.

[0044] Example 1: Preparation of perovskite thin films for 300mm×300mm glass substrates;

[0045] This embodiment provides a specific implementation scheme for a high-yield perovskite thin film vacuum crystallizer, which aims to prepare uniform and highly dense perovskite thin films on a 300mm×300mm glass substrate. The specific details are as follows:

[0046] 1. Horizontal vacuum cavity structure configuration;

[0047] The horizontal vacuum cavity structure 1 is composed of an aluminum alloy top plate 1.1 and a bottom plate 1.2, which are sealed together by O-rings and fluororubber seals to ensure the vacuum seal of the cavity. Its internal dimensions are specifically set as follows: length L = 450 mm, width W = 400 mm, and height H = 20 mm. In this design, L = 450 mm and W = 400 mm are both ≤ 1.5 times the maximum outer contour feature size of a 300 mm × 300 mm glass substrate, and H = 20 mm ≤ 100 mm. This design forces the airflow to develop into a wall-attached two-dimensional laminar flow along the substrate surface, preventing the formation of vortices or backflow zones in the middle of the cavity. This ensures a consistent solvent evaporation rate in different areas of the substrate, reduces defects such as pinholes and interface pores, and provides a structural basis for uniform crystallization.

[0048] An airflow extraction structure 1.1.1 is provided on the top plate 1.1. The structure has two strip-shaped extraction ports 1.1.1a and one strip-shaped inlet port 1.1.1b, which are perpendicularly opened through the top plate 1.1. The inner walls of the ports are polished and the connection with the top plate 1.1 is sealed by argon arc welding. The two strip-shaped extraction ports 1.1.1a and one strip-shaped inlet port 1.1.1b are arranged alternately along the length of the cavity to form an aba symmetrical airflow unit, which can construct a symmetrical extraction flow field, further improve the airflow uniformity of the entire substrate, and avoid local solvent evaporation that is too fast or too slow.

[0049] At the location adjacent to the inner wall 1.1.3 of each strip-shaped exhaust port 1.1.1a and strip-shaped inlet port 1.1.1b, a uniform flow dispersion transition surface 1.1.4 is integrally formed. This transition surface is a continuous curved surface with an equivalent radius of curvature R = 20 mm (≥ 5 mm). It can guide high-speed or concentrated airflow to complete momentum buffering and direction adjustment before contacting the cavity wall, avoid the generation of impact eddies, and ensure that the airflow is uniformly distributed on the substrate surface, thus providing a guarantee for controllable solvent evaporation and crystallization consistency.

[0050] Meanwhile, a rectifier unit 1.1.2 is fixedly installed in the downstream area of ​​each air outlet. The rectifier unit 1.1.2 adopts a 200-mesh screen structure and is fixedly connected to the top plate 1.1 by spot welding or adhesive bonding through ultrasonic, rolling and other methods. Its radius of curvature is 15mm, which has the functions of diverting and equalizing the flow, further optimizing the local flow field, weakening the airflow disturbance, and ensuring the stability of the two-dimensional laminar flow state.

[0051] 2. Substrate connection system 2 configuration;

[0052] The substrate bonding system 2 is embedded inside the horizontal vacuum cavity structure 1, specifically including four ejector pin support units 2.1 and one set of vacuum adsorption positioning units 2.2.

[0053] The ejector pin support unit 2.1 is vertically fixed to the upper surface of the base plate 1.2 to ensure support stability; its support end is attached with a flexible buffer layer 2.1.1 made of polyurethane material. The buffer layer has a Shore hardness of A20, which can realize flexible micro-area contact between the substrate and the support structure, avoid substrate warping or surface damage caused by rigid support, and at the same time ensure the flatness of the substrate during the degassing and heating process.

[0054] The vacuum adsorption positioning unit 2.2 adopts a fine groove spiral array design. All fine grooves are opened on the upper surface of the base plate 1.2, and all fine grooves are connected to the vacuum channel preset inside the base plate 1.2. The vacuum channel is connected to the external negative pressure pump. The groove diameter is 1mm. The substrate is stably fixed on the support surface through negative pressure adsorption, preventing the substrate from drifting under the action of the flow field, and further ensuring the positional stability during the film preparation process.

[0055] 3. Equipped with a vacuum pumping system, an active air intake system, and a crystallization control system;

[0056] (1) The vacuum pumping system 3 is sealed to the strip-shaped pumping port 1.1.1a via a 316L stainless steel corrosion-resistant pipeline. The interface between the pipeline and the strip-shaped pumping port 1.1.1a is secured with a compression fitting to prevent vacuum leakage. It includes a pumping speed control unit 3.1, a background vacuum control unit 3.2, and a cooperative control unit 3.3.

[0057] The pumping speed control unit 3.1 includes a manual regulating valve 3.1.1 and a variable frequency vacuum pump group 3.1.2, which are connected in series through pipelines. The regulating valve 3.1.1 is located near the strip-shaped air extraction port 1.1.1a to facilitate rapid adjustment of the pumping speed. It can achieve continuous pumping speed adjustment in the range of 50L / s to 200L / s to meet the requirements of solvent evaporation rate at different stages.

[0058] The background vacuum control unit 3.2 integrates a pressure control module 3.2.1. The pressure control module 3.2.1 is connected to the vacuum gauge tube via a signal cable to collect vacuum data in the cavity in real time. It can stably control the background vacuum in the cavity at 10 Pa, avoiding thin film boiling or turbulence caused by vacuum fluctuations.

[0059] The collaborative control unit 3.3 is connected to the pumping speed control unit 3.1 and the background vacuum control unit 3.2 via signal cables. It can dynamically coordinate the pumping speed and vacuum parameters according to the preset process curve, so as to achieve precise matching of multi-stage solvent evaporation rates and avoid crystallization defects caused by single-stage adjustment.

[0060] (2) The active air intake system 4 is connected to the strip air intake 1.1.1b through a flow control pipeline. It includes a nitrogen pipeline (as an active air intake device 4.1) and an air intake control module 4.2. The active air intake device 4.1 is connected to the input end of the air intake control module 4.2 through a high-pressure gas pipe. The output end of the air intake control module 4.2 is connected to the strip air intake 1.1.1b through a polytetrafluoroethylene pipeline. The interface between the pipeline and the strip air intake 1.1.1b is sealed with a quick-connect fitting. The air intake control module 4.2 can independently control the gas flow rate of a single air intake 1.1.1b. The adjustment range is 0.1L / min to 10L / min. It can regulate the airflow state in the cavity by supplementing nitrogen, further optimize the flow field uniformity, and assist in the orderly removal of solvent.

[0061] (3) The crystallization control system 5 includes a multi-zone temperature control module 5.1 and an atmosphere conditioning module 5.2:

[0062] The embedded heating elements of the multi-zone temperature control module 5.1 are all embedded inside the base plate 1.2, and the distribution of the heating elements corresponds to the coverage area of ​​the substrate. The temperature sensor adopts a K-type thermocouple, which is installed inside the base plate 1.2 through a threaded interface, and the sensing end of the temperature sensor is in contact with the lower surface of the substrate. The embedded heating elements and the temperature sensor achieve precise control of the substrate temperature. In this embodiment, the substrate temperature is stably controlled at 20°C to avoid uneven crystallization caused by temperature gradient.

[0063] The atmosphere control module 5.2 is connected to the cavity of the horizontal vacuum cavity structure 1 through a stainless steel pipeline. A solenoid valve is connected in series in the middle of the pipeline to control the gas flow. Dry nitrogen (dew point ≤ -40℃) can be introduced into the cavity to create an inert atmosphere environment, prevent the perovskite precursor from reacting with water vapor and oxygen in the air, and ensure the chemical stability of the film.

[0064] 4. The process is as follows:

[0065] Substrate pretreatment: After cleaning and drying a 300mm×300mm glass substrate, a FA-based perovskite precursor solution (concentration of 1.2mol / L) is coated on its surface using a doctor blade coating method to form a wet film with a thickness of about 500nm.

[0066] Substrate connection: The glass substrate coated with a wet film is sent into the horizontal vacuum cavity structure 1. The flexible buffer layer 2.1.1 of the ejector pin support unit 2.1 first contacts the substrate to achieve initial positioning. Then, the external negative pressure corresponding to the vacuum adsorption positioning unit 2.2 is activated. Through the vacuum channel inside the base plate 1.2, a vacuum negative pressure of no more than 20,000 Pa is formed in the groove to adsorb and fix the substrate.

[0067] Collaborative crystallization: Start the vacuum pumping system 3, the active air intake system 4, and the crystallization control system 5, and execute the following two stages according to the preset process curve:

[0068] Phase 1 (0-30s): The co-control unit 3.3 regulates the variable frequency vacuum pump group 3.1.2 the pumping speed is 100L / s, the gas inlet control module 4.2 adjusts the nitrogen flow rate to 0.5L / min, and the multi-zone temperature control module 5.1 maintains the substrate temperature at 20℃. In this phase, the perovskite crystals are slowly nucleated through gentle gas extraction and an inert atmosphere to avoid boiling over.

[0069] Phase 2 (30-60s): The co-control unit 3.3 increases the pumping speed to 200L / s, and the air intake control module 4.2 reduces the nitrogen flow rate to 0.1L / min while maintaining the temperature at 20℃, accelerating the removal of residual solvent. At the same time, through the symmetrical flow field and laminar flow structure, it ensures that the solvent is uniformly removed from the entire substrate.

[0070] In summary, the perovskite thin films prepared using the vacuum crystallizer of this embodiment have the following advantages compared to traditional vacuum equipment (which lacks a narrow cavity and uniform flow design, active air intake, and temperature control and atmosphere regulation):

[0071] Surface morphology: The film surface is flat and dense, without defects such as boiling marks, interface pores and pinholes, and the grain size distribution is uniform;

[0072] Cross-sectional structure: The film thickness is consistent, with no areas that are too thick or too thin, and the crystals are tightly packed with no obvious pores;

[0073] Performance potential: This film can effectively reduce carrier recombination during the subsequent fabrication of solar cell modules, laying the foundation for improving photoelectric conversion efficiency and production yield.

[0074] Example 2: Preparation of perovskite thin films for 600mm×1200mm glass substrates;

[0075] This embodiment provides a high-yield perovskite thin-film vacuum crystallizer implementation scheme for larger 600mm×1200mm glass substrates, to solve the problems of flow field uniformity, substrate stability and crystallization control for large-area substrates, as detailed below:

[0076] 1. Horizontal vacuum cavity structure configuration;

[0077] The horizontal vacuum cavity structure 1 also uses an aluminum alloy top plate 1.1 and a bottom plate 1.2, which are sealed together by a nitrile rubber sealing ring to ensure the structural strength and vacuum sealing of the large-area cavity. The internal cavity dimensions are designed as follows: length L=1400mm, width W=700mm, and height H=20mm. Among them, L=1400mm and W=700mm are both ≤1.5 times the maximum outer contour feature size of a 600mm×1200mm glass substrate, and H=20mm≤100mm, which can form a stable two-dimensional laminar flow on the surface of a large-area substrate and avoid the problem of uneven flow field caused by the increase of substrate size.

[0078] The airflow extraction structure 1.1.1 of the top plate 1.1 includes 5 strip-shaped exhaust ports 1.1.1a and 4 strip-shaped inlets 1.1.1b. All strip-shaped exhaust ports 1.1.1a and strip-shaped inlets 1.1.1b are vertically opened through the top plate 1.1, with a spacing of 150mm between the ports, and the connection between the ports and the top plate 1.1 is sealed by welding. They are arranged alternately along the length of the cavity to form an "ababababa" linear array. This array structure can establish a zoned controllable flow field over the entire 600mm×1200mm substrate, and even the edge area of ​​the substrate can obtain uniform airflow, realizing uniform removal of solvent and control of crystallization over a large area.

[0079] Each airflow inlet is provided with a uniform flow dispersion transition surface 1.1.4 near the inner wall of the cavity 1.1.3. This transition surface is a continuous curved surface with an equivalent radius of curvature R=50mm (≥5mm), which can more fully buffer the airflow of a large area flow field, avoid the accumulation of disturbances caused by the long airflow path, and ensure that the airflow remains stable from the inlet to the outlet. At the same time, a flow straightening unit 1.1.2 is provided downstream of each airflow inlet. This unit is a flat guide plate connected to the inner wall of the top plate 1.1. The edge of the guide plate has no dead angle between the airflow and the inner wall of the cavity 1.1.3. The length is 40mm, which can further straighten the airflow direction, weaken local turbulence, and ensure laminar flow.

[0080] 2. Substrate connection system configuration;

[0081] Considering the larger weight and area of ​​the 600mm×1200mm glass substrate, the substrate connection system 2 is configured with 8 pin support units 2.1 and 1 set of vacuum adsorption positioning units 2.2:

[0082] The ejector pin support unit 2.1 is arranged in a rectangular array and is vertically fixed to the upper surface of the base plate 1.2; its support end is made of a flexible buffer layer 2.1.1 of silicone material with a Shore hardness of A40, which has both flexibility and support strength, and can disperse the local pressure brought by the weight of the substrate and prevent the middle of the substrate from warping.

[0083] The vacuum adsorption positioning unit 2.2 adopts a fine groove grid array design. The fine grooves are orthogonally distributed on the upper surface of the base plate 1.2 with a groove spacing of 50mm. All fine grooves are connected to the main vacuum channel inside the base plate 1.2. The main vacuum channel is connected to an external vacuum source through a flange. The groove diameter is 0.5mm, and the grid density is higher than that of Example 1. It can stably fix a large-area substrate through a more uniform negative pressure adsorption force, preventing the substrate from drifting at the edges or deforming during the evacuation process.

[0084] 3. Equipped with a vacuum pumping, active air intake, and crystallization control system;

[0085] (1) The pumping speed range of the variable frequency vacuum pump group 3.1.2 of the vacuum pumping system 3 is increased to 300L / s~800L / s. The variable frequency vacuum pump group 3.1.2 is composed of a rotary vane and a Roots vacuum pump connected in parallel. It is connected to the regulating valve 3.1.1 of the pumping speed control unit 3.1 through the manifold to match the total solvent demand of the large-area substrate. The base vacuum control unit 3.2 stabilizes the base vacuum in the cavity at 20Pa through the pressure control module 3.2.1, and takes the average value as the vacuum feedback value to improve the control accuracy. It ensures the solvent evaporation rate and avoids film cracking caused by high vacuum. The collaborative control unit 3.3 can dynamically adjust the pumping speed of each strip pumping port 1.1.1a according to the solvent evaporation feedback of different areas of the substrate (collected in real time by the humidity sensor and temperature sensor in the cavity) to achieve precise zone control.

[0086] (2) The intake control module 4.2 of the active intake system 4 can independently control the gas flow of the four strip-shaped intake ports 1.1.1b. The intake control module 4.2 contains four independent mass flow controllers, each mass flow controller corresponds to one strip-shaped intake port 1.1.1b, and the mass flow controller is connected to the collaborative control unit 3.3 through a signal cable to realize the linkage adjustment of the flow rate; the adjustment range is 5L / min to 20L / min, which can supplement gas differently according to the flow field requirements of different areas of the substrate, and further optimize the flow field uniformity of the large-area substrate.

[0087] (3) The multi-zone temperature control module 5.1 of the crystallization control system 5 adopts a zoned heating design, dividing the substrate surface into 4 temperature control zones (2 long side zones and 2 central zones). Each zone corresponds to a set of embedded heating elements and PT100 temperature sensors. All heating elements and temperature sensors are connected to the controller of the multi-zone temperature control module 5.1 via a bus. The temperature of each zone can be independently controlled at 25℃±1℃ to avoid temperature gradients on large-area substrates. The atmosphere adjustment module 5.2 can introduce different gases into the cavity in stages: the gas input end of the atmosphere adjustment module 5.2 is connected to a nitrogen source and a DMSO vapor generator respectively, and the gas type is switched by a solenoid valve. Dry nitrogen is introduced in the early stage, and nitrogen containing 2 vol% DMSO (dimethyl sulfoxide) vapor is introduced in the later stage. DMSO vapor can regulate the crystallization kinetics of perovskite, promote grain growth and reduce defects, and adapt to the crystallization quality requirements of large-area substrates.

[0088] 4. The process is as follows:

[0089] Substrate coating: A FA-based perovskite precursor solution (concentration 1.2 mol / L) was coated on a 600 mm × 1200 mm glass substrate, with a wet film thickness of approximately 600 nm;

[0090] Substrate fixation: The substrate is sent into the horizontal vacuum cavity structure 1. After being supported by the ejector pin support unit 2.1, the external negative pressure corresponding to the vacuum adsorption positioning unit 2.2 is turned on, so that a vacuum negative pressure of no more than 20000Pa is formed in the groove, and the substrate is tightly adsorbed and fixed.

[0091] Three-stage crystallization process:

[0092] Stage 1 (0-60s): Pumping speed 600L / s, air intake 5L / min (dry nitrogen), substrate temperature 25℃, control the uniform nucleation of crystals by stabilizing the flow field and inert atmosphere;

[0093] Stage 2 (60-120s): Pumping speed 100L / s, solenoid valve switched to DMSO vapor generator side, gas intake 1L / min (nitrogen gas containing 2 vol% DMSO vapor), temperature maintained at 25℃, DMSO vapor assisted grain growth, and optimized film microstructure.

[0094] Phase 3 (120-300s): Pumping speed 100L / s, solenoid valve switches back to nitrogen source side, multi-zone temperature control module 5.1 raises substrate temperature to 60℃ to accelerate the removal of residual solvent (including DMSO) while avoiding film decomposition caused by high temperature.

[0095] In summary, the perovskite thin film fabrication on a 600mm × 1200mm substrate using the vacuum crystallizer of this embodiment has significant advantages compared to traditional vacuum equipment (lacking narrow cavity and uniform flow design, and without zoned temperature control and solvent vapor atmosphere):

[0096] Film uniformity: The film thickness deviation over the entire substrate (including edges and corners) is ≤5%, with no localized over-whitening areas or solvent residue areas;

[0097] Grain quality: The grain size distribution is uniform, with no agglomeration of fine grains;

[0098] Mass production adaptability: This solution enables stable fabrication of large-area substrates with a yield rate of over 90%, meeting the mass production needs of commercial perovskite solar cell modules at the square meter level.

[0099] It should be noted that, in this utility model, unless otherwise explicitly specified and limited, the terms "sliding," "rotating," "fixed," and "equipped" should be interpreted broadly. For example, they can refer to welded connections, bolted connections, or integral connections; they can refer to mechanical connections or electrical connections; they can refer to direct connections or indirect connections through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components, unless otherwise explicitly limited. Those skilled in the art can understand the specific meaning of the above terms in this utility model according to the specific circumstances.

[0100] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A high-yield perovskite thin film vacuum crystallizer, characterized in that the vacuum crystallizer has a horizontal vacuum cavity structure (1), a substrate connection system (2), a vacuum pumping system (3), an active air intake system (4), and a crystallization control system (5). The horizontal vacuum cavity structure (1) includes a top plate (1.1) and a bottom plate (1.2), and the horizontal vacuum cavity structure (1) is formed by the top plate (1.1) and the bottom plate (1.2) through a dynamic seal; The top plate (1.1) includes an airflow extraction structure consisting of a strip-shaped exhaust port (1.1.1a) and a strip-shaped inlet port (1.1.1b). 1.1.1) and rectification unit (1.1.2); each air inlet is equipped with rectification unit (1.1.2), and a uniform flow dispersion transition surface (1.1.4) is provided near the inner wall of the cavity (1.1.3) of the air flow path. The substrate connection system (2) is located inside the horizontal vacuum cavity structure (1). The vacuum pumping system (3) is connected to the strip-shaped pumping port (1.1.1a) through a pipeline. The active air intake system (4) is connected to the strip-shaped air intake port (1.1.1b) through a pipeline. The crystallization control system (5) is coordinated with the horizontal vacuum cavity structure (1).

2. The high-yield perovskite thin-film pump crystallizer according to claim 1, characterized in that, The horizontal vacuum cavity structure (1) is a slit structure, with an inner cavity length L and width W ≤ 1.5 times the maximum outer contour feature size of the single or multiple substrates to be processed, and a height H ≤ 100 mm.

3. The high-yield perovskite thin-film pumped crystallizer according to claim 1 or 2, characterized in that, The airflow extraction structure ( 1.1.1) includes one strip-shaped air extraction port ( 1.1.1a) and a strip-shaped air inlet (1.1.1b), wherein the strip-shaped air outlet (1.1.1a) and the strip-shaped air inlet (1.1.1b) are opened through the top plate (1.1).

4. The high-yield perovskite thin-film pump crystallizer according to claim 1 or 2, characterized in that, The airflow extraction structure ( 1.1.1) includes a strip-shaped air inlet (1.1.1b) and strip-shaped air outlets (1.1.1a) directly adjacent to its two sides, wherein the strip-shaped air outlets (1.1.1a) and the strip-shaped air inlet (1.1.1b) are opened through the top plate (1.1).

5. The high-yield perovskite thin film vacuum crystallizer according to claim 1 or 2, characterized in that the airflow pumping structure (1.1.1) includes no less than 4 strip-shaped airflow ports, including at least 1 strip-shaped air extraction port (1.1.1a) and 1 strip-shaped air inlet port (1.1.1b), the number of strip-shaped air extraction ports (1.1.1a) and strip-shaped air inlets (1.1.1b) is equal or unequal, and the strip-shaped air extraction ports (1.1.1a) and strip-shaped air inlets (1.1.1b) are opened through the top plate (1.1).

6. The high-yield perovskite thin film vacuum crystallizer according to claim 5, characterized in that, in the airflow pumping structure (1.1.1), the strip-shaped exhaust port (1.1.1a) and the strip-shaped inlet port (1.1.1b) are arranged in a linear array, a circumferential multi-ring array, or a spatial superposition of the two. The linear array refers to the strip airflow inlets arranged at equal or non-equal intervals, while the circumferential multi-ring array refers to the strip airflow inlets distributed along concentric circles or spirals.

7. The high-yield perovskite thin-film pumped crystallizer according to claim 1 or 6, characterized in that, The uniform flow dispersion transition surface (1.1.4) is a transition structure surface, which is a continuous curved surface, a chamfered structure, or a combination of multiple planes and their components, and its equivalent radius of curvature R is not less than 5 mm. The uniform flow dispersion transition surface (1.1.4) is located near the inner wall of the cavity (1.1.3) of the strip-shaped air extraction port (1.1.1a) and the strip-shaped air inlet (1.1.1b).

8. The high-yield perovskite thin-film pump crystallizer according to claim 1, characterized in that, The rectifier unit (1.1.2) is installed in the airflow extraction structure ( 1.1.1) The structure of the adjacent region is a combination of one or more structures, and its shape is a planar, curved, or a combination thereof; The rectifier unit (1.1.2) is fixedly disposed below the strip-shaped air extraction port (1.1.1a) and the strip-shaped air inlet port (1.1.1b).

9. The high-yield perovskite thin-film pump crystallizer according to claim 1, characterized in that, The substrate connection system (2) includes a pin support unit (2.1) and a vacuum adsorption positioning unit (2.2).

10. The high-yield perovskite thin-film pump crystallizer according to claim 9, characterized in that, The support end of the pin support unit (2.1) is provided with a flexible buffer layer. 2.1.1), the flexible buffer layer (2.1.1) is located at the support end of the ejector pin support unit (2.1), the flexible buffer layer ( 2.1.1) The material is selected from one or more of silicone, polyurethane, fluororubber, and composite polymer elastic materials.

11. The high-yield perovskite thin-film pumped crystallizer according to claim 1, characterized in that, The vacuum pumping system (3) includes: a pumping speed control unit (3.1), which includes a regulating valve (3.1.1) and a variable frequency vacuum pump group (3.1.2). The regulating valve (3.1.1) is located near the strip-shaped air extraction port (1.1.1a) and is used to achieve continuous pumping speed regulation within the range of 50L / s to 5000L / s; The background vacuum control unit (3.2) includes a pressure control module (3.2.1); the pressure control module (3.2.1) is connected to the vacuum pipeline of the horizontal vacuum cavity structure (1) and is used to realize continuous control of the background vacuum level in the cavity within the range of 0.1Pa to 1000Pa. The collaborative control unit (3.3) is signal-connected to the pumping speed control unit (3.1) and the background vacuum control unit (3.2).

12. The high-yield perovskite thin-film pumped crystallizer according to claim 1, characterized in that, The active air intake system (4) is connected to the strip-shaped air intake (1.1.1b) via a pipeline and includes an active air intake device (4.1) and an air intake control module (4.2). The active air intake device (4.1) is a clean air source, a nitrogen source, or a combination of a solvent vapor and a chemically reactive gas vapor generator. The air intake control module (4.2) is at least one mass flow controller, and each mass flow controller corresponds to a strip-shaped air inlet (1.1.1b). The intake control module (4.2) can independently control one or more intake ports (1.1.1b) to achieve continuous adjustment of gas mass flow rate within the range of 0.1L / min to 100L / min; The air intake control module (4.2) and the strip-shaped air intake (1.1.1b) are connected by a polytetrafluoroethylene pipe or a stainless steel pipe based on a quick-connect and compression fitting.

13. The high-yield perovskite thin-film pump crystallizer according to claim 1, characterized in that, The crystallization control system (5) includes a multi-zone temperature control module (5.1) and an atmosphere conditioning module (5.2). The atmosphere conditioning module (5.2) is connected to the horizontal vacuum cavity structure (1) through a pipeline. The pipeline is equipped with a solenoid valve, and the atmosphere conditioning module (5.2) is configured to introduce one or more of the following gases into the cavity: dry air, air with ≤60%RH humidity, inert gas, solvent vapor with ≤20% volume fraction, and chemically reactive gas.

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