A perovskite precursor ink, a method for preparing a thin film and a battery component

Abstract

The application relates to a perovskite precursor ink, a preparation method of a perovskite film and a battery assembly, which comprises a perovskite precursor active component and an organic mixed solvent; and further comprises an amphiphilic block copolymer additive; the amphiphilic block copolymer additive is composed of a perovskite-philic chain segment and a flexible hydrophobic chain segment and is connected through a covalent bond; the perovskite-philic chain segment is a polyvinylpyridine chain segment with a polymerization degree n of 10-100, and the flexible hydrophobic chain segment is a polyethylene oxide chain segment with a polymerization degree m of 20-200. In terms of crystallinity, the perovskite-philic chain segment in the additive has a strong coordination effect with lead ions, serves as a nucleation site to guide the uniform growth of crystals, effectively regulates the crystallization kinetics, and high-quality perovskite films with uniform crystal grain size and clear grain boundaries are obtained.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cell technology, and in particular to a method for preparing perovskite precursor ink, thin film and battery module. Background Technology

[0002] In recent years, atmospheric perovskite thin film fabrication technology has focused on achieving a balance between high efficiency, high stability, and low manufacturing costs. Early research primarily concentrated on passivating defects and regulating crystallization kinetics through small-molecule additives to obtain dense films in air. Subsequently, the technological frontier shifted to utilizing functional polymer additives to achieve multiple benefits. These polymers have evolved from initially offering only passivation functionality to simultaneously regulating crystallization and enhancing the mechanical adhesion of the film. Currently, the focus of this field has advanced to using molecular design to enable additives to actively release intrinsic stress during crystallization and form a protective layer in situ after film formation, thereby achieving a leap from defect passivation to bulk encapsulation. This trend aims to solve the three major challenges of crystal quality, mechanical toughness, and environmental stability of perovskite thin films in a one-step process, laying the foundation for advancing the manufacturing of large-area perovskite modules.

[0003] In the field of perovskite photovoltaic device manufacturing, especially in the development of technologies for large-area thin film preparation, the use of polymer additives to improve thin film performance has become an important research direction. In existing technologies, using flexible polymers as additives is a relatively common technique.

[0004] Currently, widely studied methods include the use of linear polymer systems such as polyurethane acrylate (PUA) and polyvinylpyrrolidone (PVP). These polymers typically possess long, flexible molecular backbones, such as the repeating urethane units and flexible carbon segments found in polyurethane acrylate. In practice, these polymers are directly introduced into the perovskite precursor ink, with concentrations typically ranging from 0.1% to 5% by weight. During subsequent film formation and crystallization, these polymer molecules spontaneously migrate and distribute themselves at the boundary regions of the perovskite grains through intermolecular forces, forming a network structure.

[0005] From the perspective of mechanism of action, this type of flexible polymer mainly works through two pathways: In terms of mechanical properties, the long polymer chains form an elastic network at the grain boundaries. When the film is subjected to external stress, these flexible segments can effectively disperse the stress through conformational changes, thereby improving the bending resistance of the film; In terms of interfacial interactions, the carbonyl and amine functional groups contained in the polymer molecules can coordinate with lead ions in the perovskite lattice. This moderate-strength coordination can modify the defect state at the grain boundaries to a certain extent.

[0006] Furthermore, some studies have found that the introduction of these polymers can indirectly affect the perovskite crystallization process. Due to the steric hindrance effect of polymer molecules at grain boundaries, the crystallization rate may be moderately slowed down, resulting in more ordered crystal growth. Simultaneously, the distribution of polymers at grain boundaries also alters the physicochemical properties of the grain boundary regions, providing an improved interfacial environment for carrier transport.

[0007] These technical solutions provide a fundamental approach to improving the mechanical properties of perovskite thin films and, through research on polymer-perovskite interfacial interactions, lay the technical foundation for subsequent, more refined molecular design. Existing research has confirmed that appropriate polymer selection and addition can significantly improve the mechanical toughness and operational stability of perovskite thin films while maintaining photoelectric conversion efficiency.

[0008] The shortcomings of existing technology are: First, in terms of controlling the crystallization process, existing additives lack effective nucleation regulation capabilities. Due to the weak and non-specific interaction between polymer molecules and perovskite precursors, sufficient nucleation sites cannot be provided in the early stages of crystallization, resulting in random and unevenly distributed crystal nuclei. This passive crystallization method makes it difficult to achieve precise control over grain size and morphology, easily leading to thin film structures with excessively wide grain size distribution and disordered grain boundaries.

[0009] Secondly, existing additives cannot achieve multifunctional synergy. A single polymer structure can only provide limited performance improvements and cannot simultaneously solve multiple key issues such as crystallization control, strain release, and environmental stability. In particular, the lack of surface self-assembly capability prevents the formation of a dense protective layer on the film surface, resulting in limited improvement in environmental stability.

[0010] Furthermore, existing technologies suffer from process compatibility issues. Some additives are difficult to completely remove or transform during subsequent processing, potentially remaining in the film and forming charge recombination centers, thus reducing device performance. Simultaneously, the interaction strength between additives and perovskite components is insufficient, which may lead to phase separation during long-term operation, affecting the long-term stability of the device. Regarding crystallization process control, existing additives lack effective nucleation regulation capabilities. Due to the weak and non-specific interaction between polymer molecules and perovskite precursors, sufficient nucleation sites cannot be provided in the early stages of crystallization, resulting in random and unevenly distributed nuclei. This passive crystallization method makes it difficult to achieve precise control over grain size and morphology, easily leading to thin film structures with excessively wide grain size distribution and disordered grain boundaries.

[0011] Existing additives also exhibit limitations in their single-function design. Their molecular structure design lacks multifunctional integration, making it impossible to simultaneously achieve multiple functions such as crystallization regulation, strain release, and surface protection. In particular, they lack surface self-assembly capabilities, failing to spontaneously form a dense, continuous encapsulation layer on the film surface, resulting in limited improvement in environmental stability.

[0012] Furthermore, existing technologies also suffer from process compatibility issues. Some additives are difficult to achieve an ideal spatial distribution after film formation, and may remain in the bulk phase to form charge recombination centers, or undergo phase separation during long-term operation, affecting the long-term stability of the device. The introduction of additives also often adversely affects the rheological properties of the precursor ink, hindering the realization of large-area uniform coating processes.

[0013] In view of the above-mentioned shortcomings, the designer has actively researched and innovated in order to create a method for preparing perovskite precursor inks, thin films and battery components, making them more industrially valuable. Summary of the Invention

[0014] To address the aforementioned technical problems, the present invention aims to provide a method for preparing perovskite precursor inks, thin films, and battery components.

[0015] To achieve the above objectives, the present invention adopts the following technical solution: One of the objectives of this invention is: A perovskite precursor ink, comprising a perovskite precursor active component and an organic mixed solvent; It also includes amphiphilic block copolymer additives; The amphiphilic block copolymer additive is composed of perovskite segments and flexible hydrophobic segments connected by covalent bonds; The perovskite-loving segments are polyvinylpyridine segments with a degree of polymerization n of 10 to 100, and the flexible hydrophobic segments are polyoxyethylene segments with a degree of polymerization m of 20 to 200.

[0016] As a further improvement of the present invention, the amphiphilic block copolymer additive is P4VP. 50 -b-PEO 100 Its polymer dispersion is 1.12.

[0017] As a further improvement of the present invention, the amphiphilic block copolymer additive is present in the perovskite precursor ink at a mass percentage of 0.05% to 0.2%.

[0018] The second objective of this invention is: A method for preparing a perovskite thin film includes the following steps: Step 1: Provide a perovskite precursor ink as described above; Step 2: On the substrate containing the hole transport layer, perovskite precursor ink is coated in an air environment using a slot coating method to form a wet film. Step 3: Perform gradient thermal annealing on the wet film to crystallize and form a perovskite film.

[0019] As a further improvement of the present invention, in step 2, the coating speed of the slit coating is 8~12 mm / s.

[0020] As a further improvement of the present invention, in step 3, the gradient thermal annealing process includes preheating at 60~80°C for 2~4 minutes, followed by annealing at 90~110°C for 28~32 minutes.

[0021] The third objective of this invention: A method for preparing a perovskite solar cell module includes the following steps: Step 1: Provide and clean the transparent conductive oxide glass substrate; Step 2: Perform the first laser scribing on the conductive layer surface of the substrate to form multiple spaced first scribing lines to define the sub-cell area; Step 3: Deposit a hole transport layer on the substrate surface; Step 4: Using any of the perovskite thin film preparation methods described above, prepare a perovskite light-absorbing layer on the hole transport layer; Step 5: Deposit an electron transport layer on the perovskite light-absorbing layer; Step 6: Deposit a buffer layer on the electron transport layer; Step 7: Perform a second laser scribing to remove the perovskite light-absorbing layer, electron transport layer, and buffer layer corresponding to the area marked in the first scribing, exposing the hole transport layer or conductive layer underneath. Step 8: Deposit a metal electrode, which forms an electrical connection with the area exposed in Step 7; Step 9: Perform a third laser scribing to remove part of the hole transport layer, perovskite light-absorbing layer, electron transport layer, buffer layer and metal electrode corresponding to the first scribing area, forming an interconnect structure that connects adjacent sub-cells in series; Step 10: Perform the fourth laser edge cleaning to remove all functional layers at the edge of the component, exposing the surrounding glass substrate; Step 11: Encapsulate the perovskite solar cell module.

[0022] As a further improvement of the present invention, in step 2, the first laser scribing uses a green laser with a wavelength of 532nm, a power of 2~4W, a frequency of 40~60kHz, and a scanning speed of 400~600mm / s. In step 7, the second laser scribing uses an infrared laser with a wavelength of 1064nm, a power of 3~5W, a frequency of 70~90kHz, and a scanning speed of 700~900mm / s; In step 9, the third laser scribing uses an ultraviolet laser with a wavelength of 355nm, a power of 1~2W, a frequency of 50~70kHz, and a scanning speed of 900~1100mm / s. In step 10, the fourth laser scribing uses a picosecond ultraviolet laser with a wavelength of 355nm, a power of 4~6W, a frequency of 190~210kHz, and a scanning speed of 200~400mm / s.

[0023] As a further improvement of the present invention, in step 3, a NiO layer with a thickness of 10-30 nm is deposited by magnetron sputtering. X The film is then annealed in air at 190-210°C for 28-32 minutes. In step 5, a C layer with a thickness of 10-30 nm is deposited using a high-vacuum thermal evaporation method. 60 film.

[0024] As a further improvement of the present invention, in step 6, a dense SnO layer with a thickness of 5-20 nm is deposited at 70-90°C through 90-110 cycles. X film; In step 8, a copper electrode with a thickness of 90-110 nm is deposited by magnetron sputtering at room temperature.

[0025] By means of the above-described solution, the present invention has at least the following advantages: Compared to existing technologies, this invention, by introducing specifically designed amphiphilic block copolymer additives and optimizing the supporting processes, brings significant and synergistic beneficial effects: 1. In terms of crystallinity, the perovskite segments in the additives have a strong coordination with lead ions, which serve as nucleation sites to guide uniform crystal growth, effectively regulate crystallization kinetics, and obtain high-quality perovskite films with uniform grain size and clear grain boundaries.

[0026] 2. In terms of in-situ encapsulation, the amphiphilic nature of the additives allows them to spontaneously migrate to the surface grain boundaries and assemble in an orderly manner during the film formation process, forming a dense hydrophobic protective layer, thereby achieving in-situ encapsulation of perovskite thin films and significantly improving the long-term stability of the components in air.

[0027] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the following are preferred embodiments of the present invention described in detail with reference to the accompanying drawings. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1This is a schematic diagram of the molecular structure of the amphiphilic block copolymer additive used in this invention; Figure 2 This is a SEM schematic diagram of the perovskite thin film prepared according to an embodiment of the present invention; Figure 3 This is a SEM schematic diagram of the perovskite thin film prepared in comparison to the present invention. Figure 4 These are XRD schematic diagrams of the perovskite thin films prepared in the embodiments and comparative examples of the present invention; Figure 5 This is a schematic diagram of the water contact angle of the perovskite thin film prepared according to an embodiment of the present invention; Figure 6 This is a schematic diagram of the water contact angle of the perovskite thin film prepared in the comparative example of the present invention; Figure 7 This is an IV curve diagram of the perovskite components (300mm×300mm) prepared in the embodiments and comparative examples of the present invention. Detailed Implementation

[0030] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0031] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0032] The core of this invention lies in providing a perovskite thin film additive that solves the problem that existing technologies cannot simultaneously achieve crystallization control and internal encapsulation, so as to prepare high-quality, high-stability large-area perovskite thin films.

[0033] The specific implementation steps of this invention are as follows: Step 1: Preparation and cleaning of ITO glass substrate Select and clean a 300mm×300mm ITO glass substrate.

[0034] Step 2: First laser marking (P1) Objective: To define the width of individual sub-cells, isolate the ITO layer, and prepare channels for subsequent tandem structures.

[0035] Process: Use a green laser (wavelength 532nm).

[0036] Laser parameters: power 3W, frequency 50kHz, scanning speed 500mm / s.

[0037] The ITO layer was etched away to expose the underlying glass substrate, forming a scribe line approximately 30 μm wide. All sub-cells were isolated by the P1 scribe line.

[0038] Step 3: Fabrication of the hole transport layer (PVD-NiO) X ) NiO with a thickness of approximately 20 nm was deposited using magnetron sputtering. X The film was then annealed in air at 200°C for 30 minutes.

[0039] Step 4: Applying a perovskite light-absorbing layer to the air slit Use precursor inks containing amphiphilic block copolymers.

[0040] Slit coating is performed in air, followed by gradient thermal annealing in an annealing furnace (70℃-3min→100℃-30min) to form a perovskite film.

[0041] Step 5: Evaporation of electron transport layer (C 60 ) A C layer approximately 20 nm thick was deposited using a high-vacuum thermal evaporation method. 60 film.

[0042] Step 6: Atomic Layer Deposition of Buffer Layer (ALD-SnO) X ) At 80°C, a dense SnO layer approximately 10 nm thick was deposited through 100 cycles. X film.

[0043] Step 7: Second laser marking (P2) Objective: To remove perovskite / C from the area marked in P1. 60 / SnO X The material exposes the underlying ITO layer, preparing for the connection of the upper and lower electrodes.

[0044] Process: An infrared laser (wavelength 1064nm) is used because perovskite strongly absorbs infrared light, and this wavelength can effectively reduce the risk of damage to the underlying ITO.

[0045] Laser parameters: power 4W, frequency 80kHz, scanning speed 800mm / s.

[0046] The perovskite material in the P1 marked area was precisely ablated to ensure the ITO surface was exposed.

[0047] Step 8: Fabrication of metal electrodes (PVD-Cu) by magnetron sputtering Using a precision metal mask, a copper electrode approximately 100 nm thick was deposited by magnetron sputtering at room temperature.

[0048] Step 9: Third laser marking (P3) Objective: To remove nickel oxide, perovskite, and carbon from the marked areas of P1 / P2. 60 SnO X The Cu layer exposes the ITO layer that was cleared in step P2, forming the final interconnect channel.

[0049] Process: Using an ultraviolet laser (wavelength 355nm), fine and clean etching can be achieved.

[0050] Laser parameters: power 1.5W, frequency 60kHz, scanning speed 1000mm / s.

[0051] Precise ablation of the stacked layers except for ITO completely exposes the ITO surface.

[0052] Step 10: Laser edge cleaning (P4) Objective: To remove all functional layers (ITO, NiO) around the perimeter of the component. X Perovskite, C 60 SnO X Cu) prevents water and oxygen intrusion and current leakage (edge ​​short circuit) caused by edge defects, ensuring the insulation and long-term stability of the components.

[0053] Process: A picosecond ultraviolet laser (wavelength 355nm) is used to achieve a clean, melt-free cutting effect.

[0054] Laser parameters: power 5W, frequency 200kHz, scanning speed 300mm / s.

[0055] A scanning cut is performed approximately 2mm inside the edge of the component to completely remove all thin film layers outside the effective area, exposing the surrounding glass substrate.

[0056] Step 11: Packaging and Testing Glass-to-glass sealing was completed in a nitrogen atmosphere glove box.

[0057] IV performance testing and stability evaluation were conducted.

[0058] First embodiment of the present invention: A perovskite precursor ink, comprising a perovskite precursor active component and an organic mixed solvent; It also includes amphiphilic block copolymer additives; The amphiphilic block copolymer additive is composed of perovskite segments and flexible hydrophobic segments connected by covalent bonds; The perovskite-loving segments are polyvinylpyridine segments with a degree of polymerization n of 10 to 100, and the flexible hydrophobic segments are polyoxyethylene segments with a degree of polymerization m of 20 to 200.

[0059] The amphiphilic block copolymer additive is P4VP 50 -b-PEO 100 Its polymer dispersion is 1.12.

[0060] The amphiphilic block copolymer additive in the perovskite precursor ink is 0.05% to 0.2% by mass.

[0061] The amphiphilic block copolymer additive in this embodiment is composed of two different polymer segments: one segment is called polyvinylpyridine, which is a "perovskite-loving segment," and the other segment is called polyethylene oxide, which is a "flexible segment."

[0062] The role of the perovskite-loving segments (polyvinylpyridine): This polymer has many nitrogen atoms. These nitrogen atoms have lone pairs of electrons, which, like "hands," can firmly grasp lead ions in the perovskite solution. This gripping effect is very strong. As a result, when the perovskite first begins to crystallize, these polymer segments can act as "crystallization guide points," allowing the crystal to grow in an orderly manner around these points. This directly solves the problems of disordered crystal nucleus formation and inconsistent grain size in traditional methods.

[0063] The role of the flexible segments (polyethylene oxide): This polymer is very flexible and inherently hydrophobic. During the drying and crystallization process of the perovskite film, the entire additive molecule becomes mobile. The flexible polyethylene oxide segments tend to move to the crystal boundaries and the outermost surface of the film.

[0064] Existing technologies may use substances like polyvinylpyridine to passivate defects or polyethylene oxide to improve film toughness. However, these are typically two separate substances added. Our design directly links these two functionally different components into a large molecule through strong chemical bonds. The advantages of doing so are: The functions work together precisely in space: during crystallization, the perovskite-loving end anchors itself to the crystal to guide growth, while the flexible end naturally extends to the grain boundaries and surface. This is like equipping each grain with a "frame" that is both sturdy and waterproof.

[0065] This single additive molecule simultaneously solves multiple problems: it guides crystallization (through the strong coordination of pyridine nitrogen with lead), releases stress (through the deformation of flexible segments), and forms a hydrophobic surface layer (through the enrichment of flexible segments on the surface). It achieves a leap from "defect passivation" to "bulk encapsulation." Few existing technologies offer such a multifunctional, integrated design.

[0066] The second embodiment of the present invention: A method for preparing a perovskite thin film includes the following steps: Step 1: Provide a perovskite precursor ink as described above; Step 2: On the substrate containing the hole transport layer, perovskite precursor ink is coated in an air environment using a slot coating method to form a wet film. Step 3: Perform gradient thermal annealing on the wet film to crystallize and form a perovskite film.

[0067] In step 2, the slit coating speed is 8~12 mm / s.

[0068] In step 3, the gradient thermal annealing process includes preheating at 60-80°C for 2-4 minutes, followed by annealing at 90-110°C for 28-32 minutes.

[0069] In the preparation method of this embodiment, the perovskite precursor ink is combined with the slot coating method, which can be operated in an air environment, and a gradient thermal annealing drying and crystallization method is adopted.

[0070] Choosing slot coating is ideal for uniform, efficient, and economical ink application on large substrates, and is the way forward for future factory production.

[0071] Operating in an air environment simplifies the harsh working environment that previously required production in a glove box to isolate water and oxygen. This is mainly because the additive itself has hydrophobic properties, which can form a protective layer during film formation, thus improving the practicality and compatibility of the process.

[0072] After coating to obtain a wet film, it is not directly baked at a high temperature. First, it is preheated at a relatively low temperature, and then gradually increased to the crystallization temperature. This "gradient heating" process is crucial. It allows the solvent to evaporate slowly and evenly, giving the additive molecules time to arrange and migrate in an orderly manner, thereby guiding the perovskite crystals to grow larger and more uniformly. If it is directly baked at a high temperature, the film is prone to cracking or disordered crystallization.

[0073] The use of inks containing special block copolymer additives, a slot coating method suitable for large-scale production, and gradient annealing in an air environment to precisely control the crystallization process—these three elements work together to ensure the final product is a high-quality, large-area, and uniformly crystalline perovskite film.

[0074] The third embodiment of the present invention: A method for preparing a perovskite solar cell module includes the following steps: Step 1: Provide and clean the transparent conductive oxide glass substrate; Step 2: Perform the first laser scribing on the conductive layer surface of the substrate to form multiple spaced first scribing lines to define the sub-cell area; Step 3: Deposit a hole transport layer on the substrate surface; Step 4: Using any of the perovskite thin film preparation methods described above, prepare a perovskite light-absorbing layer on the hole transport layer; Step 5: Deposit an electron transport layer on the perovskite light-absorbing layer; Step 6: Deposit a buffer layer on the electron transport layer; Step 7: Perform a second laser scribing to remove the perovskite light-absorbing layer, electron transport layer, and buffer layer corresponding to the area marked in the first scribing, exposing the hole transport layer or conductive layer underneath. Step 8: Deposit a metal electrode, which forms an electrical connection with the area exposed in Step 7; Step 9: Perform a third laser scribing to remove part of the hole transport layer, perovskite light-absorbing layer, electron transport layer, buffer layer and metal electrode corresponding to the first scribing area, forming an interconnect structure that connects adjacent sub-cells in series; Step 10: Perform the fourth laser edge cleaning to remove all functional layers at the edge of the component, exposing the surrounding glass substrate; Step 11: Encapsulate the perovskite solar cell module.

[0075] In step 2, the first laser scribing uses a green laser with a wavelength of 532nm, a power of 2~4W, a frequency of 40~60kHz, and a scanning speed of 400~600mm / s; In step 7, the second laser scribing uses an infrared laser with a wavelength of 1064nm, a power of 3~5W, a frequency of 70~90kHz, and a scanning speed of 700~900mm / s; In step 9, the third laser scribing uses an ultraviolet laser with a wavelength of 355nm, a power of 1~2W, a frequency of 50~70kHz, and a scanning speed of 900~1100mm / s. In step 10, the fourth laser scribing uses a picosecond ultraviolet laser with a wavelength of 355nm, a power of 4~6W, a frequency of 190~210kHz, and a scanning speed of 200~400mm / s.

[0076] In step 3, a NiO layer with a thickness of 10-30 nm is deposited using magnetron sputtering. X The film is then annealed in air at 190-210°C for 28-32 minutes. In step 5, a C layer with a thickness of 10-30 nm is deposited using a high-vacuum thermal evaporation method. 60 film.

[0077] In step 6, a dense SnO layer with a thickness of 5-20 nm is deposited at 70-90°C for 90-110 cycles. X film; In step 8, a copper electrode with a thickness of 90-110 nm is deposited by magnetron sputtering at room temperature.

[0078] The core improvement between the steps in this implementation scheme is as follows: Phase 1: Laying the Foundation (Steps 1-3) First, prepare and clean the conductive glass substrate. Then, immediately perform the first laser scribing. The purpose of this step is to scribing isolation lines on the bottom conductive layer, dividing the entire electrode surface into individual lines. This lays the foundation for the subsequent fabrication of multiple small battery cells connected in series. Only after scribing is the hole transport layer deposited on the entire board. This order is crucial; if the coating is deposited first and then the scribing is performed, it will be much more difficult.

[0079] Phase Two: Creating the Core (Step S4) Next, using the aforementioned method, a large-area perovskite light-absorbing layer is fabricated on the hole transport layer. This is the core component of the module's power generation.

[0080] Phase 3: Completing the "Sandwich" and Opening the Channel (Steps 5-7) On the perovskite layer, an electron transport layer and a buffer layer are deposited sequentially to form a complete "sandwich" structure. Then, a second laser scribing is performed. This scribing must be precisely aligned with the position of the first scribing. Its purpose is to remove all the upper material in the area scribed in the first scribing, exposing the bottom conductive layer and opening a "contact window" for connecting the upper and lower electrodes.

[0081] Phase 4: Connection and Isolation (Steps 8-9) Next, the top metal electrode is deposited. The metal naturally fills the previously opened "contact window," thus connecting with the bottom conductive layer. Then, a third laser scribing is performed. This scribing is also aligned with the areas scribed in the first two scribings. Its purpose is to cut the top metal electrode layer. In this way, the "top electrode of battery cell A" is connected to the "bottom electrode of battery cell B" through the "contact window," completing the series connection between the battery cells.

[0082] Phase 5: Sealing the edges (Step 10) Finally, a fourth laser edge cleaning is performed. A laser is used to completely remove all functional layers around the perimeter of the module, leaving only the bottom glass. This step is crucial, as it eliminates potential short-circuit points and moisture intrusion channels at the edges, significantly improving the long-term stability and safety of the module.

[0083] Combining the three implementation schemes above, this invention forms a complete, self-consistent, and interconnected innovation system, from molecular-level ink design to production-oriented thin film preparation processes and precision-integrated component manufacturing processes.

[0084] Embodiments of the present invention: This embodiment specifically describes the preparation of a perovskite thin film containing an amphiphilic block copolymer additive. 1. Preparation of precursor ink Accurately weigh the following raw materials and place them in a 50 mL glass reaction flask: Lead iodide (PbI₂): 17979.39 mg (99.99% purity, Sigma-Aldrich), Formamidinium iodide (FAI): 6036.147 mg (99.5% purity, Greatcell Solar), Methylamine iodide (MAI): 309.9915 mg (99.5% purity, Lumtec), Cesium iodide (CsI): 506.6295 mg, Methylamine chloride (MACl): 394.992 mg (99.99% purity, Sigma-Aldrich). Add 30.0 mL of mixed solvent, wherein the volume ratio of N,N-dimethylformamide (DMF, 99.9% purity) to N-methylpyrrolidone (NMP, 99.9% purity) is 4:1. Then add an accurately weighed amount of P₄VP. 50 -b-PEO 100 30 mg of an amphiphilic block copolymer (polymer dispersion Ð = 1.12, Polymer Sources, USA) was used. The mixture was stirred continuously at 1200 rpm for 12 hours in a water bath at 60 ± 1 °C. The mixture was then filtered through a 0.22 μm PTFE needle filter to obtain a homogeneous and transparent precursor ink.

[0085] 2. Thin film coating preparation The well-stirred perovskite precursor solution was injected into the injection pipe of the slot coating equipment, into a 300mm × 300mm ITO / NiO coating chamber. X Slit coating was performed on the substrate at a constant speed of 10 mm / s. The wet film was then immediately subjected to flash evaporation to rapidly remove most of the solvent, resulting in a uniform mesophase film. Finally, the mesophase film was transferred to a preheated annealing furnace, preheated at 70°C for 3 min, and then annealed at 100°C for 30 min to complete the crystallization and solidification of the perovskite film.

[0086] 3. Thin film characterization XRD, SEM and contact angle tests were performed on the films obtained in the examples and comparative examples respectively to systematically evaluate their key performance indicators such as crystallinity, grain size, film density and surface hydrophobicity.

[0087] Comparative examples of the present invention: This embodiment specifically uses an additive-free system.

[0088] The same basic formulation and process conditions as in Example 1 were used, but without the addition of any amphiphilic block copolymer additives.

[0089] like Figures 1-7 As shown, the test results of the embodiments and comparative examples of the present invention are analyzed as follows: First, please refer to Figure 1 This diagram illustrates the molecular structure of the core additive of this invention, namely, the amphiphilic block copolymer additive. The copolymer is a long polymer chain composed of two polymer segments (i.e., "blocks") with different properties connected by covalent bonds: The first segment (perovskite-loving segment): is a polyvinylpyridine segment with a degree of polymerization n of 10-100. The nitrogen atom on this segment contains a lone pair of electrons and can act as a strong Lewis base. The second segment (flexible segment): is a polyethylene oxide segment with a degree of polymerization m of 20-200. This segment exhibits excellent flexibility and chain mobility.

[0090] Figures 2-3 These are SEM images of the perovskite films prepared in the embodiments and comparative examples of this invention, respectively. As can be seen from the images, the perovskite films in the embodiments exhibit significantly optimized crystallinity: their grain size increases dramatically from 200-300 nm in the comparative example to 700-800 nm, and the size distribution is uniform. This large-size, uniform grain structure helps reduce grain boundaries, indicating that the crystallinity quality and photoelectric properties of the film are effectively improved.

[0091] Figure 4This is an XRD pattern of the films prepared in the embodiments and comparative examples of this invention. The XRD patterns show that the introduction of additives effectively regulated the crystallization process: the films exhibited better crystal orientation and higher crystallinity, while the residual diffraction peaks of PbI2 were significantly weakened. This proves that the additives not only promoted the directional growth of perovskite grains, but also improved the conversion efficiency of the precursor by inhibiting the separation of PbI2.

[0092] Figures 5-6 These are schematic diagrams showing the water contact angles of the films prepared in the embodiments and comparative examples of this invention. Test results show that the hydrophobicity of the film modified with the additives (87.780°) is significantly stronger than that of the control group (60.489°), effectively preventing environmental moisture from eroding the perovskite layer. This is attributed to the enrichment effect of the additives at the grain boundaries. This characteristic is key to improving the film's moisture resistance and device lifespan.

[0093] Figure 7 These are IV curves of the perovskite modules (300mm × 300mm) prepared according to the embodiments and comparative examples of this invention, providing a performance evaluation of the 300mm × 300mm large-area module (aperture area 655.2 cm²). 2 The results show that the component prepared by this invention achieves an aperture efficiency of 21.13%, which is a significant improvement compared to the comparative example (18.91%). IV curve analysis reveals that this improvement is due to the combined improvement of open-circuit voltage, fill factor, and short-circuit current, which reflects the effective suppression of nonradiative recombination and the optimization of carrier transport capability inside the thin film, indicating that the component has better operating stability.

[0094] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the invention. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0095] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0096] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A perovskite precursor ink, comprising a perovskite precursor active component and an organic mixed solvent; Its features are: It also includes amphiphilic block copolymer additives; The amphiphilic block copolymer additive is composed of perovskite segments and flexible hydrophobic segments connected by covalent bonds; The perovskite-loving segment is a polyvinylpyridine segment with a degree of polymerization n of 10 to 100, and the flexible hydrophobic segment is a polyoxyethylene segment with a degree of polymerization m of 20 to 200.

2. The perovskite precursor ink as described in claim 1, characterized in that, The amphiphilic block copolymer additive is P4VP. 50 -b-PEO 100 Its polymer dispersion is 1.

12.

3. The perovskite precursor ink as described in claim 1, characterized in that, The amphiphilic block copolymer additive is present in the perovskite precursor ink at a mass percentage of 0.05% to 0.2%.

4. A method for preparing a perovskite thin film, characterized in that, Includes the following steps: Step 1: Provide a perovskite precursor ink as described in any one of claims 1 to 3; Step 2: On the substrate containing the hole transport layer, the perovskite precursor ink is coated in an air environment using a slot coating method to form a wet film; Step 3: Perform gradient thermal annealing on the wet film to crystallize and form a perovskite thin film.

5. The method for preparing a perovskite thin film as described in claim 4, characterized in that, In step 2, the slit coating speed is 8~12 mm / s.

6. The method for preparing a perovskite thin film as described in claim 4, characterized in that, In step 3, the gradient thermal annealing process includes preheating at 60-80°C for 2-4 minutes, followed by annealing at 90-110°C for 28-32 minutes.

7. A method for preparing a perovskite solar cell module, characterized in that, Includes the following steps: Step 1: Provide and clean the transparent conductive oxide glass substrate; Step 2: Perform a first laser scribing on the conductive layer surface of the substrate to form multiple spaced first scribing lines to define the sub-cell area; Step 3: Deposit a hole transport layer on the surface of the substrate; Step 4: Using the perovskite thin film preparation method as described in any one of claims 4 to 6, a perovskite light-absorbing layer is prepared on the hole transport layer; Step 5: Deposit an electron transport layer on the perovskite light-absorbing layer; Step 6: Deposit a buffer layer on the electron transport layer; Step 7: Perform a second laser scribing to remove the perovskite light-absorbing layer, electron transport layer, and buffer layer corresponding to the area marked in the first scribing, exposing the hole transport layer or conductive layer underneath. Step 8: Deposit a metal electrode, which forms an electrical connection with the area exposed in Step 7; Step 9: Perform a third laser scribing to remove part of the hole transport layer, perovskite light-absorbing layer, electron transport layer, buffer layer and metal electrode corresponding to the first scribing area, forming an interconnect structure that connects adjacent sub-cells in series; Step 10: Perform the fourth laser edge cleaning to remove all functional layers at the edge of the component, exposing the surrounding glass substrate; Step 11: Encapsulate the perovskite solar cell module to obtain the module.

8. The method for preparing a perovskite solar cell module as described in claim 7, characterized in that: In step 2, the first laser scribing uses a green laser with a wavelength of 532nm, a power of 2~4W, a frequency of 40~60kHz, and a scanning speed of 400~600mm / s. In step 7, the second laser scribing uses an infrared laser with a wavelength of 1064nm, a power of 3~5W, a frequency of 70~90kHz, and a scanning speed of 700~900mm / s. In step 9, the third laser scribing uses an ultraviolet laser with a wavelength of 355nm, a power of 1~2W, a frequency of 50~70kHz, and a scanning speed of 900~1100mm / s. In step 10, the fourth laser scribing uses a picosecond ultraviolet laser with a wavelength of 355nm, a power of 4~6W, a frequency of 190~210kHz, and a scanning speed of 200~400mm / s.

9. The method for preparing a perovskite solar cell module as described in claim 7, characterized in that: In step 3, a NiO layer with a thickness of 10-30 nm is deposited using magnetron sputtering. X The film is then annealed in air at 190-210°C for 28-32 minutes. In step 5, a C layer with a thickness of 10-30 nm is deposited using a high-vacuum thermal evaporation method. 60 film.

10. The method for preparing a perovskite solar cell module as described in claim 7, characterized in that: In step 6, a dense SnO layer with a thickness of 5-20 nm is deposited at 70-90°C through 90-110 cycles. X film; In step 8, a copper electrode with a thickness of 90-110 nm is deposited by magnetron sputtering at room temperature.

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