Large-area perovskite production equipment and production process thereof
Through the perovskite production equipment integrating gas quenching components and heating plates, the crystal nucleation disorder and interface inkjet printing of bromo-iodine mixed narrow band gap perovskite is solved, and high-quality preparation of large-area films is achieved, and device performance and yield are improved.
Patent Information
- Application Number
- CN202510887519.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-30
- Publication Date
- 2025-08-12
AI Technical Summary
The prior art has problems of crystal nucleation disorder, interface unevenness and inconsistent crystal growth direction in bromine iodine mixed narrow band gap perovskite inkjet printing, resulting in poor electrical uniformity of the film and making it difficult to prepare large-area high-quality films.
A large-area perovskite production equipment, integrated gas quenching components and heating plates are adopted to scrape bubbles and cure ink through low-temperature and high-speed gas knife to form a temperature gradient, and combine gradient heating to repair ion defects to achieve the uniformity of the film and the interface bonding strength.
It significantly improves the lateral uniformity of the film and the interface bonding strength, reduces the interface recombination, improves the carrier life and mobility, provides a high-quality initial film foundation, and lays the foundation for the subsequent preparation of high-performance devices.
Smart Images
Figure CN120462024A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of bromine-iodine mixed narrow-bandgap perovskite inkjet printing, and in particular to large-area perovskite production equipment and a production process thereof. Background Art
[0002] In the field of large-area inkjet printing technology of bromine-iodine mixed narrow-bandgap perovskites, such as Sn-Pb mixed systems, there has long been a key bottleneck that restricts industrial application. Inkjet printing technology is regarded as an ideal path for large-scale production of perovskite films due to its advantages of non-contact, flexible patterning and high material utilization. However, when applied to narrow-bandgap bromine-iodine mixed perovskite systems, the properties of the material itself interact with the physical mechanism of the inkjet process, causing a series of difficult process problems. The coexistence of bromide and iodide ions significantly reduces the crystallization nucleation energy barrier, while the inherent high chemical reactivity of the Sn-Pb system causes the ink droplets to rise sharply in supersaturation as the solvent evaporates violently at the moment of impact on the substrate, triggering explosive uncontrollable nucleation. This rapid crystallization process, which is completed in sub-seconds, almost deprives the window period for process control, resulting in disordered crystal growth direction and high defect density. At the same time, the difference in hydrophilicity between bromide ions and iodide ions in the solvent (Br - The hydrophilicity is significantly higher than that of I - During the spreading and drying process of a droplet, a significant "coffee ring effect" is induced: capillary flow at the droplet's edges continuously transports solute particles outward, while rapid solvent evaporation in the center causes delayed particle deposition, ultimately forming a ring-shaped accumulation structure with thick edges and a thin center. When this effect is infinitely amplified in large-area thin films, the lateral nonuniformity of the film thickness severely degrades the electrical uniformity of the device. Summary of the Invention
[0003] The present invention overcomes the deficiencies of the prior art and provides a large-area perovskite production device and a production process thereof.
[0004] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: a large-area perovskite production equipment, comprising: a frame mechanism, a transmission mechanism arranged above the frame mechanism, and a repair mechanism arranged on one side of the transmission mechanism,
[0005] The frame mechanism includes: a base, and an inkjet print head disposed above the base; the inkjet print head is used to inkjet print a narrow bandgap perovskite ink of a bromine-iodine mixture on an inkjet medium, and the repair mechanism and the transmission mechanism are respectively disposed on both sides of the inkjet print head;
[0006] The transmission mechanism includes: a stage assembly and a transmission assembly arranged between the stage assemblies; the stage assemblies are arranged in sections; the transmission assembly is arranged in the middle of the section, and the transmission assembly is used to adjust the position of the printing medium on the stage assembly;
[0007] The repair component includes: a heating plate and an air quenching component arranged on one side of the inkjet print head; the air quenching component is used to scrape bubbles from the ink on the printing medium; the heating plate is used to perform gradient heating to repair ion defects from the bottom layer.
[0008] In a preferred embodiment of the present invention, the carrier assembly includes a linear motor and a supporting member arranged on the linear motor; the supporting member is designed in a segmented manner, with the bottom of each segment of the supporting member connected as a whole and the top being divided into several segments, and the linear motor is connected to the bottom of the supporting member.
[0009] In a preferred embodiment of the present invention, the transmission component includes a horizontal member and a vertical member; the vertical member is connected to the supporting member and the horizontal member respectively, the vertical member is used to control the up and down movement of the horizontal member, and the horizontal member is used to control the horizontal movement of the inkjet medium to adjust its position on the supporting member.
[0010] In a preferred embodiment of the present invention, the vertical member includes a vertical cylinder and a frame fixedly connected to the output shaft of the vertical cylinder; the side surfaces of the vertical cylinder are fixedly connected to the bearing members, and the frame is arranged between the bearing members.
[0011] In a preferred embodiment of the present invention, the horizontal member includes a horizontal motor and several synchronous wheels; the synchronous wheels are stacked and distributed on both sides of the frame, and the synchronous wheels on each side are connected by a connecting rod, the synchronous wheels on the same side are connected by a synchronous belt, and the synchronous wheels close to the horizontal motor are fixedly connected to the horizontal motor.
[0012] In a preferred embodiment of the present invention, the heating plate is disposed on the surface of the carrier plate, and the heating plate is used to perform gradient heating on the inkjet medium from top to bottom.
[0013] In a preferred embodiment of the present invention, the gas quenching assembly includes a low-temperature cooling fan and a slit nozzle. The slit nozzle is arranged below the inkjet print head and is used to solidify the ink just sprayed on the printing medium and freeze ion migration.
[0014] A large-area perovskite production process comprises the following steps:
[0015] S1: The carrier assembly lifts up the transmission assembly to receive the transmitted printing medium, and the transmission assembly adjusts the printing medium to the middle position of the carrier assembly;
[0016] S2: The stage assembly transfers the printing medium to the bottom of the inkjet print head for perovskite inkjet printing;
[0017] S3: The air quenching component generates a low-temperature air knife to scrape the ink on the printing medium to remove bubbles, solidify the ink, and freeze ion migration;
[0018] S4: The heating plate gradually increases the temperature of the cured ink to promote the orderly migration of the underlying ions to repair defects.
[0019] In a preferred embodiment of the present invention, in S2, the perovskite inkjet printing is specifically bromine-iodine mixed narrow-bandgap perovskite inkjet printing.
[0020] In a preferred embodiment of the present invention, in S4, the gradient heating is specifically as follows: low temperature of 80°C for 50 minutes to orderly migrate the bottom ions to repair defects; medium temperature of 95°C for 15 minutes to form penetrating columnar crystals to eliminate lateral grain boundaries; high temperature of 115°C for 1.5 minutes to strengthen the longitudinal fusion of columnar crystals, reduce lattice stress, and improve carrier mobility.
[0021] The present invention solves the defects existing in the background technology and has the following beneficial effects:
[0022] (1) The present application provides a large-area perovskite production device and its production process, which integrates an air quenching component next to the inkjet print head and uses the low-temperature high-speed air knife generated by it to act on the wet film surface immediately after printing. The surface of the liquid film is frozen by the low-temperature airflow until the ink solidifies and the ion migration is frozen. At the same time, the mechanical pressure of the high-speed airflow produces a scraper-like effect, scraping off bubbles and forcing the ink to spread evenly and tightly fit the substrate, effectively eliminating the coffee ring effect and interface bubble voids caused by uneven solvent evaporation in traditional inkjet printing. Compared with the unavoidable uneven ink spreading and poor interface problems in traditional large-area inkjet technology, the problems are solved simultaneously at the source of film formation by physical means, which significantly improves the lateral uniformity and interface bonding strength of the film, provides a flat and dense initial film for subsequent high-quality crystallization, and lays the foundation for high performance and high yield of the device.
[0023] (2) This application provides a large-area perovskite production device and its production process, which forms a significant longitudinal temperature gradient in the film instantly through gas quenching operation, and drives the thiourea molecules in the precursor solution to spontaneously migrate downward and enrich in the interface area through the temperature gradient, and react with the lead vacancy and halogen vacancy defects at the interface to undergo in-situ passivation reaction. At the same time, it freezes the ion movement and converts the highly active Br - The distribution is locked on the surface to form a Br-rich layer, which effectively passivates interface defects and significantly reduces interface recombination, thereby controlling the enrichment distribution of Br on the surface. Compared with the traditional process, the interface defect passivation requires complex post-processing or uniform addition of excess additives, and the segregation of Br is difficult to accurately control over a large area. This application greatly improves the interface quality, inhibits recombination loss, and provides a Br-rich surface crystal nucleus template for subsequent epitaxial growth, creating conditions for obtaining high-crystalline quality films and optimizing the device band structure. The surface Br enrichment forms a gradient.
[0024] (3) The present application provides a large-area perovskite production device and its production process. After the gas quenching is completed, the temperature is controlled by a heating plate. In the low-temperature section, the ion migration activity of the bottom unfrozen area is used to provide sufficient time for the bottom ions to migrate and reorganize in an orderly manner, thereby repairing the micropores in the film. In the medium-temperature section, the surface Br-rich layer formed by gas quenching and freezing is used as a crystal nucleus template. Epitaxial growth is carried out from top to bottom under the drive of the temperature gradient to form columnar grains that run through the thickness of the film. In the high-temperature section, short-term annealing is performed to strengthen grain fusion and release stress, thereby eliminating the internal pores of the film and effectively suppressing lateral grain boundaries and the carrier recombination induced by them. A highly oriented grain structure that runs through the film is obtained. Compared with traditional uniform heating or constant temperature annealing, it is difficult to simultaneously eliminate pores and regulate grain morphology. In particular, small grains and multiple grain boundaries are easily formed under large areas, which significantly reduces the defect density of the film body and greatly improves the carrier lifetime and mobility. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments described in the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive efforts.
[0026] Figure 1 It is a three-dimensional structural diagram of a preferred embodiment of the present invention;
[0027] Figure 2 It is a preferred embodiment of the present invention Figure 1 A magnified schematic diagram of part A;
[0028] In the figure: 1. Frame mechanism; 2. Transmission mechanism; 3. Repair mechanism; 4. Base; 5. Inkjet print head; 6. Heating plate; 7. Gas quenching assembly; 8. Low-temperature cooling fan; 9. Slit nozzle; 10. Stage assembly; 11. Linear motor; 12. Carrying part; 13. Transmission assembly; 14. Vertical cylinder; 15. Frame; 16. Horizontal motor; 17. Synchronous wheel; 18. Synchronous belt; 19. Connecting rod. DETAILED DESCRIPTION
[0029] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0030] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.
[0031] In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application 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 limiting the scope of protection of the present application. 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 the indicated technical features. Therefore, 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.
[0032] In the description of this application, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed connections, detachable 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; and they can refer to internal connections between two components. Those skilled in the art will understand the specific meanings of the above terms in this application based on specific circumstances.
[0033] As shown in the figure, a large-area perovskite production device includes: a frame mechanism 1, a transmission mechanism 2 arranged above the frame mechanism 1, and a repair mechanism 3 arranged on one side of the transmission mechanism 2.
[0034] The frame mechanism 1 includes: a base 4, and an inkjet print head 5 disposed above the base 4; the inkjet print head 5 is used to inkjet print a narrow bandgap perovskite ink containing a mixture of bromine and iodine on an inkjet medium, and the repair mechanism 3 and the transmission mechanism 2 are respectively disposed on both sides of the inkjet print head 5;
[0035] The transmission mechanism 2 includes: a stage assembly 10, and a transmission assembly 13 disposed between the stage assemblies 10; the stage assembly 10 is arranged in sections; the transmission assembly 13 is disposed in the middle of the section, and the transmission assembly 13 is used to adjust the position of the printing medium on the stage assembly 10;
[0036] The repair component includes: a heating plate 6, and an air quenching component 7 arranged on one side of the inkjet print head 5; the air quenching component 7 is used to scrape bubbles from the ink on the printing medium; the heating plate 6 is used to perform gradient heating to repair ion defects from the bottom layer.
[0037] It should be noted that in the process of large-scale inkjet printing of narrow-bandgap perovskite ink mixed with bromine and iodine, due to the high intrinsic reaction activity of narrow-bandgap perovskite (Sn-Pb mixed system), the coexistence of bromine and iodide ions further reduces the crystallization energy barrier; when the inkjet droplet hits the printing medium, the solvent evaporates instantaneously, resulting in a sudden increase in supersaturation and triggering explosive nucleation (completed in seconds). The process parameters cannot be precisely controlled, and the hydrophilicity of halogens (Br) is different during large-scale inkjet printing. - >I-) causes uneven spreading of droplets, triggering the "coffee ring effect", resulting in thick edges and thin middles. The present application generates a low-temperature air knife through the air quenching component 7 during the inkjet printing process. During the inkjet printing, the air knife removes bubbles and uneven spreading on the surface of the printing medium. During the air knife scraping process, the air knife produces a scraper-like effect. As the printing medium moves, the air knife scrapes from the front of the ink to the back of the ink, so that the ink is spread evenly, removes bubbles, and exerts a downward pressure on the ink, making it fit closely to the printing medium to eliminate interface voids. Moreover, the air knife is a low-temperature air knife that quickly solidifies the ink and freezes ion migration. The air quenching instantly forms a temperature gradient (cold surface, warm bottom), driving the thiourea molecules in the precursor liquid to enrich at the buried interface, and in situ passivating Pb 0 and halogen vacancies, and fixed Br - Position, forming a 5-10nm thick surface Br enriched layer to prevent bulk phase segregation, and then the heating plate 6 is used to perform gradient temperature increase to promote the orderly reconstruction of Pb-I bonds in the bottom unfrozen area and repair the micropores.
[0038] The frame mechanism 1 includes: a base 4, and an inkjet print head 5 disposed above the base 4; the inkjet print head 5 is used to inkjet print a narrow bandgap perovskite ink containing a mixture of bromine and iodine on an inkjet medium, and the repair mechanism 3 and the transmission mechanism 2 are respectively disposed on both sides of the inkjet print head 5;
[0039] It should be noted that the base 4 is specifically a supporting base, the transmission mechanism 2, the repair mechanism 3 and the inkjet print head 5 are all fixedly connected to the top of the base 4, and the inkjet print head 5 is arranged in the middle position of the base. The inkjet print head 5 is specifically a MicroFab Technologies Jetlab series II's inkjet print head 5 includes a piezoelectric ceramic actuator, a nozzle plate, an ink chamber, and a drive circuit board. The drive circuit board sends out electric pulses, causing the piezoelectric ceramic to deform and squeeze the ink chamber. The filtered perovskite solution is sprayed through the corrosion-resistant nozzle plate, and the ink is coated on the printing medium, achieving uniform film formation over a large area.
[0040] The transmission mechanism 2 includes: a stage assembly 10, and a transmission assembly 13 disposed between the stage assemblies 10; the stage assembly 10 is arranged in sections; the transmission assembly 13 is disposed in the middle of the section, and the transmission assembly 13 is used to adjust the position of the printing medium on the stage assembly 10;
[0041] In the present invention, the stage assembly 10 includes a linear motor 11 and a support 12 mounted on the linear motor. The support 12 is a segmented design, with each segment of the support 12 being connected as a whole at the bottom and having multiple segments at the top. The linear motor 11 is connected to the bottom of the support 12. The transmission assembly 13 includes a horizontal member and a vertical member. The vertical member is connected to the support 12 and the horizontal member, respectively. The vertical member is used to control the up and down movement of the horizontal member, and the horizontal member is used to control the horizontal movement of the inkjet medium to adjust its position on the support 12. The vertical member includes a vertical cylinder 14 and a frame 15 fixedly connected to the output shaft of the vertical cylinder 14. The side of the vertical cylinder 14 is fixedly connected to the support 12, and the frame 15 is disposed between the support 12. The horizontal part includes a horizontal motor 16 and several synchronous wheels 17; the synchronous wheels 17 are stacked and distributed on both sides of the frame 15, and the synchronous wheels 17 on each side are connected by a connecting rod 19, and the synchronous wheels 17 on the same side are connected by a synchronous belt 18. The synchronous wheels 17 close to the horizontal motor 16 are fixedly connected to the horizontal motor 16.
[0042] It should be noted that the carrier assembly 10 includes a linear motor 11 and a carrier 12 fixedly connected to the linear motor 11. The carrier 12 is used to carry the printing medium. The carrier 12 as a whole is a complete rectangular plate, and its horizontal upper half is a segmented design, that is, the upper half is divided into several rectangular blocks by several long strip-shaped dividing grooves, and the horizontal lower half is still a complete rectangular plate. The linear motor 11 is fixedly connected to the bottom of the carrier 12, that is, the bottom of the rectangular plate. Therefore, during the operation, the carrier 12 carrying the printing medium is transported by the linear motor 11 through the inkjet print head 5 to perform large-area inkjet printing operations.
[0043] The frame 15 is formed by a plurality of first square tubes and second square tubes fixedly connected. There are a plurality of first square tubes and second square tubes. The first square tubes are respectively arranged in the partition grooves of the support member 12. The second square tubes are arranged perpendicular to the direction of the first square tubes. The second square tubes connect the plurality of first square tubes together from both ends of the first square tube. In this way, the frame 15 is formed by the first square tubes and the second square tubes. The frame 15 can move up and down in the partition groove. The output shaft of the vertical cylinder 14 is fixedly connected to the frame 15, and the bottom of the vertical cylinder 14 is fixedly connected to the support member 12, so that when the vertical cylinder 14 is extended or retracted, the frame 15 is driven to move up and down in the partition groove.
[0044] The horizontal motor 16 is a servo motor, which is fixedly connected to the outside of the frame 15. Several synchronous wheels 17 are rotatably connected at both ends of the first square tube. The several synchronous wheels 17 are fixedly connected by a connecting rod 19, and the position of the synchronous wheel 17 coincides with the central axis of the dividing groove. The synchronous wheels 17 at both ends of the first square tube are connected by a synchronous belt 18, and the synchronous wheel 17 close to the horizontal motor 16 is fixedly connected to the horizontal motor 16.
[0045] Therefore, when the horizontal motor 16 is in operation, it rotates, driving the synchronous wheel 17 near the horizontal motor 16 to rotate, and the synchronous belt 18 drives the synchronous wheel 17 on the same side to rotate through the connecting rod 19, and drives the synchronous wheel 17 on the other side to rotate synchronously through the synchronous belt 18. The horizontal motor 16 is fixedly connected to the frame 15, and the synchronous wheel 17 is rotatably connected to the frame 15. Therefore, when inkjet printing is performed, the vertical cylinder 14 extends to drive the frame 15 to move upward, thereby driving the horizontal member to move upward, moving to the separation slot of the carrier 12, receiving the transmitted printing medium, and transferring the printing medium to the middle position of the carrier 12 via the synchronous belt 18. Thereafter, the vertical cylinder 14 contracts to drive the horizontal member to hide again in the separation slot of the carrier 12, and then the linear motor 11 drives the carrier 12 to move and inkjet printing is performed through the inkjet print head 5.
[0046] The repair component includes: a heating plate 6, and an air quenching component 7 arranged on one side of the inkjet print head 5; the air quenching component 7 is used to scrape bubbles from the ink on the printing medium; the heating plate 6 is used to perform gradient heating to repair ion defects from the bottom layer.
[0047] In a preferred embodiment of the present invention, the heating plate 6 is disposed on the surface of the carrier plate, and the heating plate 6 is used to perform gradient heating on the inkjet medium from top to bottom.
[0048] In a preferred embodiment of the present invention, the gas quenching assembly 7 includes a low-temperature cooling fan 8 and a slit nozzle 9. The slit nozzle 9 is arranged below the inkjet print head 5 and is used to solidify the ink just sprayed on the printing medium and freeze ion migration.
[0049] It should be noted that the low-temperature refrigeration blower 8 integrates a gas purification module, a vapor compression refrigeration system, and an airflow control structure. The gas purification module converts nitrogen from an external nitrogen tank into a low-oxygen, low-humidity inert medium through a molecular sieve adsorption tower and a catalytic deoxygenation unit. This gas then enters the vapor compression refrigeration circuit, flowing through the compressor boosting section, the condenser liquefaction section, and the expansion valve throttling section. Finally, in the evaporator, it undergoes intense heat exchange with the liquid refrigerant, achieving a deep drop in gas temperature. The refrigeration circuit maintains a precise -35°C temperature via a PID controller. The cooled inert gas is driven by a centrifugal blower, adjusted to a specific pressure by an internal pressure-stabilizing valve, and then discharged through a vacuum-insulated pipeline. The blower system thus completes the three functions of inert gas purification, deep cooling, and constant-pressure delivery, providing a stable gas source that meets the temperature and chemical inertness requirements for subsequent gas knife generation.
[0050] The slit nozzle 9 has a narrow and elongated flow channel configuration outlet slit at its bottom. When the low-temperature airflow passes through this slit at high speed, its flow rate increases significantly and is shaped into a uniform, high-flow-rate, low-temperature "air knife"-shaped airflow belt. The flow channel configuration realizes the transformation of the air knife shape. The flow channel configuration is specifically a 0.25mm wide tapered flow channel that triggers the Bernoulli effect, accelerating the airflow to a high-speed state of 60m / s. This low-temperature air knife is precisely sprayed through the outlet slit toward the ink dot area formed on the printing medium.
[0051] A large-area perovskite production process comprises the following steps:
[0052] S1: The carrier assembly 10 lifts the transmission assembly 13 to receive the transmitted printing medium, and the transmission assembly 13 adjusts the printing medium to the middle position of the carrier assembly 10;
[0053] S2: The stage assembly 10 transfers the printing medium to the bottom of the inkjet print head 5 for perovskite inkjet printing;
[0054] S3: The air quenching component 7 generates a low-temperature air knife to scrape the ink on the printing medium to remove bubbles, and converts the ink into solidification and freezes ion migration;
[0055] S4: The heating plate 6 gradually increases the temperature of the solidified ink to promote orderly migration of bottom ions to repair defects.
[0056] In a preferred embodiment of the present invention, in S2, the perovskite inkjet printing is specifically bromine-iodine mixed narrow-bandgap perovskite inkjet printing.
[0057] In a preferred embodiment of the present invention, in S4, the gradient heating is specifically as follows: low temperature of 80°C for 50 minutes to orderly migrate the bottom ions to repair defects; medium temperature of 95°C for 15 minutes to form penetrating columnar crystals to eliminate lateral grain boundaries; high temperature of 115°C for 1.5 minutes to strengthen the longitudinal fusion of columnar crystals, reduce lattice stress, and improve carrier mobility.
[0058] During operation, the linear motor 11 drives the carrier assembly 10 to move to the outermost side, the vertical cylinder 14 extends to push the horizontal member out of the carrier 12, the horizontal motor 16 rotates, drives the synchronous belt 18 to rotate, receives the printing medium, and transmits the printing medium to the middle position of the carrier 12, the vertical cylinder 14 retracts to the inside of the carrier 12, so that the printing medium is placed on the carrier 12, and the linear motor 11 drives the carrier 12 and the printing medium thereon to pass through the inkjet print head 5. When passing through the inkjet print head 5, the inkjet print The head 5 performs large-area inkjet printing of narrow-bandgap perovskite. The ink used is a narrow-bandgap perovskite ink mixed with bromine and iodine. During inkjet printing, the ink on the printing medium is solidified by the air knife of the low-temperature inert gas formed by the low-temperature refrigeration fan 8, freezing the ion migration. The air knife pressure scrapes away bubbles and presses the liquid film to fit tightly with the substrate, eliminating interface voids. The air quenching instantly forms a temperature gradient (cold surface, warm bottom), driving the thiourea molecules in the precursor liquid to enrich at the buried bottom interface, in situ passivating Pb o and halogen vacancies, quickly fixing the Br- position to form a Br-rich layer, preventing bulk segregation, and then gradiently heating the bottom of the printing medium through the heating plate 6, first at a low temperature of 80°C for 50 minutes to allow the bottom ions to migrate in an orderly manner to repair defects; then at a medium temperature of 95°C for 15 minutes to form penetrating columnar crystals to eliminate lateral grain boundaries; finally at a high temperature of 115°C for 1.5 minutes to strengthen the longitudinal fusion of columnar crystals, reduce lattice stress, and improve carrier mobility.
[0059] In the industrial preparation of perovskite thin films, the synergistic effects of gas quenching and gradient temperature crystallization have been combined to form a complete physical control system. The gas quenching process achieves phase change control through the dual functions of low-temperature, high-speed airflow. When the inert gas impacts the precursor wet film at extremely low temperature and high speed, the surface layer instantly completes the ink solidification transformation, and the solidified ion migration channel effectively locks the movement trajectory of the bromide ions. This rapid freezing not only blocks the bulk phase segregation of bromine and iodine during traditional slow drying, but also transforms the bromine enriched on the surface into a functional crystal growth template. At the same time, the mechanical pressure of the airflow squeezes the liquid film to eliminate bubbles, forcing the material to form a close molecular fit with the substrate, completely eliminating the problem of interfacial void defects. The longitudinal temperature gradient naturally formed during the gas quenching process drives the directional enrichment of additive molecules to the bottom interface, spontaneously completing the in situ chemical passivation of lead vacancies and halogen vacancies, creating a clean interface foundation for subsequent crystallization.
[0060] After entering the gradient heating stage, the material reorganization process is dominated by the regulated temperature field distribution. In the low-temperature insulation range, the ions in the unfrozen area of the bottom layer migrate in an orderly manner under the action of thermal activation, autonomously filling the micropore defects formed in the previous process, and realizing the densification and reconstruction of the film structure. As the temperature gradient rises, the locked surface bromine-rich layer exhibits a nucleation template effect - the high bromine content reduces the surface nucleation energy barrier, and under the continuous guidance of the longitudinal temperature gradient, the grains grow preferentially in the direction perpendicular to the substrate. This epitaxial pattern extending from the surface to the bottom forms a columnar single crystal structure that runs through the thickness of the film, effectively eliminating the obstruction of lateral grain boundaries to carrier transport. The final high-temperature annealing stage fuses the boundaries of adjacent grains through a short period of thermal activation, releasing the lattice stress during the crystallization process, and further improving the structural integrity and carrier migration ability of the material.
[0061] This physical control system simultaneously addresses core process challenges through three key pathways: transient freezing transforms elemental segregation into a growth advantage; air knife pressure and temperature gradients synergistically eliminate interface defects; and thermal field-guided epitaxial growth achieves homogenized crystal structure. The resulting high-quality perovskite films exhibit outstanding optoelectronic performance and stability, achieving industrial-grade device efficiency requirements without the need for chemical additives, providing an efficient and environmentally friendly material preparation path for large-scale photovoltaic module manufacturing.
[0062] The above description is based on the ideal embodiment of the present invention. Based on the above description, relevant personnel can make various changes and modifications without departing from the technical scope of this invention. The technical scope of this invention is not limited to the content of the specification and must be determined according to the scope of the claims.
Claims
1. A large-area perovskite production device comprising: A frame mechanism, a transmission mechanism arranged above the frame mechanism, and a repair mechanism arranged on one side of the transmission mechanism, characterized in that: The frame mechanism includes: a base, and an inkjet print head disposed above the base; the inkjet print head is used to inkjet print a bromine-iodine mixed narrow-bandgap perovskite ink on an inkjet medium, and the repair mechanism and the transmission mechanism are respectively disposed on both sides of the inkjet print head; The transmission mechanism includes: a stage assembly, and a transmission assembly arranged between the stage assemblies; the stage assemblies are arranged in sections; the transmission assembly is arranged in the middle of the section, and the transmission assembly is used to adjust the position of the printing medium on the stage assembly; The repair component includes: a heating plate, and an air quenching component arranged on one side of the inkjet print head; the air quenching component is used to scrape bubbles from the ink on the printing medium; the heating plate is used to perform gradient heating to repair ion defects from the bottom layer.
2. The large-area perovskite production equipment according to claim 1, characterized in that: The platform assembly includes a linear motor and a supporting member arranged on the linear motor; the supporting member is designed in a segmented manner, the bottom of each segment of the supporting member is connected as a whole, and the top is divided into several segments, and the linear motor is connected to the bottom of the supporting member.
3. The large-area perovskite production equipment according to claim 2, characterized in that: The transmission component includes a horizontal member and a vertical member; the vertical member is connected to the supporting member and the horizontal member respectively, the vertical member is used to control the up and down movement of the horizontal member, and the horizontal member is used to control the horizontal movement of the inkjet medium to adjust its position on the supporting member.
4. The large-area perovskite production equipment according to claim 3, characterized in that: The vertical member includes a vertical cylinder and a frame fixedly connected to the output shaft of the vertical cylinder; the side surface of the vertical cylinder is fixedly connected to the bearing members, and the frame is arranged between the bearing members.
5. The large-area perovskite production equipment according to claim 4, characterized in that: The horizontal member includes a horizontal motor and several synchronous wheels; the synchronous wheels are stacked and distributed on both sides of the frame, and the synchronous wheels on each side are connected by a connecting rod, and the synchronous wheels on the same side are connected by a synchronous belt, and the synchronous wheel close to the horizontal motor is fixedly connected to the horizontal motor.
6. The large-area perovskite production equipment according to claim 5, characterized in that: The heating plate is arranged on the surface of the carrier plate, and is used for performing gradient heating on the inkjet medium from top to bottom.
7. The large-area perovskite production equipment according to claim 1, characterized in that: The gas quenching component includes a low-temperature cooling fan and a slit nozzle. The slit nozzle is arranged below the inkjet print head and is used to solidify the ink just sprayed on the printing medium and freeze ion migration.
8. A large-area perovskite production process, the device production process according to any one of claims 1-7, characterized in that: The following steps are involved: S1: The carrier assembly lifts up the transmission assembly to receive the transmitted printing medium, and the transmission assembly adjusts the printing medium to the middle position of the carrier assembly; S2: The stage assembly transfers the printing medium to the bottom of the inkjet print head for perovskite inkjet printing; S3: The air quenching component generates a low-temperature air knife to scrape the ink on the printing medium to remove bubbles, solidify the ink, and freeze ion migration; S4: The heating plate gradually increases the temperature of the cured ink to promote the orderly migration of the underlying ions to repair defects.
9. The large-area perovskite production process according to claim 8, characterized in that: In the above S2, the perovskite inkjet printing is specifically the bromine-iodine mixed narrow-bandgap perovskite inkjet printing.
10. The large-area perovskite production process according to claim 8, characterized in that: In the S4, the gradient heating is specifically as follows: low temperature of 80°C for 50 minutes to orderly migrate the bottom ions to repair defects; medium temperature of 95°C for 15 minutes to form penetrating columnar crystals to eliminate lateral grain boundaries; high temperature of 115°C for 1.5 minutes to strengthen the longitudinal fusion of columnar crystals, reduce lattice stress, and improve carrier mobility.