Preparation method of passivation layer, perovskite crystalline silicon tandem cell and manufacturing method thereof

Abstract

The application relates to the battery technical field and discloses a preparation method of a passivation layer, a perovskite crystalline silicon laminated battery and a manufacturing method thereof. The preparation method of the passivation layer comprises the following steps: providing a passivation agent and a solvent, and preparing a saturated passivation solution by using the passivation agent and the solvent; coating the solvent on the surface of a battery substrate to form a solvent film; coating the saturated passivation solution on the surface of the solvent film to form a passivation liquid film; and performing drying treatment on the passivation liquid film to obtain the passivation layer. The technical scheme provided by the application is used for improving the preparation process of the passivation layer and solving the technical problems of poor process stability and low film layer consistency in the related art.

Description

Technical Field

[0001] This application relates to the field of battery technology, and in particular to a method for preparing a passivation layer, a perovskite-silicon tandem battery, and a method for fabricating the same. Background Technology

[0002] In perovskite-silicon tandem solar cells, a passivation layer is typically added to the surface of the perovskite absorber layer to reduce interface defects, suppress non-radiative recombination, and thus improve the device's photoelectric performance. Currently, passivation layers are mostly prepared using solution methods, which involve directly coating a low-concentration passivation solution and then performing post-treatment to form the passivation layer. However, commonly used passivation solutions contain volatile solvents and have low passivating agent concentrations, making them prone to solvent evaporation and solute aggregation during storage. This results in poor storage stability and a short shelf life, requiring immediate preparation and use. This characteristic not only reduces production efficiency and increases manufacturing costs but also disrupts process consistency due to fluctuations in solution concentration, ultimately affecting device performance and hindering the large-scale mass production of the cells. Summary of the Invention

[0003] The purpose of this application is to provide a method for preparing perovskite thin films, perovskite-silicon tandem solar cells and their fabrication methods, to improve the preparation process of the passivation layer and solve the technical problems of poor process stability and low film uniformity in related technologies.

[0004] An embodiment of the first aspect of this application provides a method for preparing a passivation layer, comprising: providing a passivating agent and a solvent, and preparing a saturated passivation solution using the passivating agent and the solvent; coating the surface of a battery substrate with the solvent to form a solvent film; coating the surface of the solvent film with the saturated passivation solution to form a passivation liquid film; and drying the passivation liquid film to obtain a passivation layer.

[0005] The passivation layer preparation process provided in this application effectively solves the problems of solvent evaporation leading to increased concentration, poor solution stability, poor film uniformity, and low batch repeatability in the prior art, which uses a combination of pure solvent and saturated passivation solution for distributed coating. This significantly improves process stability and passivation layer film quality. Furthermore, the saturated passivation solution maintains long-term stability of liquid phase concentration during storage, extending its service life and overcoming the limitation of preparing solutions on demand. This reduces material waste and labor costs associated with frequent solution preparation, improves passivation layer film consistency and batch stability, and ultimately enhances the reliability of battery devices.

[0006] In some embodiments, preparing a saturated passivation solution includes: gradually adding a passivating agent to a solvent and stirring; continuing to stir until the passivating agent can no longer dissolve, forming a mixed solution containing undissolved passivating agent; filtering the mixed solution to remove undissolved passivating agent, thereby obtaining a saturated passivation solution.

[0007] In some embodiments, the stepwise addition of the passivating agent to the solvent and the stirring process includes: adding the passivating agent to the solvent stepwise under a constant temperature of 25°C-30°C and stirring at a speed of 300 rpm-500 rpm.

[0008] In some embodiments, coating the surface of the battery substrate with a solvent includes: uniformly coating the surface of the battery substrate with a solvent at a coating amount of 1 μL / cm²-10000 μL / cm²; and / or, coating the surface of the solvent film with a saturated passivation solution includes: uniformly coating the surface of the solvent film with a saturated passivation solution at a coating amount of 1 μL / cm²-1000 μL / cm².

[0009] In some embodiments, after coating the surface of the battery substrate with a solvent, the preparation method further includes: allowing it to stand for 10-20 seconds to allow the solvent to penetrate into the pores on the surface of the battery substrate.

[0010] In some embodiments, drying the passivation liquid film includes: hot air drying the passivation liquid film at a temperature of 25°C-150°C for a time of 1s-60s.

[0011] In some embodiments, the passivating agent includes at least one of propylenediamine bromide, butylamine chloride, butylamine bromide, butylamine iodide, N,N-dimethyl-1,3-propanediamine hydrochloride, and dodecylamine bromide.

[0012] In some embodiments, the solvent includes at least one selected from ethanol, isopropanol, methanol, dimethylformamide, G-butyrolactone, dimethyl sulfoxide, and N,N-dimethylacetamide.

[0013] The second 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; and fabricating an N-type doped layer, a tunneling layer, a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer, a second electrode layer, and an antireflection layer sequentially stacked on the second side of the silicon substrate; wherein the passivation layer is fabricated using the fabrication method described in the embodiments of the first aspect.

[0014] The method for fabricating perovskite-silicon tandem solar cells provided in this application improves the film quality and process stability of the passivation layer by using the preparation method of the first aspect, thereby improving the photoelectric performance and mass production consistency of the perovskite-silicon tandem solar cells. At the same time, the saturated passivation solution provided by this method can be stored for a long time, thereby reducing material waste and saving labor costs in the fabrication process of perovskite-silicon tandem solar cells.

[0015] An embodiment of the third aspect of this application provides a perovskite-silicon tandem solar cell, comprising a first electrode layer, a P-type doped layer, a silicon substrate, an N-type doped layer, a tunneling layer, a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer, a second electrode layer, and an antireflection layer stacked sequentially along the thickness direction. The passivation layer is fabricated using the preparation method described in the embodiments of the first aspect.

[0016] The perovskite-silicon tandem solar cell provided in this application improves the photoelectric performance and mass production consistency of the cell by using the preparation method of the first aspect to fabricate the passivation layer, and also reduces material waste and saves labor costs in the preparation process of the perovskite-silicon tandem solar cell. Attached Figure Description

[0017] 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.

[0018] Figure 1 This is a schematic diagram of the structure of a crystalline silicon tandem solar cell provided in an embodiment of this application; Figure 2 A flowchart illustrating the method for preparing the passivation layer provided in this application embodiment; Figure 3 A flowchart illustrating the preparation method of the saturated passivation solution provided in the embodiments of this application; Figure 4 A flowchart illustrating the fabrication method of the perovskite-silicon tandem solar cell provided in this application embodiment.

[0019] Explanation of key component symbols: 1000, Perovskite-silicon tandem solar cells; 11. First metal electrode layer; 12. First transparent electrode layer; 13. P-type doped layer; 14. Substrate passivation layer; 15. Silicon substrate; 16. Substrate surface passivation layer; 17. N-type doped layer; 18. Tunneling layer; 21. Hole transport layer; 22. Perovskite absorber layer; 23. Passivation layer; 24. Electron transport layer; 25. Buffer layer; 26. Second transparent electrode layer; 27. Second metal electrode layer; 28. Anti-reflection layer. Detailed Implementation

[0020] 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.

[0021] 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.

[0022] 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.

[0023] In a first aspect, embodiments of this application provide a method for preparing a passivation layer.

[0024] Please refer to Figure 1 and Figure 2 The preparation method provided in this application includes: S110. Provide a passivating agent and a solvent, and prepare a saturated passivation solution using the passivating agent and the solvent.

[0025] A saturated passivation solution is a passivation solution in which the solubility of the passivating agent (solute) in the solvent reaches its limit. Specifically, it can be achieved by adding an excess of passivating agent to the solvent.

[0026] Because the saturated passivation solution has reached its solubility limit, even with slight solvent evaporation during long-term storage, its concentration remains constant and there is no large-molecule aggregation. Related experiments have verified that the saturated passivation solution can be stored for up to 180 days at 25°C. This long-term storage capability effectively reduces material waste, increasing material utilization on mass production lines by 30%-40%.

[0027] S120. A solvent is coated on the surface of the battery substrate to form a solvent film.

[0028] A battery substrate refers to the bottom substrate including the perovskite absorber layer 22. For example, a perovskite-silicon tandem solar cell 1000 includes a first electrode layer, a P-type doped layer 13, a silicon substrate 15, an N-type doped layer 17, a tunneling layer 18, a hole transport layer 21, a perovskite absorber layer 22, a passivation layer 23, an electron transport layer 24, a second electrode layer, and an antireflection layer 28, which are stacked sequentially. The battery substrate may be composed of the first electrode layer, the P-type doped layer 13, the silicon substrate 15, the N-type doped layer 17, the tunneling layer 18, the hole transport layer 21, and the perovskite absorber layer 22.

[0029] Coating the surface of a battery substrate with a solvent that does not contain a passivating agent can form a pure solvent layer, also known as a solvent film. The solvent film can wet the surface of the battery substrate, reduce interfacial tension, and thus promote smoother and more uniform spreading of the subsequent saturated passivation solution on the surface of the battery substrate.

[0030] There are many ways to coat solvents, such as spin coating, spray coating, etc.

[0031] It should be noted that the battery substrate can be pretreated before coating with solvent to ensure that the surface of the battery substrate is clean and dry.

[0032] S130. A saturated passivation solution is coated on the surface of the solvent film to form a passivation liquid film.

[0033] After the saturated passivation solution is mixed with the solvent film, the saturated passivation solution is diluted and the passivating agent is dissolved a second time, thereby forming a low-concentration passivation liquid film with uniform thickness.

[0034] There are various methods for applying saturated passivation solutions, such as spin coating and spray coating.

[0035] The two-step solution method can precisely control the coating amount of solvent and saturated passivation solution, so that the concentration deviation of the mixed composite passivation solution does not exceed 5%, the thickness of passivation layer 23 can be controlled between 5nm and 20nm, and the batch deviation does not exceed 5%.

[0036] S140. The passivation liquid film is dried to obtain passivation layer 23.

[0037] The drying process is used to cause the solvent in the passivation liquid film to evaporate. During the solvent evaporation process, the passivating agent gradually gathers and crystallizes, eventually forming a uniform and dense solid film layer on the surface of the battery substrate, namely the passivation layer 23.

[0038] There are many drying methods, such as hot table heating, air blowing drying, vacuum drying, infrared irradiation, flash drying, natural drying, inert gas purging drying, etc.

[0039] It should be noted that the saturated passivation solution in the embodiments of this application can be prepared and used immediately, or it can be stored for a period of time after preparation before use.

[0040] The passivation layer preparation process provided in this application effectively solves the problems of solvent evaporation leading to increased concentration, poor solution stability, poor film uniformity, and low batch repeatability in the prior art by using a combination of pure solvent and saturated passivation solution for distributed coating. This significantly improves process stability and the film quality of the passivation layer 23. Simultaneously, the saturated passivation solution maintains long-term stability of the liquid phase concentration during storage, extending the solution's lifespan and overcoming the limitation of preparing solutions on demand. This reduces material waste and labor costs associated with frequent solution preparation, improves the film uniformity and batch stability of the passivation layer 23, and ultimately enhances the reliability of the battery device.

[0041] In some embodiments, please refer to Figure 3 In step S110, the preparation of the saturated passivation solution includes: S111. Gradually add the passivating agent to the solvent and stir.

[0042] Specifically, the passivating agent can be added to the solvent in batches; gradually adding the passivating agent can avoid the problem of local saturation or passivating agent agglomeration caused by adding too much passivating agent at once.

[0043] The passivating agent is stirred simultaneously during the addition process to promote its dissolution.

[0044] S112. Continue stirring until the passivating agent can no longer dissolve, forming a mixed solution containing undissolved passivating agent.

[0045] The inability of the passivating agent to dissolve further indicates that it has reached a dissolution equilibrium. This can be determined by observing whether a solid precipitate appears in the solution.

[0046] S113. Filter the mixed solution to remove undissolved passivating agent and obtain a saturated passivation solution.

[0047] Specifically, the mixed solution can be filtered using a 0.22 μm organic phase filter membrane.

[0048] In some embodiments, step S111 includes: gradually adding the passivating agent to the solvent under a constant temperature of 25°C-30°C and stirring at a speed of 300rpm-500rpm.

[0049] As an example, the isothermal conditions could be 25℃, 28℃, 30℃, etc. Temperature affects the solubility of the passivating agent in the solvent; specifically, the solubility of the passivating agent in the solvent usually increases with increasing temperature. In the above design, by limiting the isothermal conditions, the impact of temperature fluctuations on the solubility of the passivating agent can be reduced, ensuring the consistency of the saturated passivation solution. Simultaneously, by limiting the temperature within a reasonable range, the dissolution rate of the passivating agent can be guaranteed, shortening the time for the passivating agent to reach dissolution equilibrium and improving preparation efficiency.

[0050] As an example, the stirring speed can be 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, etc. The stirring speed affects the dissolution rate and effect of the passivating agent. If the stirring speed is too low, the passivating agent and solvent may not mix sufficiently, the passivating agent may not dissolve completely, and the dissolution rate may be too low, prolonging the time required for complete dissolution. If the stirring speed is too high, air may be introduced, causing bubbles, affecting film quality, and also easily leading to gas splashing and contamination. In the above design, by limiting the stirring speed within a reasonable range, the dissolution effect of the passivating agent can be guaranteed, improving the reliability and efficiency of the preparation process.

[0051] The above design can improve the quality and stability of the saturated passivation solution, while also ensuring the preparation efficiency of the saturated passivation solution.

[0052] In some embodiments, step S120 includes: uniformly coating a solvent on the surface of the battery substrate, with a coating amount of 1 μL / cm²-10000 μL / cm²; and / or, step S130 includes: uniformly coating a saturated passivation solution on the surface of the solvent film, with a coating amount of 1 μL / cm²-1000 μL / cm².

[0053] For example, a slot coating device can be used to coat the solvent and the saturated passivation solution.

[0054] Solvent coating amount refers to the volume of solvent covering a unit area of ​​the battery substrate surface. It can be controlled by adjusting parameters such as the doctor blade gap, coating head movement speed, nozzle flow rate, and solvent supply. By limiting the solvent coating amount, the film-forming effect of the solvent can be ensured, and the problem of excessive dissolution and over-diluting of the saturated passivation solution can be avoided.

[0055] The saturated passivation solution coating amount refers to the volume of saturated passivation solution covering a unit area of ​​solvent film surface. The coating amount can be controlled by adjusting parameters such as the doctor blade gap, coating head movement speed, nozzle flow rate, and saturated passivation solution supply. By limiting the coating amount of the saturated passivation solution, the density of the mixed passivation solution can be controlled, thereby improving the film quality of the passivation layer 23. Understandably, the coating amount of the saturated passivation solution can be adapted and adjusted according to the solvent coating amount and the design requirements of the passivation layer 23.

[0056] In the above design, by specifying the coating amount of solvent and saturated passivation solution, the controllability and stability of the preparation process can be improved, and the thickness of the passivation layer 23 can be precisely controlled.

[0057] In some embodiments, after coating the surface of the battery substrate with a solvent, the preparation method further includes: allowing it to stand for 10-20 seconds to allow the solvent to penetrate into the pores on the surface of the battery substrate.

[0058] Specifically, after coating the surface of the battery substrate with solvent, it is left to stand for a period of time to allow the solvent to fully penetrate into the pores on the surface of the battery substrate through capillary action, and then a saturated passivation solution is coated.

[0059] The surface of the battery substrate, namely the perovskite absorber layer 22, typically has numerous micropores and other defects. The settling process allows the solvent to fully contact the battery substrate surface, reducing interfacial voids and thus minimizing defects in the subsequent passivation layer 23 formation, while also improving the bonding effect between the passivation layer 23 and the battery substrate. Simultaneously, by controlling the settling time, excessive solvent evaporation and subsequent film rupture can be avoided.

[0060] In some embodiments, step S140, drying the passivation liquid film includes: hot air drying the passivation liquid film at a temperature of 25°C-150°C for a time of 1s-60s.

[0061] As an example, the temperature for hot air drying can be 25℃, 50℃, 75℃, 100℃, 125℃, 150℃, etc.

[0062] For example, the hot air drying time can be 1s, 10s, 20s, 30s, 40s, 50s, 60s, etc.

[0063] Hot air drying refers to the process of blowing heated, clean air to accelerate the evaporation of solvent in a passivation liquid film; air, nitrogen, or other gas streams can be used. The drying rate can be controlled by adjusting parameters such as hot air temperature and air velocity.

[0064] In the above embodiments, by using hot air drying and controlling the drying temperature and duration, the film formation rate and quality of the passivation layer 23 can be improved, thus solving the problems of unstable performance and low mass production efficiency of the passivation layer 23 in related technologies.

[0065] In some embodiments, the passivating agent includes at least one of propylenediamine bromide (PDADBr), butylamine chloride (BACl), butylamine bromide (BABr), butylamine iodide (BAI), N,N-dimethyl-1,3-propanediamine hydrochloride (DMePDADCl), and dodecylamine bromide (DDDADBr).

[0066] Understandably, the type of passivator can be selected based on the design requirements of the perovskite-silicon tandem solar cell 1000.

[0067] The above embodiments improve the practicality of the preparation method by providing a variety of passivating agents.

[0068] In some embodiments, the solvent includes at least one of ethanol, isopropanol, methanol, dimethylformamide (DMF), G-butyrolactone (GBL), dimethyl sulfoxide (DMSO), and N,N-dimethylacetamide (DMA).

[0069] Understandably, the type of solvent can be selected based on the design requirements of the perovskite-silicon tandem solar cell 1000; the solvent needs to be able to dissolve the passivating agent while ensuring that it does not damage the structure of the perovskite absorber layer 22.

[0070] The above embodiments improve the practicality of the preparation method by providing a variety of solvents.

[0071] In summary, the preparation method provided in this application, which prepares the passivation layer 23 by stepwise coating of solvent and saturated passivation solution, can solve the problems of increased passivation solution concentration due to solvent evaporation, poor stability of passivation solution, poor uniformity of passivation layer 23 film formation, and low batch repeatability. It significantly improves the stability of the process and the film quality of passivation layer 23. At the same time, the saturated passivation solution provided by this preparation method can be stored for a long time, thereby reducing the material waste and labor costs caused by frequent solution preparation.

[0072] Secondly, embodiments of this application provide a method for preparing a perovskite-silicon tandem solar cell.

[0073] Please refer to Figure 1 and Figure 4 The manufacturing method provided in this application includes: S210. A silicon substrate 15 is provided, the silicon substrate 15 including a first surface and a second surface disposed opposite to each other.

[0074] S220. A P-type doped layer 13 and a first electrode layer are sequentially stacked on the first side of the silicon substrate 15.

[0075] S230. An N-type doped layer 17, a tunneling layer 18, a hole transport layer 21, a perovskite absorption layer 22, a passivation layer 23, an electron transport layer 24, a second electrode layer, and an antireflection layer 28 are sequentially stacked on the second side of a silicon substrate 15; wherein the passivation layer 23 is fabricated using the preparation method provided in the embodiments of the first aspect.

[0076] The method for fabricating a perovskite-silicon tandem solar cell provided in this application improves the film quality and process stability of the passivation layer 23 by using the preparation method of the first aspect, thereby improving the photoelectric performance and mass production consistency of the perovskite-silicon tandem solar cell 1000. At the same time, the saturated passivation solution provided by this method can be stored for a long time, thereby reducing material waste and saving labor costs in the fabrication process of the perovskite-silicon tandem solar cell 1000.

[0077] Thirdly, embodiments of this application provide a perovskite-silicon tandem solar cell 1000.

[0078] Please refer to Figure 1 The perovskite-silicon tandem solar cell 1000 provided in this application embodiment includes a first electrode layer, a P-type doped layer 13, a silicon substrate 15, an N-type doped layer 17, a tunneling layer 18, a hole transport layer 21, a perovskite absorption layer 22, a passivation layer 23, an electron transport layer 24, a second electrode layer, and an antireflection layer 28, which are sequentially stacked along the thickness direction. The passivation layer 23 is fabricated using the preparation method provided in the embodiments of the first aspect.

[0079] Regardless of the specific details, the first electrode layer includes a first transparent electrode layer 12 and a first metal electrode layer 11, the second electrode layer includes a second transparent electrode layer 26 and a second metal electrode layer 27, the two surfaces of the silicon substrate 15 may be respectively provided with a substrate passivation layer 14 and a substrate surface passivation layer 16, and a buffer layer 25 may be provided between the electron transport layer 24 and the second electrode layer.

[0080] Optionally, the hole transport layer 21 can be made of self-assembled small molecule materials, such as 2PACz, MeO-2PACz, Me-4PACz, MeO-4PACz, 4PACz, etc.

[0081] Optionally, the perovskite absorber layer 22 comprises a perovskite material with the general structural formula ABX3, wherein the A-site is an organic cation, including CH3NH3. + (MA + ), NH2CH=NH2 + (FA + CH3CH2NH3+ Cs + At least one of them, wherein the B-site is a metal cation, including Pb 2+ Sn 2+ At least one of them, wherein the X-position is a halide anion, including F - Cl - ,Br - I - At least one of them.

[0082] Optionally, the electron transport layer 24 may be made of at least one of zinc oxide, tin dioxide, titanium dioxide, methyl [6,6]-phenyl C61 butyrate, C60, and 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline.

[0083] Optionally, the material of the buffer layer 25 includes at least one of zinc oxide, tin dioxide, and titanium dioxide.

[0084] Optionally, the materials of the first metal electrode layer 11 and the second metal electrode layer 27 include at least one of silver, gold, copper, aluminum, and carbon.

[0085] Optionally, the antireflective layer 28 may be made of at least one of magnesium fluoride, lithium fluoride, sodium fluoride, and silicon oxide.

[0086] The perovskite-silicon tandem solar cell 1000 provided in this application embodiment improves the photoelectric performance and mass production consistency of the cell by using the preparation method of the first aspect to fabricate the passivation layer 23, and also reduces material waste and saves labor costs in the fabrication process of the perovskite-silicon tandem solar cell 1000.

[0087] To verify the technical effects of the passivation layer preparation method and the perovskite-silicon tandem solar cell fabrication method provided in the embodiments of this application, several specific embodiments are provided below for explanation and illustration.

[0088] Example 1: A method for fabricating a perovskite-silicon tandem solar cell.

[0089] The perovskite-silicon tandem solar cell 1000 includes a first metal electrode layer 11, a first transparent electrode layer 12, a P-type doped layer 13, a substrate passivation layer 14, a silicon substrate 15, a substrate surface passivation layer 16, an N-type doped layer 17, a tunneling layer 18, a hole transport layer 21, a perovskite absorption layer 22, a passivation layer 23, an electron transport layer 24, a buffer layer 25, a second transparent electrode layer 26, a second metal electrode layer 27, and an anti-reflection layer 28, which are sequentially stacked along its thickness direction.

[0090] The manufacturing method provided in this embodiment specifically includes the following steps: S1. A silicon substrate 15 is provided, the silicon substrate 15 including a first surface and a second surface disposed opposite to each other.

[0091] S2. A substrate passivation layer 14 and a P-type doped layer 13 are sequentially stacked on the first side of the silicon substrate 15.

[0092] S3. A substrate surface passivation layer 16 and an N-type doped layer 17 are sequentially stacked on the second side of the silicon substrate 15.

[0093] S4. A first transparent electrode layer 12 is fabricated on the surface of the P-type doped layer 13.

[0094] For example, the first transparent electrode layer 12 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.

[0095] S5. A first metal electrode layer 11 is formed on the surface of the first transparent electrode layer 12.

[0096] For example, the first metal electrode layer 11 is fabricated using vapor deposition: the sample is placed in the vapor deposition chamber, and the vacuum degree for vapor deposition is 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 12. The evaporation thickness of the silver layer is 200 nm.

[0097] S6. A tunneling layer 18 is fabricated on the surface of the N-type doped layer 17.

[0098] The tunneling layer 18 can be prepared by magnetron sputtering, with a controlled power of 30W-200W and a film thickness of 1nm-50nm.

[0099] For example, a tunneling layer 18 was fabricated using magnetron sputtering: the sample was placed in a magnetron sputtering device, the power was controlled at 60W, the running time was 1h, and the film thickness was 40nm.

[0100] S7. Create a hole transport layer 21 on the surface of the tunneling layer 18.

[0101] Hole transport layer 21 can be prepared using solution film formation methods such as spin coating, blade coating, and spray coating, regardless of location.

[0102] For example, hole transport layer 21 is prepared by spin coating: prepare hole transport layer 21 dispersion, weigh out a quantitative amount of 2 PACz and dissolve it in IPA solvent, the dispersion concentration is 1 mg / ml, and sonicate for 10 min; spin coat the hole transport layer 21 dispersion evenly onto the sample surface, set the spin coating speed to 6000 rpm and the spin coating time to 25 s; after spin coating, perform annealing treatment, the annealing temperature is 100℃ and the annealing time is 10 min.

[0103] S8. A perovskite absorber layer 22 is fabricated on the surface of the hole transport layer 21.

[0104] For example, perovskite absorber layer 22 was prepared using a spin-coating flash method: a perovskite precursor solution was prepared, and a quantitative amount of perovskite material was dissolved in 1 ml of DMF and DMSO solvents at a solvent ratio of 8:2; the sample was placed on the spin coater platform, 120 μL of perovskite precursor solution was weighed and spin-coated onto the sample surface, and the spin-coating speed was set to 3500 rpm and the spin-coating time was 30 s; the sample was placed on the flash stage, and the flash temperature was set to 30 °C and the flash time was 30 s; after flash evaporation, annealing was performed at 100 °C for 15 min, and the thickness of the perovskite absorber layer 22 was 500 nm.

[0105] S9. A passivation layer 23 is formed on the surface of the perovskite absorption layer 22.

[0106] For example, the passivation layer 23 is prepared using the two-step solution method of the first aspect: a saturated passivating agent solution is prepared; a pure solvent is coated on the surface of the sample and allowed to stand for 5 seconds to form a solvent film, wherein the coating amount of the solvent is 100 μL / cm²; a saturated passivation solution is coated on the surface of the solvent film to form a passivation liquid film, wherein the coating amount of the saturated passivation solution is 5 μL / cm²; and hot air drying is performed to form the passivation layer 23, wherein the drying temperature is 100°C, the drying time is 30 seconds, and the thickness of the passivation layer 23 is 10 nm.

[0107] S10. An electron transport layer 24 is fabricated on the surface of the passivation layer 23.

[0108] Electron transport layer 24 can be prepared by spin coating, spray coating or vapor deposition, regardless of location.

[0109] For example, electron transport layer 24 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 was performed at Pa, the evaporation voltage was adjusted to the evaporation temperature, and the evaporation rate was controlled at 0.1 Å / S-0.15 Å / S to deposit C60 onto the passivation layer 23. The evaporation thickness of C60 was 20 nm.

[0110] S11. A buffer layer 25 is fabricated on the surface of the electron transport layer 24.

[0111] For example, a buffer layer 25 is fabricated using atomic deposition: the vacuum level of the atomic deposition equipment is set to 0.5 Pa × 10⁻⁶. - 4 Pa, the deposition channel temperature is 60℃, the deposition chamber temperature is 70℃, SnO2 is deposited onto the electron transport layer 24 by evaporation, and the SnO2 deposition thickness is 15nm.

[0112] S12, a second transparent electrode layer 26 on the surface of the buffer layer 25.

[0113] For example, a second transparent electrode layer 26 is fabricated using magnetron sputtering: the sample is placed in a magnetron sputtering device, an IZO target is set, the power is controlled at 50W, the running time is 1 h, and the film thickness is 100nm.

[0114] S13. A second metal electrode layer 27 is formed on the surface of the second transparent electrode layer 26.

[0115] For example, the second metal electrode layer 27 is fabricated using vapor deposition: the sample is placed in the vapor deposition chamber, and the vacuum degree for vapor deposition is 2×10⁻⁶. -4 The silver was deposited onto the second transparent electrode layer 26 at a pressure of Pa. The deposition voltage was adjusted to the evaporation temperature, and the evaporation rate was controlled to be 2.5 Å / S. The silver layer was deposited with a deposition thickness of 100 nm.

[0116] S14. An anti-reflection layer 28 is fabricated on the surface of the second metal electrode layer 27.

[0117] For example, the antireflective layer 28 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 The evaporation process is carried out at Pa, the evaporation voltage is adjusted to the evaporation temperature, and the evaporation rate is controlled at 2 Å / S to deposit magnesium fluoride onto the second electrode layer. The evaporation thickness of magnesium fluoride is 100 nm.

[0118] Example 2: A method for preparing a perovskite-silicon tandem solar cell.

[0119] The difference between this embodiment and Embodiment 1 is that in step S9 of Embodiment 1, the saturated passivation solution is prepared and used immediately, while in Embodiment 2, the saturated passivation solution is prepared and stored for 90 days before use.

[0120] Example 3: A method for preparing a perovskite-silicon tandem solar cell.

[0121] The difference between this embodiment and Embodiment 1 is that in step S9 of Embodiment 1, the saturated passivation solution is prepared and used immediately, while in Embodiment 3, the saturated passivation solution is prepared and stored for 180 days before use.

[0122] Example 4: A method for preparing a perovskite-silicon tandem solar cell.

[0123] The difference between this embodiment and Embodiment 1 is as follows: In step S9 of Embodiment 1, a two-step solution method is used to prepare the passivation layer 23, that is, a solvent and a saturated passivation solution are provided. First, a layer of pure solvent is coated, and then a layer of saturated passivation solution is coated. In Embodiment 4, a one-step solution method is used to prepare the passivation layer 23, that is, a low-concentration passivation solution is directly prepared, the passivation solution is coated on the surface of the sample, and the passivation layer 23 is directly formed after drying. The concentration of the passivation solution is 2 mg / mL, the coating amount is 5 μL / cm², the drying temperature is 100℃, the drying time is 30s, and the thickness of the passivation layer 23 is 10 nm.

[0124] Example 5: A method for preparing a perovskite-silicon tandem solar cell.

[0125] The difference between this embodiment and embodiment four is that in embodiment four, the passivation solution is prepared and used immediately, while in embodiment five, the passivation solution is prepared and stored for 90 days before use.

[0126] Example 6: A method for preparing a perovskite-silicon tandem solar cell.

[0127] The difference between this embodiment and embodiment four is that in embodiment four, the passivation solution is prepared and used immediately, while in embodiment six, the passivation solution is prepared and stored for 180 days before use.

[0128] The performance of the perovskite-silicon tandem solar cells 1000 prepared in the above embodiments was determined 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: Example 1 33.1 98.1 Example 2 33.0 98.2 Example 3 33.2 98.3 Example 4 33.1 98.2 Example 5 30.2 84.1 Example 6 28.2 61.4 Based on the above test results, it can be seen that when the passivation layer 23 is prepared using the two-step solution method provided in this application embodiment, even if the saturated passivation solution is stored for up to 180 days, the device yield can still be maintained at a relatively high level of about 98%, and the average photoelectric conversion efficiency can still be maintained at around 33%, showing excellent and stable performance. When the passivation layer 23 is prepared using the traditional one-step solution method, as the storage time of the passivation solution is extended from 0 days to 180 days, the device yield drops sharply from 98.2% to 61.4%, and the average photoelectric conversion efficiency continues to decrease from 33.1% to 28.8%, showing obvious problems with passivation effect and yield decay over time.

[0129] 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 preparing a passivation layer, characterized in that, include: A passivating agent and a solvent are provided, and a saturated passivation solution is prepared using the passivating agent and the solvent. The passivating agent includes at least one selected from propylenediamine bromide, butylamine chloride, butylamine bromide, butylamine iodide, N,N-dimethyl-1,3-propanediamine hydrochloride, and dodecylamine bromide. The solvent includes at least one selected from ethanol, isopropanol, methanol, dimethylformamide, G-butyrolactone, dimethyl sulfoxide, and N,N-dimethylacetamide. The solvent is coated onto the surface of the battery substrate to form a solvent film; The saturated passivation solution is coated on the surface of the solvent film, so that the saturated passivation solution mixes with the solvent film to form a passivation liquid film; The passivation liquid film is dried to obtain a passivation layer.

2. The method for preparing the passivation layer as described in claim 1, characterized in that, The preparation of the saturated passivation solution includes: The passivating agent is gradually added to the solvent while stirring; Continue stirring until the passivating agent can no longer dissolve, forming a mixed solution containing undissolved passivating agent; The mixed solution is filtered to remove the undissolved passivating agent, resulting in the saturated passivation solution.

3. The method for preparing the passivation layer as described in claim 2, characterized in that, The step of gradually adding the passivating agent to the solvent and stirring includes: gradually adding the passivating agent to the solvent under a constant temperature of 25℃-30℃ and stirring at a speed of 300rpm-500rpm.

4. The method for preparing the passivation layer as described in claim 1, characterized in that, The step of coating the solvent onto the surface of the battery substrate includes: uniformly coating the solvent onto the surface of the battery substrate at a coating amount of 1 μL / cm. 2 -10000μL / cm 2 ; and / or, the coating of the saturated passivation solution onto the surface of the solvent film comprises: uniformly coating the saturated passivation solution onto the surface of the solvent film at a coating amount of 1 μL / cm 2 -1000μL / cm 2 .

5. The method for preparing the passivation layer as described in claim 1, characterized in that, After coating the surface of the battery substrate with the solvent, the preparation method further includes: allowing it to stand for 10-20 seconds to allow the solvent to penetrate into the pores on the surface of the battery substrate.

6. The method for preparing the passivation layer as described in claim 1, characterized in that, The drying process of the passivation liquid film includes: hot air drying of the passivation liquid film at a temperature of 25℃-150℃ for a time of 1s-60s.

7. A method for preparing 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 absorber layer, a passivation layer, an electron transport layer, a second electrode layer, and an antireflection layer are sequentially stacked on the second side of the silicon substrate. The passivation layer is prepared using the preparation method described in any one of claims 1-6.

8. A perovskite-silicon tandem solar cell, characterized in that, The material comprises a first electrode layer, a P-type doped layer, a silicon substrate, an N-type doped layer, a tunneling layer, a hole transport layer, a perovskite absorption layer, a passivation layer, an electron transport layer, a second electrode layer, and an antireflection layer, which are sequentially stacked along the thickness direction. The passivation layer is fabricated using the preparation method described in any one of claims 1-6.

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