Vapor deposition apparatus and vapor deposition method

Abstract

The application belongs to the technical field of evaporation, and discloses an evaporation device and an evaporation method. The evaporation device comprises an evaporation assembly, which is arranged above a substrate to be evaporated in use. The evaporation assembly comprises an upper top plate, a bottom evaporation plate and a side plate, and the upper top plate, the side plate and the bottom evaporation plate form a closed structure. The evaporation assembly further comprises a plurality of containers for placing evaporation materials. The evaporation assembly further comprises a first heating assembly for heating the evaporation materials in the containers. The bottom evaporation plate comprises oppositely arranged first and second plate materials, and the bottom evaporation plate is reversible, so that the first and second plate materials can alternately receive the evaporation materials. The device adopts a planar evaporation source to generate a vertically collimated molecular beam, which can improve the utilization rate of the materials and the deposition uniformity, and is conducive to obtaining a film without holes, uniform thickness and uniform composition. The device can be used in cooperation with a vacuum pump to make the substrate in a high vacuum state, reduce the deposition temperature, and reduce the thermal damage and chemical corrosion of the substrate.

Description

Technical Field

[0001] This application relates to the field of vapor deposition technology, and more specifically, to vapor deposition equipment and vapor deposition methods. Background Technology

[0002] Three-terminal perovskite tandem solar cells (such as perovskite / silicon tandem cells and perovskite / perovskite tandem cells) achieve high efficiency through spectral splitting and voltage superposition, representing one of the most promising technological pathways to break the Shockley-Quisser efficiency limit of single-junction solar cells. Their core structure typically includes a bottom cell, a top cell, and an intermediate composite layer (or transparent conductive layer) connecting the two. The complexity of this structure places extremely stringent requirements on the fabrication process, especially the non-destructive and uniform deposition of the top cell and the intermediate connecting layer.

[0003] Currently, mainstream technologies for fabricating functional layers (such as electron transport layers, hole transport layers, and electrodes) and intermediate interconnecting layers in top-cell solar cells suffer from the following inherent drawbacks:

[0004] Poor compatibility of solution methods: When preparing the top film layer using solution methods such as spin coating and blade coating, the solvent is very likely to erode the already completed perovskite active layer and interface, leading to irreversible degradation of device performance and severely restricting the efficiency and stability of stacked devices.

[0005] Traditional vacuum evaporation processes suffer from damage and waste: Although vacuum thermal evaporation technology has the advantages of being solvent-independent and producing dense films, current evaporation source technologies (mainly point and line sources) used in the photovoltaic field suffer from the following fundamental bottlenecks: Interfacial thermal damage and particulate contamination: Point source / line source evaporation temperatures are high (typically >300°C), and a "bottom coating" method (evaporation source below, substrate above) is required. High-temperature thermal radiation can easily damage heat-sensitive materials (such as perovskite materials), and microparticles or condensates generated during evaporation are easily shed and contaminate the substrate under gravity, leading to short circuits or leakage in devices.

[0006] Extremely low material utilization and high cost: Due to their divergent evaporation characteristics, point and line sources generally have material utilization rates of less than 20%. This results in a huge waste of raw materials when depositing precious metal electrodes (such as gold and silver) or expensive organic transport materials, which seriously hinders their technical and economic viability.

[0007] Film thickness and composition uniformity are difficult to control: On large-area substrates, traditional point / line sources that rely on complex mechanical scanning cannot guarantee nanoscale uniformity of film thickness and composition, and uniformity is a prerequisite for achieving the key "current matching" in high-efficiency tandem solar cells.

[0008] There is a bottleneck in the fabrication of the intermediate interconnect layer: the fabrication of the intermediate transparent conductive layer (such as ITO) usually adopts magnetron sputtering. The high-energy particles generated by this process will bombard and damage the fragile perovskite and organic interface layers below, forming defects, which become the main limiting point for device performance and stability.

[0009] In summary, existing technologies for fabricating three-terminal perovskite tandem solar cells, especially their top structures, face three core challenges: interface damage, material waste, and insufficient uniformity. Developing a low-temperature, non-destructive, highly uniform, and material-utilizing thin-film deposition technology has become crucial for advancing three-terminal perovskite tandem solar cells from the laboratory to industrialization. Summary of the Invention

[0010] This application aims to at least partially alleviate or resolve at least one of the aforementioned problems.

[0011] In one aspect of this application, a vapor deposition apparatus is provided, comprising a vapor deposition assembly. In use, the vapor deposition assembly is placed above a substrate to be vapor-deposited. The vapor deposition assembly includes an upper top plate, a bottom vapor deposition plate, and side plates. The bottom vapor deposition plate is disposed opposite to the upper top plate, and the upper top plate, side plates, and bottom vapor deposition plate form a closed structure. The vapor deposition assembly also includes multiple containers located between the upper top plate and the bottom vapor deposition plate for holding vapor deposition material. Each container has an opening facing the upper top plate, and discharge holes are provided between adjacent containers. The vapor deposition assembly further includes a first heating assembly for heating the vapor deposition material in the containers. The bottom vapor deposition plate includes a first plate and a second plate disposed opposite to each other, and the bottom vapor deposition plate is flip-up, allowing the first plate and the second plate to alternately receive vapor deposition material.

[0012] This equipment uses a planar evaporation source to generate a vertically collimated molecular beam, which can improve the utilization rate of materials and the uniformity of deposition. It is beneficial to obtain thin films that are free of pores, have uniform thickness, and uniform composition, thus helping to meet the stringent requirements of current matching for film uniformity in three-terminal tandem batteries. This equipment can be used in conjunction with a vacuum pump to keep the substrate in a high vacuum state, thereby reducing the deposition temperature and minimizing thermal damage and chemical corrosion to the substrate.

[0013] In some embodiments, the first plate and the second plate have a porous structure.

[0014] In some embodiments, the first plate and the second plate are each independently selected from at least one of porous molybdenum metal felt and porous ceramic plate.

[0015] In some embodiments, the pore diameter of the first plate is 0.01 mm to 2 mm.

[0016] In some embodiments, the pore diameter of the second plate is 0.01 mm to 2 mm.

[0017] In some embodiments, the bottom vapor deposition plate further includes a second heating component, a third heating component, and a heat insulation plate between the two, wherein the second heating component is located between the first plate and the heat insulation plate, and the third heating component is located between the heat insulation plate and the second plate.

[0018] In some embodiments, the bottom vapor-deposited plate further includes a first thermally conductive metal plate located between the first plate and the insulation plate; and / or, the bottom vapor-deposited plate further includes a second thermally conductive metal plate located between the insulation plate and the second plate.

[0019] In some embodiments, the first heat-conducting metal plate is selected from at least one of molybdenum, tungsten, tantalum, rhenium, and copper alloys.

[0020] In some embodiments, the second heating component is located between the first heat-conducting metal plate and the heat insulation plate, or the second heating component is disposed in the first heat-conducting metal plate.

[0021] In some embodiments, the second heat-conducting metal plate is selected from at least one of molybdenum, tungsten, tantalum, rhenium, and copper alloys.

[0022] In some embodiments, the third heating component is located between the heat insulation plate and the second heat-conducting metal plate, or the third heating component is disposed in the second heat-conducting metal plate.

[0023] In some embodiments, one or more first microbalance sensors are embedded on the first plate, and / or one or more second microbalance sensors are embedded on the second plate.

[0024] In some embodiments, the first microbalance sensor is a quartz crystal microbalance sensor.

[0025] In some embodiments, the second microbalance sensor is a quartz crystal microbalance sensor.

[0026] In some embodiments, the vapor deposition equipment satisfies at least one of the following conditions: the width of the discharge hole is 1cm-2cm; the vapor deposition equipment further includes a control system; the vapor deposition equipment further includes a vapor deposition chamber for placing the vapor deposition components and the substrate to be vapor-deposited.

[0027] In another aspect of this application, a vapor deposition method is proposed, using the aforementioned vapor deposition equipment. The vapor deposition method includes the following steps: placing a vapor deposition assembly and a substrate to be vapor deposited in a vapor deposition chamber, with the vapor deposition assembly positioned above the substrate; connecting the vapor deposition chamber to a vacuum pump and evacuating it; using a first heating assembly to perform a first heating treatment on the vapor deposition material in the container, causing the vapor deposition material to escape from the discharge hole and adhere to a first plate or a second plate; flipping the bottom vapor deposition plate and performing a second heating treatment on the second plate or the first plate facing the substrate, causing the vapor deposition material on the second plate or the first plate to be deposited on the substrate. Using the above method for vapor deposition, with the vapor deposition assembly positioned above the substrate, full-surface coating can be achieved. For the substrate, the bottom vapor deposition plate can serve as a planar evaporation source, generating a vertically collimated molecular beam that deposits onto the substrate. This significantly improves the utilization rate of the vapor deposition material and facilitates isotropic deposition, ensuring the deposition of high-quality thin films on large-area multilayer structures and complex multilayer structures with steps. Furthermore, by evacuating the substrate, a high-vacuum environment can be created, which can reduce the vapor deposition temperature of the material on the bottom vapor deposition plate, thereby reducing thermal damage and chemical corrosion to the substrate.

[0028] In some embodiments, one of the first and second plates receives the vapor deposition material while the other serves as the deposition surface, providing the vapor deposition material to the substrate.

[0029] In some embodiments, a predetermined thickness is set by the control system, and the bottom vapor deposition plate is automatically flipped after the vapor deposition material on the substrate side of the bottom vapor deposition plate is exhausted or the thickness reaches the predetermined thickness.

[0030] In some embodiments, the vapor deposition method satisfies at least one of the following conditions: the vacuum level of the environment in which the substrate is located is ≤10. -7 The container is located in an environment with a vacuum level of 10. -2 Togo-10 -5 The distance between the bottom vapor deposition plate and the substrate is 50mm-800mm; the temperature of the first heat treatment is 300℃-600℃; and the temperature of the second heat treatment is 100℃-180℃. Attached Figure Description

[0031] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This invention illustrates a schematic diagram of a vapor deposition apparatus and a substrate according to an embodiment of this application. Figure 2 This invention illustrates a schematic diagram of a vapor deposition apparatus and a substrate according to another embodiment of the present application. Figure 3This shows a schematic diagram of the vapor deposition apparatus and substrate according to yet another embodiment of this application; Figure 4 This shows a schematic diagram of the vapor deposition apparatus and substrate according to yet another embodiment of this application; Figure 5 This invention provides a schematic diagram of the structure of a bottom vapor-deposited plate according to an embodiment of the present application. Figure 6 A schematic diagram of the structure of the bottom vapor deposition plate according to another embodiment of this application is shown.

[0032] Explanation of reference numerals in the attached figures: 100: Evaporation assembly; 110: Top plate; 120: Bottom evaporation plate; 121: First plate; 122: Second plate; 123: First micro balance sensor; 124: Second micro balance sensor; 125: Second heating assembly; 126: Third heating assembly; 127: Heat insulation plate; 128: First thermally conductive metal plate; 129: Second thermally conductive metal plate; 130: Side plate; 140: Container; 141: Opening; 150: Discharge hole; 10: Substrate; 20: Evaporation material. Detailed Implementation

[0033] The embodiments of this application are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0034] In the description of this application, it should be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this application.

[0035] Unless the context otherwise requires, throughout the specification and claims, the term "comprising" is interpreted as open-ended and encompassing, meaning "including, but not limited to." In the description of the specification, terms such as "one embodiment," "some embodiments," "exemplary embodiment," "exemplary," or "some examples," etc., are intended to indicate that a particular feature, structure, material, or characteristic associated with that embodiment or example is included in at least one embodiment or example of this application. The illustrative representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the aforementioned particular features, structures, materials, or characteristics may be included in any suitable manner in any one or more embodiments or examples.

[0036] The terms "first," "second," and "third," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first," "second," or "third" may explicitly or implicitly include one or more of that feature. In the description of the embodiments of this application, unless otherwise stated, "a plurality of" means two or more.

[0037] Connection or link: can refer to a mechanical or physical connection relationship, that is, A and B are connected or linked. It can mean that there are fastened components (such as screws, bolts, rivets, etc.) between A and B, or that A and B are in contact with each other and are difficult to separate. A and B can be fixed, detachable, or integrated; they can be directly connected or indirectly connected through an intermediate medium.

[0038] In this application, "parallel," "perpendicular," and "equal" include the described situation and situations that are similar to the described situation, within an acceptable deviation range, which is determined by those skilled in the art taking into account the measurement under discussion and the error associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "parallel" includes absolute parallelism and approximate parallelism, where the acceptable deviation range for approximate parallelism can be, for example, a deviation within 5°; "perpendicular" includes absolute perpendicularity and approximate perpendicularity, where the acceptable deviation range for approximate perpendicularity can also be, for example, a deviation within 5°. "Equal" includes absolute equality and approximate equality, where the acceptable deviation range for approximate equality can be, for example, a difference between the two equals being less than or equal to 5% of either one.

[0039] This document describes exemplary embodiments with reference to sectional views and / or plan views, which are idealized exemplary drawings. In the drawings, the thickness of layers and regions is enlarged for clarity. Therefore, variations in shape relative to the drawings are contemplated due to, for example, manufacturing techniques and / or tolerances. Therefore, exemplary embodiments should not be construed as limited to the shapes of the regions shown herein, but rather include shape deviations due to, for example, manufacturing processes. Thus, the regions shown in the drawings are schematic in nature, and their shapes are not intended to show the actual shapes of the regions of the device, nor are they intended to limit the scope of the exemplary embodiments.

[0040] Furthermore, the scenarios described in the embodiments of this application are for the purpose of more clearly illustrating the technical solutions of the embodiments of this application, and do not constitute a limitation on the technical solutions provided in the embodiments of this application. As those skilled in the art will know, with the emergence of new scenarios, the technical solutions provided in the embodiments of this application are also applicable to similar technical problems.

[0041] As mentioned above, the film preparation methods in related technologies have the following problems: (1) Interfacial physical and chemical damage issues: Thermal damage: Traditional point source / line source evaporation has a high evaporation temperature (usually >300°C), and high-temperature thermal radiation can damage the heat-sensitive perovskite substrate material.

[0042] High-energy particle bombardment damage: When using magnetron sputtering to prepare the TCO (transparent conductive oxide) intermediate bonding layer, high-energy particles in the plasma bombard and damage the underlying perovskite and organic interfaces, forming defects that restrict device performance and stability.

[0043] (2) Problems of low material utilization and high cost: When using traditional point / line source deposition of precious metal electrodes and expensive organic transport materials, the material utilization rate is less than 20%, which leads to a significant increase in raw material costs. In addition, the waste disposal burden is heavy and the economic feasibility is poor.

[0044] (3) Challenges in controlling the uniformity and consistency of the film layer: Traditional point / line source methods rely on complex mechanical scanning, which makes it difficult to guarantee the uniformity of film thickness and composition.

[0045] In order to at least partially alleviate or even solve at least one of the aforementioned technical problems, this application provides a vapor deposition apparatus. In some embodiments, reference is made to... Figures 1 to 6 The vapor deposition equipment includes a vapor deposition component 100, which is placed above the substrate 10 to be vapor deposited during use. For the preparation of the functional layer and intermediate connecting layer in the top cell of a tandem battery, traditional vapor deposition equipment typically uses a "bottom deposition" method, requiring the substrate to be placed above the evaporation source using a carrier plate. This results in material waste at the edges due to obstruction by the substrate carrier plate. However, in this application, the evaporation source is located above the substrate, allowing the vapor deposition material to cover the entire surface of the substrate without obstruction, achieving "full-surface deposition" and reducing waste in terms of space layout.

[0046] refer to Figures 1 to 6The vapor deposition assembly 100 includes an upper top plate 110, a bottom vapor deposition plate 120, and a side plate 130. The bottom vapor deposition plate 120 is disposed opposite to the upper top plate 110, and the upper top plate 110, side plate 130, and bottom vapor deposition plate 120 form a closed structure. The vapor deposition assembly 100 also includes a plurality of containers 140 located between the upper top plate 110 and the bottom vapor deposition plate 120 for holding vapor deposition material 20. Each container 140 has an opening 141 facing the upper top plate 110, and a discharge hole 150 is provided between adjacent containers 140. The vapor deposition assembly 100 also includes a first heating assembly (not shown) for heating the vapor deposition material 20 in the containers 140. The bottom vapor deposition plate 120 includes a first plate 121 and a second plate 122 disposed opposite to each other, and the bottom vapor deposition plate 120 is flip-up, allowing the first plate 121 and the second plate 122 to alternately receive vapor deposition material 20.

[0047] refer to Figures 2 to 4 The vapor deposition assembly 100 is an integrally enclosed structure, with an upper top plate 110 on its upper side. In some embodiments, the upper top plate 110 can be tightened with hexagonal screws. When it is necessary to clean the container (e.g., a crucible) or fill the container with vapor deposition material, it can be disassembled using an hexagonal screwdriver. For example, the upper top plate 110 can be a stainless steel sheet.

[0048] The side plate 130 can be a one-piece structure, such as a one-piece stainless steel structure, or the side plate 130 can be composed of multiple plates connected in sequence. In some embodiments, the cross-section of the side plate 130 in the horizontal direction (perpendicular to the height direction of the side plate 130) can be rectangular, or it can be set to other shapes as needed.

[0049] For example, the multiple containers 140 can be a single, integral structure, with edge portions fixed to the side plates by welding or bolting. In some embodiments, the multiple containers can be arranged in an array to... Figure 3 The X direction shown is the row direction, and multiple containers can be arranged in one row and multiple columns or multiple rows and multiple columns. The specific shape and size of the container 140 are not particularly limited in this application, as long as it can hold the vapor-deposited material. In some embodiments, the container can be bottle-shaped or bowl-shaped. The specific material of the container 140 is also not particularly limited in this application, as long as it can maintain structural stability during the vapor deposition process and does not react with the vapor-deposited material. In some embodiments, the container 140 can be made of glass or metal.

[0050] refer to Figure 2 and Figure 3Each adjacent container 140 has a discharge port 150. A first heating assembly heats the vapor-deposited material 20 within the container 140, causing it to sublimate and escape from the opening 141 of the container 140. The material then moves downwards through the discharge port 150 and deposits on the surface of the bottom vapor-deposited plate 120 facing the upper top plate 110, thus completing the reception of the vapor-deposited material. (Reference) Figure 2 and Figure 3 After passing through the discharge hole 150, the vapor-deposited material 20 can diffuse and deposit on the bottom vapor-deposited plate 120. The vapor-deposited material 20 escaping from the same discharge hole 150 can diffuse outward at an angle θ, thereby depositing on the entire surface of the bottom vapor-deposited plate 120 facing the top plate 110.

[0051] In some embodiments, the first heating element may be disposed below the container 140 or at other suitable locations. The first heating element may be a commonly used heating element, such as a resistance wire.

[0052] In some embodiments, a heating component may be provided on the side of the upper top plate 110 facing the container or inside the upper top plate 110, which is more conducive to the deposition of sublimated vapor-deposited material downwards and reduces the contact between the vapor-deposited material and the upper top plate.

[0053] In some embodiments, the discharge hole 150 is along Figure 4 The cross-section in the CC' direction (horizontal plane) shown can be a regular shape or an irregular shape. For example, the cross-section of the discharge hole 150 along the CC' direction can be circular, rectangular or irregular. The cross-sections of multiple discharge holes 150 along the CC' direction can be the same or different.

[0054] In some embodiments, reference Figure 4 The width d of the discharge hole 150 can be 1cm-2cm, which facilitates the dispersion and deposition of the vapor-deposited material through the discharge hole onto the bottom vapor-depositing plate. When the cross-section of the discharge hole 150 along the CC' direction is circular, the width d of the discharge hole 150 refers to the diameter of the circle; when the cross-section of the discharge hole 150 along the CC' direction is rectangular, the width d of the discharge hole 150 refers to the length of the shorter side of the rectangle; when the cross-section of the discharge hole 150 along the CC' direction is irregular, the width of the discharge hole can be obtained by measuring the distance between any two points on the cross-section multiple times and taking the average value.

[0055] The lower side of the vapor deposition assembly 100 is a flip-up bottom vapor deposition plate 120, for reference. Figure 5 and Figure 6 The bottom vapor deposition plate 120 includes a first plate 121 and a second plate 122. During use, the bottom vapor deposition plate 120 can be flipped so that the first plate 121 and the second plate 122 alternately receive vapor deposition materials.

[0056] Figure 2 and Figure 3 The two different states of the vapor deposition assembly during the vapor deposition process are shown respectively. Figure 2 In the process, the vapor deposition material in container 140 is heated by a first heating component (not shown in the figure). The vapor deposition material sublimates and is deposited onto the surface of the first or second plate of the bottom vapor deposition plate 120 through the opening 140 and the discharge hole 150 to form a pre-coating. Afterward, the bottom vapor deposition plate 120 is flipped so that the plate with the vapor deposition material is facing the substrate, and the vapor deposition material on it is moved along... Figure 3 The material is deposited perpendicularly and collimated in the Y direction onto substrate 10, while another substrate can continue to receive the evaporated material escaping from the outlet. After the desired film layer has been formed by evaporation, substrate 10 can be deposited along... Figure 3 Move out of the vapor deposition chamber in the X direction (horizontal direction) as shown.

[0057] In some embodiments, the shape of the surface of the bottom evaporation plate used to receive the evaporation material can be the same as the shape of the substrate, for example, it can be rectangular, and the surface size can be comparable to the substrate size (the surface size is the same as or slightly smaller than the substrate size), which is more conducive to achieving full-area coating. In other embodiments, the size of the surface of the bottom evaporation plate used to receive the evaporation material can be smaller than the substrate size, and after the film deposition in a certain area is completed, the substrate can be moved to continue film deposition in other areas.

[0058] In some embodiments, the vapor deposition apparatus further includes a vapor deposition chamber for housing the vapor deposition assembly 100 and the substrate 10 to be vapor deposited. The vapor deposition chamber has a vacuum pump interface, which can be evacuated by an external vacuum pump to place the substrate 10 in a high vacuum environment, thereby reducing the heating temperature required for the bottom vapor deposition plate during the deposition process.

[0059] In some embodiments, the first plate 121 and the second plate 122 have a porous structure, such as porous metal felt. In some specific embodiments, the first plate 121 and the second plate 122 may each be independently selected from at least one of porous molybdenum metal felt and porous ceramic plate. Porous (sintered) molybdenum metal felt has a large specific surface area. Porous molybdenum metal felt and porous ceramic plate can physically capture more vapor of the vapor deposition material like a "sponge," which is beneficial for forming a thicker and more uniform pre-coating layer. Furthermore, the porous structure can prevent the lateral flow of the pre-coating layer in the molten or softened state, suppress the flow of vapor deposition material, and maintain the uniformity of its thickness distribution, thereby facilitating the deposition of a uniformly thick film layer on the entire surface of the substrate. In addition, the porous structure plate has a complex internal surface structure, which can enhance the thermal radiation efficiency and help reduce the operating temperature required to heat the pre-coating layer on it.

[0060] In some embodiments, the first plate 121 and the second plate 122 may have a micron-scale porous structure. This is more conducive to capturing vapor of the vapor-deposited material, forming a thick and uniform pre-coating.

[0061] In some embodiments, the pore diameter of the first plate 121 can be 0.01mm to 2mm, for example, 0.01mm, 0.05mm, 0.1mm, 0.5mm, 1mm, 2mm, etc. In some embodiments, the pore diameter of the second plate 122 can be 0.01mm to 2mm, for example, 0.01mm, 0.05mm, 0.1mm, 0.5mm, 1mm, 2mm, etc. The pore diameters of the first and second plates being within the above ranges are beneficial for capturing the vapor-deposited material and forming a pre-coating layer of suitable and uniform thickness.

[0062] In some embodiments, micron-level roughness can be formed on the first or second plate by methods such as surface sandblasting, chemical etching, and laser treatment to increase the surface area and film adhesion, and prevent the pre-coating from falling off during transport.

[0063] In some embodiments, reference Figure 5 and Figure 6 One or more first microbalance sensors 123 may be embedded on the first plate 121, and one or more second microbalance sensors 124 may be embedded on the second plate 122. The first microbalance sensor 123 or the second microbalance sensor 124 can sense the mass of the load on its surface and calculate the thickness of the load. This allows for a prompt to flip the bottom vapor deposition plate when the deposited vapor deposition material on the plate reaches a predetermined thickness or when the vapor deposition material on the plate is exhausted. In some embodiments, a precise groove can be machined on the first plate 121 to embed the first microbalance sensor 123, making its surface coplanar with the working surface of the first plate 121; a precise groove can be machined on the second plate 122 to embed the second microbalance sensor 124, making its surface coplanar with the working surface of the second plate 122. In some embodiments, the first and second microbalance sensors have electrodes. Electrode wires can be led out through micropores on the back of the first or second plate and connected to a vacuum connection transition interface. The sensors can transmit pre-coating information to the control system, which can use modules such as digital-to-electrical conversion to regulate whether the bottom vapor deposition plate is flipped. The mechanical flipping system for flipping the bottom vapor deposition plate can be a conventional vacuum mechanical control system, and no special limitation is made in this application.

[0064] In some embodiments, the number of first microbalance sensors 123 may be one. In other embodiments, the number of first microbalance sensors 123 may be multiple, see reference. Figure 5 and Figure 6Multiple first microbalance sensors 123 can be evenly distributed and embedded in the first plate 121.

[0065] In some embodiments, the number of second microbalance sensors 124 may be one. In other embodiments, the number of second microbalance sensors 124 may be multiple, see reference... Figure 5 and Figure 6 Multiple second microbalance sensors 124 can be evenly distributed and embedded in the second plate 122.

[0066] In some embodiments, the first microbalance sensor 123 can be a quartz crystal microbalance sensor (QCM), and the second microbalance sensor 124 can be a quartz crystal microbalance sensor. One or more QCMs are embedded in the substrate; the QCMs can sense the surface mass load through changes in the crystal resonant frequency and directly calculate the thickness.

[0067] In some embodiments, reference Figure 5 and Figure 6 The bottom vapor deposition plate 120 also includes a second heating component 125, a third heating component 126, and a heat insulation plate 127 between them. The second heating component 125 is located between the first plate 121 and the heat insulation plate 127, and the third heating component 126 is located between the heat insulation plate 127 and the second plate 122. Thus, the first plate 121 and the second plate 122 can be heated separately by the second heating component 125 and the third heating component 126, thereby depositing the vapor deposition material on the first plate 121 or the second plate 122 onto the substrate 10. The heat insulation plate 127 separates the second heating component 125 and the third heating component 126, allowing independent heating on both sides without interference; it also blocks heat from above the bottom vapor deposition plate, preventing heat transfer to the substrate and thus avoiding thermal radiation damage to the substrate.

[0068] In some embodiments, the second heating component 125 and the third heating component 126 may include resistance wires. In other embodiments, the second heating component 125 and the third heating component 126 may also employ other heating structures.

[0069] The specific material of the insulation board 127 is not specifically limited in this application. Those skilled in the art can choose a ceramic board or other insulation board with excellent thermal insulation performance according to actual needs.

[0070] In some embodiments, reference Figure 6The bottom vapor-deposited plate 120 may further include a first thermally conductive metal plate 128, which is located between the first plate 121 and the insulation plate 127; the bottom vapor-deposited plate 120 may also include a second thermally conductive metal plate 129, which is located between the insulation plate 127 and the second plate 122. The thermally conductive metal plate has high thermal stability, a high melting point, and is completely stable without deformation at the evaporation temperature of organic materials (130℃-300℃); it has excellent thermal conductivity, which ensures that heat is rapidly and evenly distributed across the entire plate surface, thus facilitating "uniform re-evaporation".

[0071] In some embodiments, the first thermally conductive metal plate 128 is selected from at least one of molybdenum, tungsten, tantalum, rhenium, and copper alloy, and the second thermally conductive metal plate 129 is selected from at least one of molybdenum, tungsten, tantalum, rhenium, and copper alloy. Molybdenum, tungsten, tantalum, and rhenium have extremely high melting points (>2600℃), and copper alloys also have high melting points. All of the above materials can maintain good structural stability at the evaporation temperature of the vapor deposition material and are not easily deformed. Furthermore, the heat generated by the second heating component or the third heating component can be quickly and evenly distributed across the entire plate surface, which is beneficial for uniformly heating the pre-coating layer and thus for depositing a film layer of uniform thickness on the substrate.

[0072] For example, the heating temperature of the second heating component 125 and the third heating component 126 can be room temperature to 300°C.

[0073] In some embodiments, reference Figure 6 The second heating component 125 can be located between the first heat-conducting metal plate 128 and the heat insulation plate 127, and the third heating component 126 can be located between the heat insulation plate 127 and the second heat-conducting metal plate 129. In other embodiments, the second heating component 125 can be disposed in the first heat-conducting metal plate 128, and the third heating component 126 can be disposed in the second heat-conducting metal plate 129, that is, the heating components are built into the metal plates.

[0074] In some embodiments, the vapor deposition equipment may further include a control system, which may include an automation control component that can control the bottom vapor deposition plate to automatically flip, control the first heating component to heat the vapor deposition material in the container, control the second heating component to heat the first plate, and control the third heating component to heat the second plate, etc.

[0075] The deposition principle and beneficial effects of the vapor deposition equipment of this application are described in detail below: (1) It can achieve "full-surface coating" and reduce material waste.

[0076] Traditional "bottom coating" (evaporation source below, substrate above) methods can lead to material waste at the edges due to substrate obstruction. However, the "top surface source" (evaporation source above, substrate below) method of this application allows the vertically collimated molecular beam to cover the entire surface of the substrate without obstruction, solving the edge loss caused by substrate obstruction and achieving "full-surface coating", thus reducing waste in terms of spatial layout.

[0077] (2) The bottom vapor deposition plate is a surface evaporation source (surface source), which can achieve uniform film deposition.

[0078] This application uses a "large-area planar structure" as its surface source. Compared with the "point divergence" and "line divergence" of traditional point / line sources, its sublimated molecular beam is spatially uniform and has strong vertical consistency. It can adapt to complex stepped structures (such as the intermediate connecting layer of a tandem battery), achieving pore-free and highly conformal coverage. This ensures that pore-free, highly conformal, and uniformly thick films are obtained on large-area, stepped, complex tandem structures, precisely solving the stringent requirements for uniformity in current matching in three-terminal structures. Furthermore, it can increase the material utilization rate to over 60%.

[0079] (3) "Low temperature deposition and high vacuum environment" can reduce damage to the substrate.

[0080] Vacuum degree ≤10 -7 In the high vacuum state of Torr, air molecules (such as oxygen and water vapor) are largely expelled, which not only avoids beam divergence caused by collisions between vapor from the vaporized material and air molecules (ensuring vertical collimation), but also prevents chemical erosion of the perovskite substrate and organic interface by water and oxygen (achieving interface non-destruction). Under high vacuum conditions, the operating temperature of the bottom vaporization plate (surface source) can be as low as 100℃-180℃, far below the decomposition temperature of perovskite, thus thermodynamically eliminating thermal damage.

[0081] (4) Easier equipment maintenance.

[0082] The top-mounted surface source configuration makes it easy to modularly lift, disassemble, and maintain the evaporation source module from the top of the cavity; material replenishment and component replacement can be carried out without affecting the substrate area below.

[0083] In another aspect of this application, a vapor deposition method is proposed, which uses the aforementioned vapor deposition equipment to perform vapor deposition, and the vapor deposition method includes the following steps: S10: Place the vapor deposition assembly 100 and the substrate 10 to be vaporized in the vapor deposition chamber, with the vapor deposition assembly 100 positioned above the substrate 10.

[0084] In some embodiments, reference Figure 4The distance L between the bottom vapor deposition plate 120 and the substrate 10 can be 50mm-800mm, for example, the distance L can be 50mm, 70mm, 100mm, 300mm, 500mm, 800mm, etc. The vapor deposition equipment of this application can shorten the distance between the vapor deposition source and the substrate, which is beneficial to depositing a film layer with uniform thickness on the substrate.

[0085] In some embodiments, the vapor deposition assembly 100 can be fixed to the top of the vapor deposition chamber using tools such as screws. In other embodiments, the vapor deposition assembly 100 can also be placed above the substrate using a support such as a bracket.

[0086] S20: Connect the vapor deposition chamber to the vacuum pump and evacuate the vacuum.

[0087] In some embodiments, the vacuum level of the environment surrounding the substrate 10 can be ≤10 by vacuuming. -7 Torr, a high-vacuum environment, can provide an ultra-clean inert atmosphere for deposition, avoiding chemical erosion of the interface by water and oxygen, and can also reduce the deposition temperature, thus reducing thermal damage to the substrate.

[0088] In some embodiments, the vacuum level of the environment in which the container 140 is located can be 10. -2 Togo-10 -5 The top plate, side plates, and bottom evaporation plate of the vapor deposition assembly form a closed system. During the vacuuming process, it is difficult to reduce the vacuum level to the level of the substrate environment. A higher temperature can be used to heat the vapor deposition material in the container, causing the material to sublimate and deposit rapidly onto the bottom evaporation plate. This helps to shorten the evaporation time and improve the evaporation efficiency.

[0089] S30: The first heating component is used to perform a first heating treatment on the vapor deposition material 20 in the container 140, so that the vapor deposition material 20 escapes from the discharge hole 150 and adheres to the first plate 121 or the second plate 122.

[0090] In some embodiments, the temperature of the first heat treatment can be 300℃-600℃, for example, 350℃, 400℃, 450℃, 500℃, 550℃, etc. For the electron transport layer, hole transport layer, electrode, and other functional layers in the top cell of a perovskite tandem solar cell, as well as the intermediate connection layer between the top and bottom cells, the above-mentioned temperature allows the solid vapor deposition material to sublimate, escape from the opening, and be dispersed and deposited on the bottom vapor deposition plate through the discharge hole.

[0091] S40: Flip the bottom vapor deposition plate 120 and perform a second heat treatment on the second plate 122 or the first plate 121 facing the substrate 10, so that the vapor deposition material 20 on the second plate 122 or the first plate 121 is deposited on the substrate 10.

[0092] In some embodiments, the temperature of the second heat treatment can be 100℃-180℃, for example, the temperature of the second heat treatment can be 110℃, 125℃, 150℃, 170℃, etc. During the deposition process, the substrate can be placed in a high vacuum environment by evacuation, which can reduce the deposition temperature of the vapor-deposited material. Vertical collimation sublimation can be generated and deposited on the substrate at 100℃-180℃.

[0093] In some embodiments, reference Figure 3 , Figure 5 and Figure 6 One of the first plate 121 and the second plate 122 receives the vapor deposition material 20, while the other serves as the deposition surface to provide the vapor deposition material 20 to the substrate 10.

[0094] In some embodiments, a predetermined thickness can be set by the control system. After the vapor deposition material 20 on the plate facing the substrate 10 of the bottom vapor deposition plate 120 is exhausted or the thickness reaches the predetermined thickness, the bottom vapor deposition plate 120 is automatically flipped, and the plate that has completed pre-deposition turns to face the substrate, which is called the new deposition surface.

[0095] In this application, the flipping action of the bottom vapor deposition plate achieves "efficient, non-destructive, and uniform deposition," which is applied across multiple key dimensions, including material pretreatment, deposition efficiency, utilization improvement, and process stability. 1. Achieve a continuous cycle of "pre-deposition-deposition", breaking through the bottleneck of traditional vapor deposition efficiency.

[0096] For ease of explanation, we define the following: regardless of how the bottom vapor deposition plate is flipped, the side facing the container is side A, and the side facing the substrate is side B.

[0097] Flip the bottom vapor deposition plate to create an "alternating working mode" between side A and side B: When material sublimation deposition is performed with side B facing the substrate, side A simultaneously receives the sublimated vaporized material in the container (e.g., crucible) (pre-deposition), without waiting for the completion of a single deposition before replenishing the material; once the material on side B is exhausted or the set deposition amount is reached, the bottom vaporization plate quickly flips over, and side A, which has completed pre-deposition, turns to face the substrate (becoming the new "deposition surface"), while the original side B turns to face the container (starting a new pre-deposition).

[0098] This design allows "material replenishment" and "actual deposition" to proceed in parallel, completely avoiding the time wasted in traditional vapor deposition by "stopping the machine to replenish materials" or "waiting for material sublimation and adhesion," greatly improving continuous production efficiency and providing a process foundation for mass industrialization.

[0099] 2. Key design features that ensure material utilization exceeds 60% and reduce waste.

[0100] Combining the "closed structure" of the surface source system, the flipping action improves material utilization on two levels: Pre-deposition stage: The A side (facing the container) uses the "sponge-like capture" of the porous plate (porous molybdenum felt / porous ceramic plate) to attach the sublimated material in the container to the plate surface to the maximum extent, and avoid the material from randomly diffusing and escaping into the cavity; Deposition stage: After flipping, the material pre-deposited on the plate surface is vertically collimated and sublimated directly onto the substrate below, reducing edge waste caused by traditional point source / line source "divergent evaporation"; Compared to traditional vapor deposition (material utilization rate <20%), the flip design allows the material to form a closed loop from "capture-deposition", with only a small amount lost on the surface source sidewall (side plate), ultimately achieving a breakthrough in utilization rate >60%, which can significantly reduce the waste of precious metals and expensive organic transport materials.

[0101] 3. Ensure film thickness uniformity to support the core requirement of "current matching" for tandem batteries.

[0102] The flipping action, combined with the structural design of the bottom vapor deposition plate, ensures uniform deposition from the source: Pre-deposition stage: The porous plate and high thermal conductivity metal plate on side A allow the material to adhere evenly to form a "pre-coating layer of uniform thickness", avoiding local material accumulation or gaps; Deposition stage: After flipping, the pre-coating layer is uniformly heated by a high thermal conductivity metal plate, thereby achieving "isotropic sublimation" and generating a vertically collimated molecular beam, ensuring the formation of a pore-free film with uniform thickness on a large-area substrate and complex stepped structure; The combination of "uniform pre-coating" and "uniform sublimation" can meet the key requirement of "current matching" for nanoscale film thickness uniformity in three-terminal perovskite tandem solar cells, and avoid the device performance degradation problem caused by "local over / under-material" in traditional evaporation.

[0103] 4. Avoid interface damage and maintain the stability of the "low temperature process".

[0104] The flipping action indirectly ensures the core advantage of "low-temperature deposition": The material adhesion during the pre-deposition stage is completed under high-temperature heating (300°C-600°C) in the container, but this high temperature only applies to the "A side facing the container" and there is no direct thermal radiation contact with the substrate below (the substrate is under a vacuum of ≤10). - 7 Torr's high vacuum environment results in extremely low thermal conductivity. During the deposition stage, the heating temperature of the vapor deposition plate is only 100°C-180°C (far lower than the decomposition temperature of perovskite). When the material sublimates from the pre-coating, no additional high-temperature excitation is required, which avoids the thermal radiation damage to the substrate caused by the traditional vapor deposition "direct high-temperature evaporation". The flipping action physically isolates the "high-temperature pre-coating" from the "low-temperature deposition," ensuring that the material can fully sublimate and adhere, while completely avoiding the damage of high temperature to the perovskite substrate and organic interface, thus achieving the goal of "interface-free".

[0105] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A vapor deposition apparatus, characterized in that, Includes a vapor deposition assembly, which, in use, is placed above the substrate to be vapor deposited; The vapor deposition assembly includes an upper top plate, a bottom vapor deposition plate, and a side plate. The bottom vapor deposition plate is disposed opposite to the upper top plate, and the upper top plate, the side plate, and the bottom vapor deposition plate constitute a closed structure. The vapor deposition assembly also includes multiple containers located between the upper top plate and the bottom vapor deposition plate for holding vapor deposition materials. Each container has an opening facing the upper top plate, and a discharge hole is provided between adjacent containers. The vapor deposition assembly further includes a first heating assembly for heating the vapor deposition material in the container; The bottom vapor deposition plate includes a first plate and a second plate disposed opposite to each other, and the bottom vapor deposition plate is flip-up, and the first plate and the second plate can alternately receive vapor deposition material.

2. The vapor deposition equipment according to claim 1, characterized in that, The first plate and the second plate have a porous structure; Optionally, the first plate and the second plate are each independently selected from at least one of porous molybdenum metal felt and porous ceramic plate; Optionally, the pore diameter of the first plate is 0.01 mm to 2 mm; Optionally, the pore diameter of the second plate is 0.01 mm to 2 mm.

3. The vapor deposition equipment according to claim 1, characterized in that, The bottom vapor deposition plate also includes a second heating component, a third heating component, and a heat insulation plate between them. The second heating component is located between the first plate and the heat insulation plate, and the third heating component is located between the heat insulation plate and the second plate.

4. The vapor deposition equipment according to claim 3, characterized in that, The bottom vapor-deposited plate also includes a first thermally conductive metal plate, which is located between the first plate and the heat insulation plate. And / or, the bottom vapor-deposited plate further includes a second thermally conductive metal plate, the second thermally conductive metal plate being located between the heat insulation plate and the second plate; Optionally, the first heat-conducting metal plate is selected from at least one of molybdenum, tungsten, tantalum, rhenium, and copper alloy; Optionally, the second heating component is located between the first heat-conducting metal plate and the heat insulation plate, or the second heating component is disposed in the first heat-conducting metal plate; Optionally, the second heat-conducting metal plate is selected from at least one of molybdenum, tungsten, tantalum, rhenium, and copper alloy; Optionally, the third heating component is located between the heat insulation plate and the second heat-conducting metal plate, or the third heating component is disposed in the second heat-conducting metal plate.

5. The vapor deposition equipment according to claim 1, characterized in that, One or more first micro balance sensors are embedded on the first plate, and / or one or more second micro balance sensors are embedded on the second plate; Optionally, the first microbalance sensor is a quartz crystal microbalance sensor; Optionally, the second microbalance sensor is a quartz crystal microbalance sensor.

6. The vapor deposition equipment according to any one of claims 1-5, characterized in that, At least one of the following conditions must be met: The width of the discharge hole is 1cm-2cm; The vapor deposition equipment also includes a control system; The vapor deposition equipment also includes a vapor deposition chamber for placing the vapor deposition components and the substrate to be vapor deposited.

7. A vapor deposition method, characterized in that, Evaporation deposition using the vapor deposition equipment according to any one of claims 1-6 includes the following steps: The vapor deposition assembly and the substrate to be vaporized are placed in the vapor deposition chamber, with the vapor deposition assembly positioned above the substrate; Connect the vapor deposition chamber to a vacuum pump and evacuate it. The first heating component is used to perform a first heating treatment on the vapor-deposited material in the container, so that the vapor-deposited material escapes from the discharge hole and adheres to the first plate or the second plate. Flip the bottom vapor deposition plate and perform a second heat treatment on the second or first plate facing the substrate, so that the vapor deposition material on the second or first plate is deposited on the substrate.

8. The method according to claim 7, characterized in that, One of the first and second plates receives the vapor deposition material while the other serves as the deposition surface, supplying the vapor deposition material to the substrate.

9. The method according to claim 7, characterized in that, The system sets a predetermined thickness, and the bottom vapor deposition plate is automatically flipped after the vapor deposition material on the substrate side of the bottom vapor deposition plate is exhausted or the thickness reaches the predetermined thickness.

10. The method according to any one of claims 7-9, characterized in that, At least one of the following conditions must be met: The vacuum level of the environment in which the substrate is located is ≤10. -7 Entrust; The vacuum level of the environment in which the container is located is 10. -2 Togo-10 -5 Entrust; The distance between the bottom vapor deposition plate and the substrate is 50mm-800mm; The temperature of the first heat treatment is 300℃-600℃; The temperature of the second heat treatment is 100℃-180℃.

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