Perovskite crystalline silicon laminated cell, manufacturing method thereof, photovoltaic module and photovoltaic system

Abstract

The invention relates to the technical field of batteries, and discloses a perovskite crystalline silicon laminated battery, a manufacturing method thereof, a photovoltaic module and a photovoltaic system. The manufacturing method of the perovskite crystalline silicon laminated cell comprises the following steps: providing a silicon substrate, wherein the silicon substrate comprises a first surface and a second surface which are oppositely arranged; manufacturing a P-type doped layer and a first electrode layer which are stacked in sequence on the first surface of the silicon substrate; an N-type doped layer, a tunneling layer, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, a second electrode layer and an antireflection layer which are sequentially stacked are manufactured on the second surface of the silicon substrate; wherein the step of manufacturing the buffer layer comprises the step of forming the buffer layer on one side, far away from the perovskite layer, of the electron transport layer by adopting a plasma enhanced atomic layer deposition method. According to the technical scheme provided by the invention, the long-term stability of the perovskite crystalline silicon laminated cell can be improved.

Description

Technical Field

[0001] This application relates to the field of battery technology, and in particular to a perovskite crystalline silicon tandem solar cell and its fabrication method, photovoltaic module and photovoltaic system. Background Technology

[0002] Perovskite-silicon tandem solar cells are a novel type of photovoltaic device composed of perovskite and crystalline silicon cells. This type of cell utilizes the complementary absorption characteristics of perovskite and crystalline silicon materials for different wavelengths of sunlight, achieving efficient segmented utilization of the solar spectrum. This breaks through the theoretical efficiency limit of traditional single-crystal silicon cells, achieving higher photoelectric conversion efficiency.

[0003] However, the long-term stability of this type of battery is not as good as that of mature crystalline silicon batteries. Insufficient stability will cause the photoelectric conversion efficiency of the battery to decay rapidly over time, which will seriously affect the performance and actual service life of the battery. Summary of the Invention

[0004] The purpose of this application is to provide a perovskite-silicon tandem solar cell, its fabrication method, photovoltaic module, and photovoltaic system, which can improve the long-term stability of the perovskite-silicon tandem solar cell.

[0005] An embodiment of the first aspect of this application provides a method for fabricating a perovskite-silicon tandem solar cell, comprising: providing a silicon substrate, the silicon substrate including a first side and a second side disposed opposite to each other; fabricating a P-type doped layer and a first electrode layer sequentially stacked on the first side of the silicon substrate; fabricating an N-type doped layer, a tunneling layer, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, a second electrode layer, and an antireflection layer sequentially stacked on the second side of the silicon substrate; wherein, fabricating the buffer layer comprises: forming a buffer layer on the side of the electron transport layer away from the perovskite layer using plasma-enhanced atomic layer deposition.

[0006] The fabrication method provided in this application uses plasma-enhanced atomic layer deposition to fabricate a buffer layer. This process can achieve high-density growth of the buffer layer under low-temperature conditions and significantly reduce the defect density of the buffer layer. The buffer layer prepared in this way can meet the design requirements of perovskite-silicon tandem solar cells in terms of low-temperature compatibility, interface stability and high-efficiency transmission. Therefore, this solution can significantly improve the long-term stability and reliability of perovskite-silicon tandem solar cells.

[0007] In some embodiments, forming a buffer layer on the side of the electron transport layer away from the perovskite layer using plasma-enhanced atomic layer deposition includes: depositing a SnO2 thin film on the side of the electron transport layer away from the perovskite layer using an atomic layer deposition apparatus; and modifying the surface of the SnO2 thin film using a plasma generator, wherein the working gas in the plasma generator includes argon and oxygen.

[0008] In some embodiments, the plasma generating apparatus includes a magnetron sputtering apparatus.

[0009] In some embodiments, the power of the magnetron sputtering device is 30W-300W, and / or the flow rate of the working gas in the magnetron sputtering device is 5sccm-50sccm, and / or the flow ratio of argon to oxygen is 280:1-1:1, and / or the chamber substrate heating temperature of the magnetron sputtering device is 25℃-80℃, and / or the working time of the magnetron sputtering device is 1min-30min.

[0010] In some embodiments, the deposition vacuum degree of the atomic layer deposition equipment is 0-1×10⁻⁶. 4 Pa, and / or the deposition pipe temperature of the atomic layer deposition equipment is 50℃-150℃, and / or the deposition chamber temperature of the atomic layer deposition equipment is 40℃-150℃.

[0011] In some embodiments, the thickness of the SnO2 film is 10nm-20nm.

[0012] In some embodiments, before fabricating the P-type doped layer, the fabrication method includes: fabricating a first passivation layer on a first side of a silicon substrate; and / or, before fabricating the N-type doped layer, the fabrication method includes: fabricating a second passivation layer on a second side of a silicon substrate; and / or, before fabricating the electron transport layer, the fabrication method includes: fabricating a third passivation layer on the side of the perovskite layer away from the silicon substrate.

[0013] An embodiment of the second aspect of this application provides a perovskite-silicon tandem solar cell, which is fabricated using the method of the first aspect.

[0014] The perovskite-silicon tandem solar cell provided in this application improves the long-term stability and reliability of the cell by adopting the manufacturing method of the first aspect.

[0015] An embodiment of the third aspect of this application provides a photovoltaic module, including a perovskite-silicon tandem cell, which is fabricated using the fabrication method of the first aspect.

[0016] The photovoltaic module provided in this application, by adopting the manufacturing method of the first aspect, improves the long-term stability and reliability of the perovskite-silicon tandem cell and the photovoltaic module containing the perovskite-silicon tandem cell.

[0017] An embodiment of the fourth aspect of this application provides a photovoltaic system, including the photovoltaic module of the third aspect.

[0018] The photovoltaic system provided in this application improves the long-term stability and reliability of the photovoltaic modules by adopting photovoltaic modules from a third aspect. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a schematic diagram of the structure of a perovskite-silicon tandem solar cell provided in an embodiment of this application; Figure 2 One of the flowcharts for a method of fabricating a perovskite-silicon tandem solar cell provided in the embodiments of this application; Figure 3 This is the second flowchart of a method for fabricating a perovskite-silicon tandem solar cell provided in an embodiment of this application.

[0021] Explanation of key component symbols: 1000, Perovskite-silicon tandem solar cells; 11. First electrode layer; 111. First transparent electrode layer; 112. First metal electrode layer; 12. P-type doped layer; 13. First passivation layer; 14. Silicon substrate; 15. Second passivation layer; 16. N-type doped layer; 21. Tunneling layer; 31. Hole transport layer; 32. Perovskite layer; 33. Third passivation layer; 34. Adhesion layer; 35. Electron transport layer; 36. Buffer layer; 37. Second electrode layer; 371. Second transparent electrode layer; 372. Second metal electrode layer; 38. Antireflection layer. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0023] It should be noted that when a component is referred to as "fixed to" or "set on" another component, it can be directly or indirectly attached to that other component. When a component is referred to as "connected to" another component, it can be directly or indirectly connected to that other component. The terms "upper," "lower," "left," "right," etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are for descriptive convenience only, not indicating or implying that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the patent. The terms "first" and "second" 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. "A plurality" means two or more, unless otherwise explicitly defined.

[0024] In this specification, references to "one embodiment," "some embodiments," or simply "embodiment" mean that one or more embodiments of this application include a specific feature, structure, or characteristic described in connection with that embodiment. Therefore, the phrases "in one embodiment," "in some embodiments," "in other embodiments," "in still other embodiments," etc., appearing in different parts of this specification do not necessarily refer to the same embodiment, but rather mean "one or more, but not all, embodiments," unless otherwise specifically emphasized. Furthermore, in one or more embodiments, specific features, structures, or characteristics may be combined in any suitable manner.

[0025] The instability of perovskite-silicon tandem solar cells is caused by multiple factors, such as the intrinsic defects of the perovskite material itself, the interfacial compatibility issues between the various film layers inside the device, and the environmental sensitivity of the material.

[0026] In typical tandem solar cell structures, the perovskite top cell has a buffer layer. However, due to the thermal stability limitations of the crystalline silicon bottom cell, the buffer layer must be fabricated at low temperatures. This temperature window constraint prevents the buffer layer from forming an ordered crystalline structure, forcing it to exist in an amorphous state. Amorphous structures inherently suffer from high defect density, high surface roughness, and weak chemical stability, all of which significantly impact the long-term stability of perovskite-crystalline silicon tandem solar cells.

[0027] Based on the above problems, this application provides a perovskite-silicon tandem solar cell and its fabrication method, photovoltaic module and photovoltaic system. By optimizing the fabrication process of the perovskite-silicon tandem solar cell, the long-term stability and reliability of the perovskite-silicon tandem solar cell can be effectively improved.

[0028] In a first aspect, embodiments of this application provide a method for fabricating a perovskite-silicon tandem solar cell.

[0029] Please refer to Figure 1and Figure 2 The manufacturing method provided in this application includes: S100, A silicon substrate 14 is provided, the silicon substrate 14 including a first surface and a second surface disposed opposite to each other.

[0030] The silicon substrate 14 can be a high-purity single-crystal silicon wafer, and is not limited to any particular type; it can be P-type doped or N-type doped. The first and second surfaces of the silicon substrate 14 can have a textured surface.

[0031] The silicon substrate 14 has a certain thickness and can serve as a support substrate for the perovskite crystalline silicon tandem solar cell 1000, providing reliable mechanical support for other functional layers.

[0032] S200, A P-type doped layer 12 and a first electrode layer 11 are sequentially stacked on the first side of the silicon substrate 14.

[0033] Specifically, a P-type doped layer 12 is formed on the first surface of the silicon substrate 14, and a first electrode layer 11 is formed on the side of the P-type doped layer 12 away from the silicon substrate 14.

[0034] S300: An N-type doped layer 16, a tunneling layer 21, a hole transport layer 31, a perovskite layer 32, an electron transport layer 35, a buffer layer 36, a second electrode layer 37, and an anti-reflection layer 38 are sequentially stacked on the second side of the silicon substrate 14. The fabrication of the buffer layer 36 includes forming the buffer layer 36 on the side of the electron transport layer 35 away from the perovskite layer 32 using plasma-enhanced atomic layer deposition.

[0035] Specifically, an N-type doped layer 16 is formed on the second surface of the silicon substrate 14, a tunneling layer 21 is formed on the side of the N-type doped layer 16 away from the silicon substrate 14, a hole transport layer 31 is formed on the side of the tunneling layer 21 away from the N-type doped layer 16, a perovskite layer 32 is formed on the side of the hole transport layer 31 away from the tunneling layer 21, an electron transport layer 35 is formed on the side of the perovskite layer 32 away from the hole transport layer 31, a buffer layer 36 is formed on the side of the electron transport layer 35 away from the perovskite layer 32, a second electrode layer 37 is formed on the side of the buffer layer 36 away from the electron transport layer 35, and an anti-reflection layer 38 is formed on the side of the second electrode layer 37 away from the buffer layer 36.

[0036] The buffer layer 36 is an ultrathin functional layer disposed between the electron transport layer 35 and the second electrode layer 37. Its main functions are to improve energy level matching between the upper and lower film layers, reduce contact barriers, and block the diffusion of metal ions from the outer electrode layer. The material of the buffer layer 36 can be, but is not limited to, small organic molecules, inorganic compounds, etc. The buffer layer 36 is prepared using plasma-enhanced atomic layer deposition (PEALD). Specifically, an ultrathin film is deposited on the surface of the substrate on which the buffer layer 36 is to be formed, and then plasma is introduced for surface modification to form the desired buffer layer 36.

[0037] On the one hand, plasma, with its directionality and high kinetic energy, can bombard the thin film surface, promoting the migration and rearrangement of atoms on the surface and filling the microporous structure, thereby effectively improving the compactness of the buffer layer 36. Increased compactness of the buffer layer 36 improves the contact effect between the upper and lower film layers, reduces the risk of film delamination, and effectively blocks the diffusion of metal ions from the electrode layer to the perovskite layer 32, thus enhancing the battery's stability. On the other hand, the highly active oxides within the plasma can fill oxygen vacancies on the thin film surface, thereby reducing the defect density of the buffer layer 36. Reduced defect density in the buffer layer 36 reduces interfacial recombination and lowers the contact resistance between film layers, thus enhancing the battery's electrical performance. Furthermore, the energy of the plasma can promote the transformation of amorphous thin films into nanocrystalline or microcrystalline structures under low-temperature conditions, forming nanoscale microcrystalline grains. This further optimizes the optical and electrical properties of the buffer layer 36, thereby improving the battery's photoelectric conversion efficiency.

[0038] The fabrication method provided in this application uses plasma-enhanced atomic layer deposition to fabricate the buffer layer 36. This process can achieve high-density growth of the buffer layer 36 under low-temperature conditions and significantly reduce the defect density of the buffer layer 36. The buffer layer 36 prepared in this way can meet the design requirements of the perovskite-silicon tandem solar cell 1000 in terms of low-temperature compatibility, interface stability and high-efficiency transmission. Therefore, this solution can significantly improve the long-term stability and reliability of the perovskite-silicon tandem solar cell 1000.

[0039] In some embodiments, please refer to Figure 1 , Figure 2 and Figure 3 In step S300, a buffer layer 36 is formed on the side of the electron transport layer 35 away from the perovskite layer 32 using plasma-enhanced atomic layer deposition, including: S310. An SnO2 thin film is deposited on the side of the electron transport layer 35 away from the perovskite layer 32 using an atomic layer deposition apparatus.

[0040] SnO2 is an inorganic oxide material with high electron mobility, high light transmittance, and good chemical stability. The buffer layer 36 is designed as SnO2, which enables excellent energy level matching and optimizes electron transport performance.

[0041] S320. Surface modification of SnO2 thin films is performed using a plasma generator, wherein the working gas in the plasma generator includes argon and oxygen.

[0042] Argon is an inert gas. The Ar⁺ ions produced by its ionization have a physical sputtering effect, which can bombard the surface of SnO2 thin films, causing the atoms and lattice of the SnO2 thin film to shift and rearrange, thereby improving the compactness of the SnO2 thin film.

[0043] Oxygen is used to provide highly reactive oxygen radicals and O⁺ ions to oxidize oxygen vacancies in SnO2 films, thereby reducing n-type doping and defect states in SnO2 films and improving the insulation (hole blocking) and stability of SnO2 films.

[0044] In the above embodiments, on the one hand, SnO2 is selected as the material of buffer layer 36, and plasma surface modification is performed using a mixture of argon and oxygen gas, which can obtain a high-quality, low-defect, and high-stability buffer layer 36; on the other hand, the deposition and surface modification of buffer layer 36 are carried out in two steps, which can independently optimize the deposition parameters and plasma processing parameters, reduce the mutual interference between the deposition and plasma processing, and thus help to further improve the film quality of buffer layer 36.

[0045] In some embodiments, the plasma generating apparatus includes a magnetron sputtering apparatus.

[0046] Magnetron sputtering equipment can generate low-temperature plasma using an electric field, and then use charged particles to bombard the surface of thin films to achieve physical and chemical modification of the film surface.

[0047] On the one hand, magnetron sputtering equipment can generate high-density plasma and has high modification efficiency; on the other hand, magnetron sputtering equipment uses electrical energy rather than thermal energy to process plasma, which can achieve efficient modification under low-temperature conditions and meet the low-temperature process requirements of perovskite crystalline silicon tandem solar cells 1000.

[0048] In some embodiments, the power of the magnetron sputtering device is 30W-300W, and / or the flow rate of the working gas in the magnetron sputtering device is 5sccm-50sccm, and / or the flow ratio of argon to oxygen is 280:1-1:1, and / or the chamber substrate heating temperature of the magnetron sputtering device is 25℃-80℃, and / or the working time of the magnetron sputtering device is 1min-30min.

[0049] The power of the magnetron sputtering equipment directly affects the plasma density and ion energy. If the magnetron sputtering equipment power is too low, it may result in insufficient plasma density and weak ion bombardment energy, leading to insignificant modification effects. Conversely, if the magnetron sputtering equipment power is too high, it may result in excessively high plasma density and excessively strong ion bombardment energy, easily causing damage to the film surface. Limiting the power of the magnetron sputtering equipment to 30W-300W is beneficial for improving the surface modification effect of the film while reducing the risk of film damage.

[0050] The working gas flow rate refers to the total flow rate of argon and oxygen into the chamber of the magnetron sputtering equipment. The gas flow rate affects the working gas pressure and plasma stability within the equipment. If the working gas flow rate is too low, the number of gas molecules will be insufficient, making it difficult for the plasma to maintain a stable discharge. If the working gas flow rate is too high, the chamber pressure will be too high, shortening the mean free path of the ions and reducing the bombardment energy, thus affecting the modification effect. Limiting the working gas flow rate to 5 sccm-50 sccm is beneficial for maintaining a stable working gas pressure and improving the stability and efficiency of surface modification.

[0051] The argon to oxygen flow rate ratio refers to the ratio of their volumetric flow rates. Argon is used to provide physical bombardment, while oxygen is used to provide chemical oxidation. By adjusting the ratio of argon to oxygen, different modification effects can be achieved. Setting the argon to oxygen flow rate ratio in a wide range of 280:1 to 1:1 can cover a variety of modification modes and has high applicability.

[0052] The heating temperature of the chamber substrate is used to control the actual temperature of the substrate on which the buffer layer 36 is to be fabricated. In this embodiment, the substrate includes all functional layers fabricated before the buffer layer 36. If the heating temperature of the chamber substrate is too low, it may lead to insufficient surface reaction kinetics, affecting the surface modification efficiency; if the heating temperature of the chamber substrate is too high, it may cause decomposition of some functional layers within the substrate, affecting the product quality of the perovskite silicon tandem solar cell 1000. Limiting the heating temperature of the chamber substrate to 25℃-80℃ can meet the low-temperature process requirements of the perovskite silicon tandem solar cell 1000, and also promotes the chemical reaction on the thin film surface, effectively improving the surface modification efficiency.

[0053] The operating time of the magnetron sputtering equipment determines the duration for which plasma continuously acts on the thin film. Limiting the operating time of the magnetron sputtering equipment to 1-30 minutes is beneficial for balancing surface modification effects and production efficiency.

[0054] It should be noted that the settings of the above process parameters are related, and in practical applications, they can be adjusted in a coordinated manner according to the initial state of the SnO2 film to be processed.

[0055] In some embodiments, the deposition vacuum degree of the atomic layer deposition equipment is 0-1×10⁻⁶. 4 Pa, and / or the deposition pipe temperature of the atomic layer deposition equipment is 50℃-150℃, and / or the deposition chamber temperature of the atomic layer deposition equipment is 40℃-150℃.

[0056] The deposition vacuum level of an atomic layer deposition (ALD) system refers to the operating pressure of the reaction chamber. The deposition vacuum level affects the film deposition effect; specifically, if the deposition vacuum is too high, it may lead to uneven film deposition or particle formation during the deposition process. The deposition vacuum level is typically limited to 0-1 × 10⁻⁶.4 Pa can balance the requirements of thin film deposition efficiency and thin film deposition quality.

[0057] The deposition pipeline of an atomic layer deposition (ALD) system is used to transport gaseous precursors, and its temperature directly affects the transport state of these precursors. If the pipeline temperature is too low, the precursors may liquefy or crystallize within the pipeline, leading to blockages. Conversely, if the pipeline temperature is too high, the precursors may undergo thermal decomposition, generating impurity gases that negatively impact the reliability of subsequent thin film deposition. Limiting the deposition pipeline temperature to 50℃-150℃ meets the transport requirements of various precursor types, ensuring that the precursors remain in a stable gaseous state, thus contributing to a stable and continuous supply.

[0058] The deposition chamber temperature of an atomic layer deposition (ALD) system refers to the ambient temperature of the substrate on which the buffer layer 36 is to be fabricated. If the deposition chamber temperature is too low, it may result in a slow film deposition rate and poor film quality; if the chamber temperature is too high, it may cause decomposition of some functional layers within the substrate, failing to meet the requirements of low-temperature processes. Limiting the deposition chamber temperature to 40℃-150℃ balances the SnO2 film deposition rate, deposition effect, and the low-temperature process requirements of the perovskite-silicon tandem solar cell 1000.

[0059] It should be noted that the settings of the above process parameters are related, and in practical applications, they can be adjusted in conjunction with the design requirements of the SnO2 thin film to be processed.

[0060] In some embodiments, the thickness of the SnO2 film is 10nm-20nm.

[0061] For example, the thickness of the SnO2 film can be 10 nm, 15 nm, or 20 nm.

[0062] The buffer layer 36 is mainly used to improve the energy level matching between the upper and lower film layers, reduce the contact barrier, and block the diffusion of metal ions from the outer electrode layer. The thickness of the buffer layer 36 directly affects the film quality, metal ion blocking effect, light transmittance, and electron transport effect. In the above embodiments, by limiting the thickness of the SnO2 film within a reasonable range, the performance requirements of film quality, metal blocking, light transmittance, and electron transport can be balanced, thereby improving the structural reliability of the buffer layer 36.

[0063] In some embodiments, please refer to Figure 1 The first electrode layer 11 includes a first transparent electrode layer 111 and a first metal electrode layer 112, with the first metal electrode layer 112 disposed on the side of the first transparent electrode layer 111 away from the P-type doped layer 12; the second electrode layer 37 includes a second transparent electrode layer 371 and a second metal electrode layer 372, with the second metal electrode layer 372 disposed on the side of the second transparent electrode layer 371 away from the buffer layer 36.

[0064] The first transparent electrode layer 111 and the second transparent electrode layer 371 are disposed on the inner side, possessing good transparency, and are used to guide incident light into the battery and to transport photogenerated carriers to the outer metal electrode layer. The materials of the first transparent electrode layer 111 and the second transparent electrode layer 371 can be the same or different, and are not limited to any one of indium tin oxide, indium zinc oxide, and aluminum zinc oxide; for example, in one specific embodiment, the materials of the first transparent electrode layer 111 and the second transparent electrode layer 371 are both indium tin oxide.

[0065] The first metal electrode layer 112 and the second metal electrode layer 372 are disposed on the outer side for collecting and discharging photogenerated charge carriers, enabling the battery to form a complete closed circuit and thereby generate current. The materials of the first metal electrode layer 112 and the second metal electrode layer 372 can be the same or different, and are not limited to any one of silver, gold, copper, aluminum, and carbon; for example, in one specific embodiment, the materials of the first metal electrode layer 112 and the second metal electrode layer 372 are both silver.

[0066] In some embodiments, before fabricating the P-type doped layer 12, the fabrication method includes: fabricating a first passivation layer 13 on a first surface of the silicon substrate 14; and / or, before fabricating the N-type doped layer 16, the fabrication method includes: fabricating a second passivation layer 15 on a second surface of the silicon substrate 14; and / or, before fabricating the electron transport layer 35, the fabrication method includes: fabricating a third passivation layer 33 on the side of the perovskite layer 32 away from the silicon substrate 14.

[0067] The first passivation layer 13 is directly deposited on the first surface of the silicon substrate 14, which can passivate the surface defects of the first surface of the silicon substrate 14 and provide a good contact interface for the P-type doped layer 12, thereby improving the stability and photoelectric performance of the battery.

[0068] The second passivation layer 15 is directly deposited on the second side of the silicon substrate 14, which can passivate the surface defects on the second side of the silicon substrate 14 and provide a good contact interface for the N-type doped layer 16, thereby improving the stability and photoelectric performance of the battery.

[0069] The third passivation layer 33 is directly deposited on the upper surface of the perovskite layer 32. It can passivate the surface defects of the perovskite layer 32, optimize the energy level matching between the perovskite layer 32 and the electron transport layer 35, and enhance the interface stability, thereby improving the battery stability and photoelectric performance.

[0070] The fabrication method provided in this application mainly improves the preparation process of the buffer layer 36. Specifically, by introducing plasma to modify the surface of the buffer layer 36, the film quality of the buffer layer 36 is improved, thereby enhancing the long-term stability and reliability of the battery. The specific preparation process of the buffer layer 36 and the setting of various operating parameters during the preparation process are particularly important. Several specific embodiments are provided below for explanation.

[0071] Example 1: Fabrication of buffer layer 36 using atomic layer deposition (ALD). Specifically, an ALD thin film of SnO2 is deposited on the side of electron transport layer 35 away from perovskite layer 32 using an ALD apparatus, with a deposition vacuum of 0.5 × 10⁻⁶. 4 Pa, deposition channel temperature is 60℃, deposition chamber temperature is 70℃, and SnO2 film thickness is 15nm.

[0072] Example 2: Fabrication of buffer layer 36 using ionosphere-enhanced atomic layer deposition (ILD). Specifically, a SnO2 thin film is deposited on the side of electron transport layer 35 away from perovskite layer 32 using an atomic layer deposition apparatus, with a deposition vacuum of 0.5 × 10⁻⁶. 4 The deposition pipeline temperature was 60℃, the deposition chamber temperature was 70℃, and the SnO2 film thickness was 15nm. Surface modification of the SnO2 film was performed using a magnetron sputtering device with a power of 100W. The working gas was a mixture of argon and oxygen with a flow rate of 28.1 sccm and an argon to oxygen flow ratio of 28:0.1. The chamber substrate heating temperature was 25℃, and the working time was 10min.

[0073] Example 3: Buffer layer 36 was fabricated using plasma-enhanced atomic layer deposition. The difference between this example and Example 2 is that the chamber substrate heating temperature of the magnetron sputtering equipment was set to 50°C.

[0074] Example 4: Fabrication of buffer layer 36 using plasma-enhanced atomic layer deposition. The difference between this example and Example 2 is that the chamber substrate heating temperature of the magnetron sputtering equipment is set to 80°C.

[0075] The defect density, surface roughness, and relative peak intensity of the buffer layer 36 in the above embodiments were measured using characterization techniques such as X-ray photoelectron spectroscopy, atomic force microscopy, and X-ray diffraction. The test results are as follows:

[0076] Comparing Example 1 with Examples 2, 3, and 4, it can be seen that using plasma-enhanced atomic layer deposition to fabricate buffer layer 36 can effectively reduce the defect density and surface roughness of buffer layer 36. Comparing Example 2, 3, and 4, it can be seen that increasing the chamber substrate heating temperature of the magnetron sputtering equipment can further reduce the defect density and surface roughness of buffer layer 36.

[0077] The photoelectric conversion efficiency and annual degradation rate of the perovskite-silicon tandem solar cells 1000 prepared in the above embodiments were measured using a solar simulator. Specifically, a standard solar intensity calibration was performed on a 1.0 cm² area. 2 The test object underwent a long-term IV test, with the starting voltage set to 2V, the cutoff voltage to 0V, and the range to 100mA. The test results were rounded to two decimal places. The test results are as follows:

[0078] Comparing Example 1 with Examples 2, 3, and 4, it can be seen that using plasma-enhanced atomic layer deposition to fabricate buffer layer 36 can effectively improve the photoelectric conversion efficiency of perovskite-silicon tandem solar cell 1000 and reduce the annual battery degradation rate. Comparing Example 2, 3, and 4, it can be seen that setting the heating temperature of the chamber substrate to an intermediate value (e.g., 50°C) results in even better improvement.

[0079] In one specific embodiment provided in this application, the method for fabricating a perovskite-silicon tandem solar cell 1000 includes: S1: A silicon substrate 14 is provided, the silicon substrate 14 including a first surface and a second surface disposed opposite to each other.

[0080] S2: A first passivation layer 13 is formed on the first side of the silicon substrate 14.

[0081] The first passivation layer 13 can be prepared by vapor deposition, spin coating, or spray coating, regardless of the location.

[0082] S3: A P-type doped layer 12 is formed on the side of the first passivation layer 13 away from the silicon substrate 14.

[0083] S4: A first transparent electrode layer 111 is formed on the side of the P-type doped layer 12 away from the first passivation layer 13.

[0084] The first transparent electrode layer 111 can be fabricated using magnetron sputtering, regardless of the location, with the equipment power limited to 50W-200W.

[0085] For example, the first transparent electrode layer 111 is fabricated using magnetron sputtering: the sample is placed in a magnetron sputtering device, an ITO target is set, the power is controlled at 60W, the running time is 1.5h, and the film thickness is 100nm.

[0086] S5: A first metal electrode layer 112 is formed on the side of the first transparent electrode layer 111 away from the P-type doped layer 12.

[0087] The first metal electrode layer 112 can be fabricated using vapor deposition, with the vapor deposition vacuum degree limited to 5 × 10⁻⁶. -5 Pa-2×10 -4 Pa, the evaporation temperature is limited to 500℃-2000℃, and the evaporation rate is limited to 0.1Å / S-5Å / S.

[0088] For example, the first metal electrode layer 112 is fabricated using vapor deposition: the sample is placed on a mask and placed in the vapor deposition chamber, and the vapor deposition vacuum degree is set to 2 × 10⁻⁶. -4 Evaporation is performed at Pa, the evaporation voltage is adjusted to the evaporation temperature, and the evaporation rate is controlled at 2.5 Å / S to deposit silver onto the first transparent electrode layer 111. The evaporation thickness of the silver layer is 200 nm.

[0089] S6: A second passivation layer 15 is formed on the second side of the silicon substrate 14.

[0090] The second passivation layer 15 can be prepared using methods such as vapor deposition, spin coating, or spray coating, regardless of the location.

[0091] S7: An N-type doped layer 16 is formed on the side of the second passivation layer 15 away from the silicon substrate 14.

[0092] S8: A tunneling layer 21 is formed on the side of the N-type doped layer 16 away from the second passivation layer 15.

[0093] The tunneling layer 21 can be fabricated using atomic layer deposition, magnetron sputtering, or wet chemical methods, regardless of the location.

[0094] For example, a tunneling layer 21 is fabricated using magnetron sputtering: the sample is placed in a magnetron sputtering device, the power is controlled at 60W, the running time is 1h, and the film thickness is 100nm.

[0095] S9: A hole transport layer 31 is fabricated on the side of the tunneling layer 21 away from the N-type doped layer 16.

[0096] Hole transport layer 31 can be fabricated using magnetron sputtering, with the equipment power limited to 30W-90W.

[0097] For example, a hole transport layer 31 is fabricated using magnetron sputtering: the sample is treated with an ultraviolet-ozone generator for 15 minutes, and the treated sample is placed in a magnetron sputtering device with a control power of 60W and a running time of 1 hour to prepare nickel oxide on the substrate surface with a film thickness of 40nm.

[0098] S10: Fabricate a perovskite layer 32 on the side of the hole transport layer 31 away from the tunneling layer 21.

[0099] The perovskite layer 32 can be fabricated using either flash evaporation or wet solution methods, regardless of the location. When fabricating the perovskite layer 32 using flash evaporation, the perovskite precursor solution is uniformly coated onto the surface of the hole transport layer 31. The spin coating speed is limited to 1000 rpm - 6000 rpm, and the spin coating time is limited to 20 s - 120 s. After spin coating, a flash evaporation operation is performed, with the flash evaporation time limited to 10 s - 60 s and the flash evaporation temperature limited to 0 - 100 ℃. After flash evaporation, an annealing treatment is performed, with the annealing temperature limited to 50 ℃ - 150 ℃ and the annealing time limited to 5 min - 40 min.

[0100] For example, perovskite layer 32 was prepared using flash evaporation: a perovskite precursor solution was prepared, and perovskite raw material powder was weighed and dissolved in 1 ml of DMF and DMSO solvent in equal proportions. The mixture was magnetically stirred for 30 min, with a solvent ratio of 8:2. The sample was placed on the spin coater platform, and the spin coater speed was set to 3500 rpm and the spin coater time was set to 30 s. 120 μL of perovskite precursor solution was coated onto the sample surface. After spin coater coating, the sample was placed on the flash evaporation platform, and the flash evaporation time was set to 30 s and the flash evaporation temperature was set to 30 °C. The film thickness was approximately 500 nm. After the flash evaporation, the sample was annealed at 100 °C for 15 min.

[0101] S11: A third passivation layer 33 is fabricated on the side of the perovskite layer 32 away from the hole transport layer 31.

[0102] The third passivation layer 33 can be fabricated using methods such as vapor deposition, spin coating, or spraying, regardless of the location. When fabricating the third passivation layer 33 using vapor deposition, the vapor deposition vacuum degree is limited to 1 Pa - 5 × 10⁻⁵. -4Pa, the evaporation temperature is limited to 50℃-400℃, the evaporation rate is limited to 0.05Å / S-1Å / S, and after evaporation, annealing is performed at a temperature limited to 0-150℃ for a time limited to 0-30 min. When preparing the third passivation layer 33 using spin coating, the dispersion is uniformly coated onto the substrate surface. Propylene diamine iodine is dissolved in organic solvents such as methanol, ethanol, or isopropanol, ultrasonically dissolved, and then spin-coated. The concentration of propylene diamine iodine is limited to 0.1 mg / ml-6 mg / ml, and the ultrasonic time is limited to 0-3 minutes. For the spin coating process, the spin speed is limited to 1000 rpm-7000 rpm, and the spin coating time is limited to 20 s-120 s. After spin coating, annealing is performed at a temperature of 40℃-160℃ for 5 min-40 min. When the third passivation layer 33 is prepared by spraying, the dispersion is sprayed onto the substrate surface at a spraying rate of 0-100 cm / s. After spraying, annealing is performed at a temperature of 20℃-170℃ for 0-30 min.

[0103] For example, the third passivation layer 33 is prepared by vapor deposition: 3 mg of propylenediamine iodine is weighed and placed in a crucible, the sample is placed on a mask, and then placed in the vapor deposition chamber. The vapor deposition vacuum degree is 2 × 10⁻⁶. -4 Evaporation was performed at Pa, adjusting the evaporation voltage to the evaporation temperature and controlling the evaporation rate at 0.1 Å / S. Propylene diamine iodine was deposited onto the perovskite absorber layer with a film thickness of 4 nm. After the evaporation, annealing was performed at a temperature of 100 °C for 8 min.

[0104] S12: An adhesion layer 34 is formed on the side of the third passivation layer 33 away from the perovskite layer 32.

[0105] The adhesion layer 34 can be fabricated using a vapor deposition method, whereby the material of the adhesion layer 34 is evaporated onto the surface of the substrate, and the vapor deposition vacuum degree is limited to 1 Pa - 5 × 10⁻⁵. -4 Pa, the evaporation temperature is limited to 50℃-400℃, the evaporation rate is limited to 0.05Å / S-1Å / S, and the film thickness is limited to 1nm-5nm.

[0106] S12: An electron transport layer 35 is fabricated on the side of the third passivation layer 33 away from the perovskite layer 32.

[0107] The electron transport layer 35 can be fabricated using spin coating, inkjet printing, or vapor deposition, regardless of the application method. When using spin coating, the dispersion is uniformly coated onto the substrate surface, with the spin coating speed limited to 500 rpm-4000 rpm and the spin coating time limited to 10 s-80 s. When using vapor deposition, the material is evaporated onto the substrate surface, with the vapor deposition vacuum degree limited to 5 × 10⁻⁶. -5 Pa-5×10-4 Pa, the evaporation temperature is limited to 100℃-400℃, and the evaporation rate is limited to 0.05Å / S-1Å / S.

[0108] For example, electron transport layer 35 is fabricated using vapor deposition: the sample is placed on a mask and placed in the vapor deposition chamber, and the vapor deposition vacuum is set to 1×10⁻⁶. -4 Evaporation is performed at Pa, adjusting the evaporation voltage to the evaporation temperature, and controlling the evaporation rate between 0.1 Å / s and 0.15 Å / s. C 60 The film is deposited onto the third passivation layer 33, with a thickness of 20 nm.

[0109] S13: A buffer layer 36 is fabricated on the side of the electron transport layer 35 away from the third passivation layer 33.

[0110] For example, an atomic layer deposition (ALD) apparatus is used to deposit a SnO2 thin film, with the deposition vacuum level set to 0.5 × 10⁻⁶. 4 The deposition pipeline temperature was 60℃, the deposition chamber temperature was 70℃, and the SnO2 film thickness was 15nm. Surface modification of the SnO2 film was performed using a magnetron sputtering device with a power of 100W, using argon and oxygen as the working gases at a flow rate of 28.1 sccm and an argon to oxygen ratio of 28:0.1. The chamber substrate temperature was 50℃, and the device operating time was 10min.

[0111] S14: A second transparent electrode layer 371 is fabricated on the side of the buffer layer 36 away from the electron transport layer 35.

[0112] The second transparent electrode layer 371 can be fabricated using either magnetron sputtering or vapor deposition. When fabricating the second transparent electrode layer 371 using magnetron sputtering, the material is sputtered onto the surface of the substrate, and the power is controlled to be limited to 30W-200W. When fabricating the second transparent electrode layer 371 using vapor deposition, the material is evaporated onto the surface of the substrate, and the vapor deposition vacuum degree is limited to 1×10⁻⁶. - 5 Pa-5×10 -4 Pa, the evaporation temperature is limited to 1000℃-2000℃, and the evaporation rate is limited to 0.05Å / S-3Å / S.

[0113] For example, the second transparent electrode layer 371 is fabricated using magnetron sputtering: the sample is placed in a magnetron sputtering device, an ITO target is set, the power is controlled at 50W, the running time is 1h, and the film thickness is 100nm.

[0114] S15: A second metal electrode layer 372 is formed on the side of the second transparent electrode layer 371 away from the buffer layer 36.

[0115] For example, the second metal electrode layer 372 is fabricated using vapor deposition: the sample is placed on a mask and placed in the vapor deposition chamber, and the vapor deposition vacuum degree is set to 2×10⁻⁶. -4 Evaporation was performed at Pa, the evaporation voltage was adjusted to the evaporation temperature, and the evaporation rate was controlled at 2.5 Å / S to deposit silver onto the second transparent electrode layer 371. The evaporation thickness of the silver layer was 100 nm.

[0116] S16: An antireflection layer 38 is formed on the side of the second metal electrode layer 372 away from the second transparent electrode layer 371.

[0117] The antireflection layer 38 can be fabricated using magnetron sputtering or vapor deposition methods, regardless of the location; however, when fabricating the antireflection layer 38 using vapor deposition, the evaporation rate is limited to 0-5 Å / s.

[0118] For example, an antireflective layer 38 is fabricated using vapor deposition: the sample is placed on a mask and placed in the vapor deposition chamber, and the vapor deposition vacuum is set to 2 × 10⁻⁶. -4 Evaporation was performed at Pa, the evaporation voltage was adjusted to the evaporation temperature, and the evaporation rate was controlled at 2 Å / S. Magnesium fluoride was deposited onto the second metal electrode layer 372 with a film thickness of 100 nm. After completion, the annealing station temperature was set to 100 °C, and annealing was performed for 8 minutes.

[0119] In summary, the fabrication method of the perovskite-silicon tandem solar cell provided in this application, by using plasma-enhanced atomic layer deposition to fabricate the buffer layer 36, can improve the compactness of the buffer layer 36 and reduce the defect density of the buffer layer 36. This allows the buffer layer 36 to meet the design requirements of the perovskite-silicon tandem solar cell 1000 in terms of low-temperature compatibility, interface stability, and high-efficiency transmission, thereby effectively improving the long-term stability and reliability of the perovskite-silicon tandem solar cell 1000.

[0120] Secondly, embodiments of this application provide a perovskite-silicon tandem solar cell 1000, which is manufactured using the manufacturing methods of the embodiments of the first aspect.

[0121] In one specific embodiment, please refer to Figure 1The perovskite-silicon tandem solar cell 1000 includes, from bottom to top, a first metal electrode layer 112, a first transparent electrode layer 111, a P-type doped layer 12, a first passivation layer 13, a silicon substrate 14, a second passivation layer 15, an N-type doped layer 16, a tunneling layer 21, a hole transport layer 31, a perovskite layer 32, a third passivation layer 33, an adhesion layer 34, an electron transport layer 35, a buffer layer 36, a second transparent electrode layer 371, a second metal electrode layer 372, and an antireflection layer 38, stacked sequentially. The first metal electrode layer 112, the first transparent electrode layer 111, the P-type doped layer 12, the first passivation layer 13, the silicon substrate 14, the second passivation layer 15, and the N-type doped layer 16 together constitute a crystalline silicon bottom cell. The hole transport layer 31, the perovskite layer 32, the third passivation layer 33, the adhesion layer 34, the electron transport layer 35, the buffer layer 36, the second transparent electrode layer 371, the second metal electrode layer 372, and the antireflection layer 38 together constitute a perovskite top cell. The tunneling layer 21 serves as a connecting layer to connect the crystalline silicon bottom cell and the perovskite top cell.

[0122] The first passivation layer 13, the second passivation layer 15, and the third passivation layer 33 can be propylenediamine iodine, including but not limited to at least one of propylenediamine bromide, butylamine chloride, butylamine bromide, butylamine iodide, N,N-dimethyl-1,3-propanediamine hydrochloride, and dodecylamine bromide; the first passivation layer 13, the second passivation layer 15, and the third passivation layer 33 can also be magnesium fluoride, including but not limited to at least one of lithium fluoride and sodium fluoride.

[0123] The hole transport layer 31 can be at least one of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], poly-3-hexylthiophene, nickel oxide, molybdenum trioxide, cuprous iodide, and cuprous thiocyanate. The thickness of the hole transport layer 31 is 1 nm to 600 nm.

[0124] The general structural formula of the perovskite layer 32 material is ABX3; where the A site is an organic cation, including CH3NH3. + NH2CH=NH2 + CH3CH2NH3 + Cs + At least one of the following; the B site is a metal cation, including Pb. 2+ Sn 2+ At least one of them; the X-position is a halide anion, including F - Cl - ,Br - I - At least one of the following. The thickness of the perovskite layer 32 is 1 nm to 600 nm.

[0125] Electron transport layer 35 can be zinc oxide, tin dioxide, titanium dioxide, or [6,6]-phenyl C 61At least one of methyl butyrate, C60, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. The thickness of the electron transport layer 35 is 1 nm to 600 nm.

[0126] The buffer layer 36 can be at least one of zinc oxide, tin dioxide, and titanium dioxide. The thickness of the buffer layer 36 is 0-30 nm.

[0127] The adhesion layer 34 can be N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane.

[0128] The first metal electrode layer 112 and the second metal electrode layer 372 can be at least one of silver, gold, copper, aluminum, and carbon.

[0129] The antireflection layer 38 is used to reduce the reflection loss of incident light on the battery surface, increase light absorption, and improve short-circuit current. The antireflection layer 38 can be a single layer or multiple layers of dielectric film. The thickness of the antireflection layer 38 is 1nm-600nm.

[0130] The perovskite-silicon tandem solar cell 1000 provided in this application improves the long-term stability and reliability of the cell by adopting the manufacturing method of the first aspect.

[0131] Thirdly, embodiments of this application provide a photovoltaic module, including a perovskite-silicon tandem cell 1000, which is manufactured using the manufacturing methods described in the embodiments of the first aspect.

[0132] A photovoltaic module may include multiple perovskite-silicon tandem cells 1000, which can be connected in series or in parallel and can be packaged to form an independent power generation module.

[0133] The photovoltaic module provided in this application, by adopting the manufacturing method of the first aspect, improves the long-term stability and reliability of the perovskite crystalline silicon tandem cell 1000 and the photovoltaic module containing the perovskite crystalline silicon tandem cell 1000.

[0134] Fourthly, embodiments of this application provide a photovoltaic system, including the photovoltaic module described in the third aspect.

[0135] A photovoltaic system can include multiple photovoltaic modules. Multiple photovoltaic modules and supporting equipment can form a complete power generation system that can convert solar energy into usable alternating current and connect to the power grid or supply local loads.

[0136] The photovoltaic system provided in this application improves the long-term stability and reliability of the photovoltaic modules by adopting photovoltaic modules from a third aspect.

[0137] The above-described embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application, and should all be included within the protection scope of this application.

Claims

1. A method for fabricating a perovskite-silicon tandem solar cell, characterized in that, include: A silicon substrate is provided, the silicon substrate including a first surface and a second surface disposed opposite to each other; A P-type doped layer and a first electrode layer are sequentially stacked on the first side of the silicon substrate. An N-type doped layer, a tunneling layer, a hole transport layer, a perovskite layer, an electron transport layer, a buffer layer, a second electrode layer, and an antireflection layer are sequentially stacked on the second side of the silicon substrate. The process of fabricating the buffer layer includes forming the buffer layer on the side of the electron transport layer away from the perovskite layer using plasma-enhanced atomic layer deposition.

2. The manufacturing method as described in claim 1, characterized in that, The buffer layer is formed on the side of the electron transport layer away from the perovskite layer using plasma-enhanced atomic layer deposition (PEALD), comprising: A SnO2 thin film was deposited on the side of the electron transport layer away from the perovskite layer using an atomic layer deposition apparatus. The surface of the SnO2 thin film is modified using a plasma generator, wherein the working gas in the plasma generator includes argon and oxygen.

3. The manufacturing method as described in claim 2, characterized in that, The plasma generating equipment includes a magnetron sputtering device.

4. The manufacturing method as described in claim 3, characterized in that, The power of the magnetron sputtering device is 30W-300W, and / or the flow rate of the working gas in the magnetron sputtering device is 5sccm-50sccm, and / or the flow ratio of argon to oxygen is 280:1-1:1, and / or the chamber substrate heating temperature of the magnetron sputtering device is 25℃-80℃, and / or the working time of the magnetron sputtering device is 1min-30min.

5. The manufacturing method as described in claim 2, characterized in that, The deposition vacuum degree of the atomic layer deposition equipment is 0-1×10⁻¹⁰. 4 Pa, and / or the deposition pipe temperature of the atomic layer deposition apparatus is 50℃-150℃, and / or the deposition chamber temperature of the atomic layer deposition apparatus is 40℃-150℃.

6. The manufacturing method as described in claim 2, characterized in that, The thickness of the SnO2 thin film is 10nm-20nm.

7. The manufacturing method according to any one of claims 1-6, characterized in that, Before fabricating the P-type doped layer, the fabrication method includes: fabricating a first passivation layer on a first surface of the silicon substrate; And / or, before fabricating the N-type doped layer, the fabrication method includes: fabricating a second passivation layer on the second side of the silicon substrate; And / or, prior to fabricating the electron transport layer, the fabrication method includes: fabricating a third passivation layer on the side of the perovskite layer away from the silicon substrate.

8. A perovskite-silicon tandem solar cell, characterized in that, It is manufactured using the manufacturing method described in any one of claims 1-7.

9. A photovoltaic module, characterized in that, The invention includes a perovskite-silicon tandem solar cell, which is manufactured using the manufacturing method described in any one of claims 1-7.

10. A photovoltaic system, characterized in that, Including the photovoltaic module as described in claim 9.

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