Method for manufacturing perovskite thin film battery and perovskite thin film battery

Abstract

The present invention discloses a method for manufacturing a perovskite thin film battery and a perovskite thin film battery, comprising: S1, providing a perovskite battery; S2, performing line etching on the connecting portion in the laser processing area to form a second etching line, S3, performing point etching at the intersection of adjacent laser processing areas to form an etching hole; wherein, after step S1, the process is performed in accordance with a preset first method or a second method, the first method is to perform step S3 after completing step S2 for all laser processing areas; the second method is to perform step S3 at the intersection of the laser processing area and the adjacent laser processing area after completing step S2 for the first laser processing area, and then perform step S2 for the next laser processing area, and then perform step S3 at the new adjacent intersection, and alternately perform steps S2 and S3 until all laser processing areas are processed. The technical solution of the present invention can avoid the problem that the top electrode layers of adjacent sub-battery units still maintain electrical connection at certain points.

Description

Technical Field

[0001] The present invention relates to the technical field of thin film battery production, and in particular to a method for manufacturing a perovskite thin film battery and a perovskite thin film battery. Background Art

[0002] Perovskite thin-film cells are one of the most eye-catching emerging technologies in the photovoltaic field in recent years. They use perovskite materials as light absorption layers and are usually composed of a multilayer structure including a transparent base layer, a bottom electrode layer, a hole transport layer, a perovskite light absorption layer, an electron transport layer, and a top electrode layer. Compared with traditional silicon-based solar cells, the most significant advantage of perovskite thin-film cells is their excellent flexibility and customizability. Such cells can be made on flexible substrates, such as plastic or metal foil, allowing them to be bent, folded, or even rolled up without affecting their performance. This flexible property greatly expands the application scenarios of solar cells, allowing them to be easily integrated into non-planar structures such as curved buildings, wearable devices, and vehicle shells. More importantly, perovskite thin-film cells can be cut according to specific application requirements. This unique tailorability enables them to adapt to installation spaces of various shapes and sizes, greatly improving the flexibility of solar energy utilization. For example, in the field of building integrated photovoltaics (BIPV), perovskite thin-film cells can be cut into specific shapes and perfectly integrated into the exterior design of the building. In addition, perovskite thin-film batteries also have the advantages of simple manufacturing process, low cost, and rapid efficiency improvement. Its photoelectric conversion efficiency has increased from the initial 3.8% to more than 25%. These characteristics make perovskite thin-film batteries show great application potential in portable electronic devices, smart buildings, aerospace and other fields, and are considered to be an important candidate for the next generation of high-efficiency, low-cost, and highly customizable solar cells.

[0003] The efficient operation of perovskite thin-film batteries depends on the precise design of their internal structure. In order to improve the output voltage and overall performance of perovskite thin-film batteries, perovskite thin-film batteries are usually divided into multiple sub-battery units, which are arranged in sequence in the width direction of the perovskite thin-film battery and connected in series. In order to achieve this series structure, precise laser scribing is required at the connection between two adjacent sub-battery units. The main purpose is to separate the top electrode layers of adjacent sub-battery units, while ensuring that the top electrode layer of one sub-battery unit is electrically connected to the bottom electrode layer of the adjacent sub-battery unit.

[0004] However, there is a contradiction between the long strip structure of perovskite thin-film batteries and the limited working area of ​​the laser equipment. This requires the laser equipment to perform multiple scribing operations in the length direction of the battery. This segmented processing method increases the risk of scribing discontinuities between adjacent laser processing areas in the length direction of the battery. Specifically, the scribing endpoint of the previous laser processing area may not be accurately aligned with the scribing starting point of the next laser processing area, so that the top electrode layers of adjacent sub-battery units may not be completely separated at these junctions. This discontinuous scribing may cause the top electrode layers of adjacent sub-battery units that should have been separated to remain electrically connected at certain points. This not only affects the expected series effect, but may also cause local short circuits or leakage currents, seriously damaging the overall output performance of the battery. Summary of the invention

[0005] The main purpose of the present invention is to propose a method for manufacturing a perovskite thin film battery, aiming to solve the technical problem of the prior art perovskite thin film battery, in which the top electrode layers of adjacent sub-battery units that should have been separated still maintain electrical connection at certain points.

[0006] To achieve the above-mentioned purpose, the method for manufacturing a perovskite thin film battery proposed in the present invention comprises:

[0007] S1. Provide a perovskite cell, wherein the perovskite cell comprises a plurality of laser processing regions sequentially connected in its length direction, and the perovskite cell comprises a plurality of sub-cell units spaced apart in its width direction, any two adjacent sub-cell units are connected by a connecting portion, and each of the sub-cell units and each of the connecting portions comprises a transparent base layer, a bottom electrode layer, a hole transport layer, a light absorption layer, an electron transport layer and a top electrode layer arranged in a stacked manner;

[0008] A first etching line is formed on the bottom electrode layer of the connecting portion, and the first etching line is used to separate the bottom electrode layers of two adjacent sub-battery units. A conductive material is also provided on the connecting portion, and the location of the conductive material and the location of the first etching line are offset in the width direction of the perovskite battery. The conductive material penetrates the top electrode layer, the electron transport layer, the light absorption layer, and the hole transport layer of the connecting portion, and the conductive material is used to electrically connect the top electrode layer of one of the two adjacent sub-battery units and the bottom electrode layer of the other;

[0009] S2, performing line etching on the connecting portion in the laser processing area to form a second etching line that penetrates the top electrode layer, the electron transport layer, the light absorption layer and the hole transport layer of the connecting portion, wherein the second etching line is located on a side of the conductive material that is away from the first etching line;

[0010] S3, performing point etching at the intersection of adjacent laser processing areas to form an etching hole that penetrates the top electrode layer, the electron transport layer, the light absorption layer, the hole transport layer and the bottom electrode layer of the connecting portion, wherein the diameter of the etching hole is greater than or equal to the width of the connecting portion;

[0011] Among them, after step S1, the process is performed in a preset first manner or a second manner. The first manner is to perform step S3 after completing step S2 for all laser processing areas. The second manner is to perform step S3 at the intersection of the laser processing area and the adjacent laser processing area after completing step S2 for the first laser processing area, and then perform step S2 for the next laser processing area, and then perform step S3 at the new adjacent intersection, and alternately perform steps S2 and S3 until all laser processing areas are processed.

[0012] In some embodiments, when the first method is adopted, S3 includes:

[0013] S31a, scanning the intersection of adjacent laser processing areas to obtain structural information of the connection portion of the intersection, wherein the structural information includes position and size data of the first etching line, the conductive material, and the second etching line;

[0014] S32a, forming a mask pattern for etching holes on the top electrode layer based on the acquired structural information;

[0015] S33a, setting laser spot etching parameters according to the mask pattern, including laser power, pulse frequency and scanning path;

[0016] S34a, performing etching using set laser spot etching parameters to form etching holes that penetrate the top electrode layer, the electron transport layer, the light absorption layer, the hole transport layer and the bottom electrode layer of the connecting portion.

[0017] In some embodiments, the S32a includes:

[0018] S321a, determining the boundary of each of the connecting parts on the top electrode layer based on the acquired structural information;

[0019] S322a, calculating the center position and diameter of the etching hole within the boundary of each connecting portion;

[0020] S323a, marking a circular etching area on the top electrode layer according to the calculated center position and diameter;

[0021] S324a, applying a local electric field around the circular etching area;

[0022] S325a, spraying charged photosensitive material particles toward the periphery of the circular etching area, so that the photosensitive material particles are deposited on the top electrode layer to form an annular distribution structure centered on the circular etching area;

[0023] S326a, selectively exposing the deposited photosensitive material particles using an ultraviolet light source to form a solidified pattern corresponding to the circular etching area;

[0024] S327a, cleaning the uncured photosensitive material with a developer, so that the cured pattern forms a mask pattern of etching holes on the top electrode layer.

[0025] In some embodiments, the S325a includes:

[0026] Dissolving a photosensitive material in an organic solvent to prepare a precursor solution;

[0027] Atomizing the precursor liquid into charged droplets using a piezoelectric nozzle;

[0028] The charged droplets are sprayed around the circular etching area, and during the flight of the droplets, the solvent is evaporated by an infrared heater, and the charged particles are accelerated and oriented by the local electric field to form solid photosensitive material particles;

[0029] By adjusting the intensity distribution of the local electric field and the spray angle of the piezoelectric nozzle, the solid photosensitive material particles are controlled to be deposited on the top electrode layer to form an annular distribution structure centered on the circular etching area.

[0030] In some embodiments, the photosensitive material is a positive photoresist, and the organic solvent is propylene glycol methyl ether acetate.

[0031] In some embodiments, the piezoelectric nozzle has a spraying frequency of 1 kHz to 100 kHz, and a diameter of the sprayed charged droplets is 1 μm to 50 μm.

[0032] In some embodiments, the temperature of the infrared heater is 50°C to 200°C.

[0033] In some embodiments, the strength of the local electric field is 0.1 kV / cm to 10 kV / cm.

[0034] In some embodiments, the inner diameter of the annular distribution structure is equal to the diameter of the circular etching area, and the outer diameter of the annular distribution structure is 0.5 μm to 10 μm larger than the inner diameter of the annular distribution structure.

[0035] In some embodiments, when the second method is adopted, S3 includes:

[0036] S31b, calculating the optimal etching hole position and size based on the second etching line end position of the laser processing area where the line etching has been completed, the first etching line position, the conductive material position, and the expected second etching line position of the next laser processing area;

[0037] S32b, performing point etching at the calculated optimal etching hole position to form a main etching hole that penetrates the top electrode layer, the electron transport layer, the light absorption layer, the hole transport layer and the bottom electrode layer of the connecting portion;

[0038] S33b. Perform local etching on the peripheral wall of the main etching hole on a side adjacent to the next laser processing area to form a secondary etching hole, wherein the secondary etching hole penetrates the top electrode layer, the electron transport layer and the light absorbing layer, and the central axis of the secondary etching hole intersects with the central axis of the expected second etching line of the next laser processing area.

[0039] In some embodiments, the S33b includes:

[0040] S331b, based on the direction of the completed second etching line, extending the track of the completed second etching line in the main etching hole;

[0041] S332b, determining the intersection point between the track and the peripheral wall of the main etching hole, and taking the intersection point as the center of the auxiliary etching hole;

[0042] S333b, taking the center of the secondary etching hole as a reference, forming a secondary etching hole on the peripheral wall of the main etching hole.

[0043] In some embodiments, the diameter of the etched hole is less than 1 mm.

[0044] The present invention also provides a perovskite thin film battery, which is manufactured by the above-mentioned method for manufacturing a perovskite thin film battery, wherein the perovskite thin film battery comprises a perovskite battery, wherein the perovskite battery comprises a plurality of laser processing regions sequentially connected in its length direction, wherein the perovskite battery comprises a plurality of sub-battery units spaced apart in its width direction, wherein any two adjacent sub-battery units are connected by a connecting portion, and each of the sub-battery units and each of the connecting portions comprises a transparent base layer, a bottom electrode layer, a hole transport layer, a light absorption layer, an electron transport layer and a top electrode layer which are stacked;

[0045] A first etching line is formed on the bottom electrode layer of the connecting portion, and the first etching line is used to separate the bottom electrode layers of two adjacent sub-battery units. A conductive material is also provided on the connecting portion, and the location of the conductive material and the location of the first etching line are offset in the width direction of the perovskite battery. The conductive material penetrates the top electrode layer, the electron transport layer, the light absorption layer, and the hole transport layer of the connecting portion, and the conductive material is used to electrically connect the top electrode layer of one of the two adjacent sub-battery units and the bottom electrode layer of the other;

[0046] A second etching line is formed on the connecting portion, which passes through the top electrode layer, electron transport layer, light absorption layer and hole transport layer of the connecting portion. An etching hole is formed at the intersection of any two adjacent laser processing areas, which passes through the top electrode layer, electron transport layer, light absorption layer, hole transport layer and bottom electrode layer of the connecting portion. The etching holes are respectively connected to the second etching lines of the two adjacent laser processing areas.

[0047] The method for manufacturing a perovskite thin-film battery of the technical solution of the present invention performs point etching at the intersection of adjacent laser processing areas to form etching holes that penetrate the top electrode layer, electron transport layer, light absorption layer, hole transport layer and bottom electrode layer of the entire connection, thereby ensuring that the top electrode layers of adjacent sub-battery units are completely separated at the intersection. The introduction of this point etching technology effectively avoids the misalignment or discontinuity of the scribing that may have occurred, thereby preventing the top electrode layers of adjacent sub-battery units from maintaining unnecessary electrical connections at certain points. Secondly, by designing the diameter of the etching hole to be greater than or equal to the width of the connection, the method further ensures that the etching hole can completely cover the connection area and completely cut off any residual electrical connection that may exist. This design not only ensures effective isolation between sub-battery units, but also improves the stability and reliability of the entire battery structure.

[0048] In addition, the flexibility of the method of the present invention is reflected in the fact that it provides two optional manufacturing methods. The first method is suitable for large-scale batch production by first completing the line etching of all laser processing areas and then performing point etching; the second method adopts a strategy of alternating line etching and point etching, which is more suitable for small batch or customized production. The combination of these two methods enables the method to adapt to different production needs and equipment conditions. In particular, in the second method, point etching is performed immediately after completing the line etching of each laser processing area. This instant processing method can better control the accuracy of each processing step, and can promptly detect and correct possible problems. In this way, the method not only solves the problem of discontinuous scribing, but also improves the controllability of the entire manufacturing process and the consistency of the product. In general, the method of the present invention effectively improves the manufacturing accuracy and product quality of perovskite thin-film batteries through a carefully designed etching process and a flexible manufacturing strategy, and provides reliable technical support for the large-scale production of large-area, high-performance perovskite thin-film batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.

[0050] Figure 1 It is a flow chart of an embodiment of a method for manufacturing a perovskite thin film battery in an embodiment of the present invention;

[0051] Figure 2 A partial cross-sectional view of a perovskite cell;

[0052] Figure 3 A top view of a perovskite cell;

[0053] Figure 4 This is a comparison picture before and after the etching hole is formed.

[0054] Description of Figure Numbers:

[0055] a. Laser processing area; 1. Sub-battery unit; 2. Connecting part; 3. Transparent base layer; 4. Bottom electrode layer; 5. Hole transport layer; 6. Light absorption layer; 7. Electron transport layer; 8. Top electrode layer; 9. First etching line; 10. Conductive material; 11. Second etching line; 12. Etching hole.

[0056] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0057] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0058] It should be noted that if the embodiments of the present invention involve directional indications (such as up, down, left, right, front, back...), the directional indications are only used to explain the relative position relationship, movement status, etc. between the components under a certain specific posture (as shown in the accompanying drawings). If the specific posture changes, the directional indication will also change accordingly.

[0059] In addition, the descriptions of "first", "second", etc. in the present invention are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, "and / or" in the full text includes three solutions. Taking A and / or B as an example, it includes technical solution A, technical solution B, and technical solution that satisfies both A and B. In addition, the technical solutions between the various embodiments can be combined with each other, which must be based on the ability of ordinary technicians in the field to implement. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0060] Figure 1 A flowchart of an embodiment of a method for manufacturing a perovskite thin film battery; Figure 2 A partial cross-sectional view of a perovskite cell; Figure 3 A top view of a perovskite cell; Figure 4 This is a comparison chart before and after the etching hole is formed. It should be noted that Figure 2 The cross-sectional view shown only shows two sub-cells, and does not show all the sub-cells of the entire perovskite cell. In addition, the dotted line in Figure 2 is not part of the perovskite cell structure. Figure 2 The dashed line represents the boundary of the connection. Figure 3 The dotted lines in the figure are not part of the perovskite cell structure, but are only used to illustrate the laser processing area of ​​the perovskite cell.

[0061] like Figure 2 and Figure 3 As shown, the perovskite cell includes a transparent base layer 3, a bottom electrode layer 4, a hole transport layer 5, a perovskite light absorbing layer 6, an electron transport layer 7 and a top electrode layer 8 from bottom to top.

[0062] Specifically, the transparent base layer 3 is generally a flexible polymer material (such as PET or PEN), which is used to provide mechanical support and protection while allowing light to pass through.

[0063] Common materials for the bottom electrode layer 4 include fluorine-doped tin oxide (FTO) or indium tin oxide (ITO). This layer has good electrical conductivity and light transmittance and serves as an electrode of the battery.

[0064] Common materials for the hole transport layer 5 are nickel oxide (NiOx) or poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate). (PEDOT:PSS). The function of this layer is to selectively transport holes, block electrons, and improve the charge separation efficiency.

[0065] The perovskite light-absorbing layer 6 is usually composed of perovskite materials such as CH3NH3PbI3, which is the core layer of the battery and is responsible for absorbing photons and generating electron-hole pairs.

[0066] Common materials for the electron transport layer 7 are titanium dioxide (TiO2) or fullerene derivatives (such as PCBM). This layer selectively transports electrons and blocks holes, further improving the charge separation efficiency.

[0067] The top electrode layer 8 is usually made of metal materials such as gold, silver or aluminum. This layer serves as the other electrode of the battery and collects electrons.

[0068] The production process of the above perovskite cell is usually as follows:

[0069] The first step: depositing a bottom electrode layer 4 on a clean transparent substrate 3, usually by magnetron sputtering or chemical vapor deposition.

[0070] Step 2: Use laser etching technology to form multiple first etching lines 9 on the bottom electrode layer 4 to separate the bottom electrode layer 4 into multiple bottom electrode units. One bottom electrode unit corresponds to one sub-battery unit 1. Simply put, one bottom electrode unit constitutes an electrode of the corresponding sub-battery unit 1.

[0071] Step 3: depositing the hole transport layer 5 on the bottom electrode layer 4. At this time, part of the material of the hole transport layer 5 will flow into the space of the first etching line 9, that is, in the process of depositing the hole transport layer 5, the material of the hole transport layer 5 will fill the etched part of the bottom electrode layer 4.

[0072] Step 4: depositing a light absorbing layer 6 on the hole transport layer 5 .

[0073] Step 5: depositing an electron transport layer 7 on the light absorbing layer 6 .

[0074] Afterwards, in some embodiments, laser equipment is used for scribing to form a first series etching line that passes through the electron transport layer 7, the light absorption layer 6 and the hole transport layer 5, and then the top electrode layer 8 is deposited on the electron transport layer 7. In the process of forming the top electrode layer 8, the material of the top electrode layer 8 will flow into the first series etching line. This part of the material will be subsequently used as a conductive material 10 to realize the material used for connecting two adjacent sub-battery units 1 in series.

[0075] In other embodiments, the top electrode layer 8 can also be directly deposited on the electron transport layer 7, and then a second series etching line penetrating the top electrode layer 8, the electron transport layer 7, the light absorption layer 6 and the hole transport layer 5 is formed by a laser device, and then some conductive materials are added to the second series etching holes 12. This part of the material will be subsequently used as the conductive material 10 to realize the material for connecting two adjacent sub-battery units 1 in series.

[0076] The last step: by laser scribing on the side of the conductive material 10 away from the first etching line 9, a second etching line 11 is formed that passes through the top electrode layer 8, the electron transport layer 7, the light absorption layer 6 and the hole transport layer 5. At this point, the first etching line 9, the conductive material 10 and the second etching line 11 are arranged in sequence from left to right in the width direction of the perovskite battery. The second etching line 11 divides the top electrode layer 8 into multiple top electrode units. Similarly, one top electrode unit corresponds to one sub-battery unit 1. Simply put, one top electrode unit constitutes an electrode of the corresponding sub-battery unit 1.

[0077] The above processing process can form a perovskite battery formed by connecting multiple sub-battery units 1 in series.

[0078] As mentioned in the background technology, since the perovskite cell is very long and the working surface of the laser equipment is limited, multiple laser processes are required along the length of the perovskite cell to complete the production of the entire cell. This segmented processing method may result in the following Figure 4 The problem shown on the left is that the end of the etching line in the previous area may not be accurately connected to the starting point of the etching line in the next area. This discontinuity may cause the top electrode layer 8 of adjacent sub-battery units 1 that should have been completely separated to remain electrically connected at some points.

[0079] To this end, the present invention proposes a method for manufacturing a perovskite thin film battery.

[0080] In the embodiment of the present invention, Figure 1 As shown, the method for manufacturing the perovskite thin film battery includes:

[0081] S1. Provide a perovskite battery, wherein the perovskite battery comprises a plurality of laser processed regions a connected in sequence in its length direction, and the perovskite battery comprises a plurality of sub-battery units 1 arranged at intervals in its width direction, and any two adjacent sub-battery units 1 are connected by a connecting portion 2, and each of the sub-battery units 1 and each of the connecting portions 2 comprises a transparent base layer 3, a bottom electrode layer 4, a hole transport layer 5, a light absorption layer 6, an electron transport layer 7 and a top electrode layer 8 arranged in a stacked manner;

[0082] A first etching line 9 is formed on the bottom electrode layer 4 of the connecting portion 2, and the first etching line 9 is used to separate the bottom electrode layers 4 of two adjacent sub-battery units 1. A conductive material 10 is also provided on the connecting portion 2, and the position of the conductive material 10 and the position of the first etching line 9 are offset in the width direction of the perovskite battery. The conductive material 10 penetrates the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, and the hole transport layer 5 of the connecting portion 2, and the conductive material 10 is used to electrically connect the top electrode layer 8 of one of the two adjacent sub-battery units 1 and the bottom electrode layer 4 of the other;

[0083] Specifically, the perovskite cell is divided into multiple laser processing areas a along its length, which represent the range that the laser equipment can process in one operation. This division is due to the limitation of the laser equipment worktable, and multiple processing is required to complete the production of the entire cell.

[0084] Both the sub-battery unit 1 and the connecting portion 2 have a transparent base layer 3, a bottom electrode layer 4, a hole transport layer 5, a light absorbing layer 6, an electron transport layer 7 and a top electrode layer 8. The length of each sub-battery unit 1 is the same as the length of the connecting portion 2, and both extend from the initial laser processing area a to the terminal laser processing area a.

[0085] Sub-cells 1 are the effective areas where photoelectric conversion actually takes place in perovskite thin-film cells. In these areas, the functional layers work together to convert light energy into electrical energy. Each sub-cell 1 is a relatively independent photovoltaic unit that can generate a certain voltage and current.

[0086] The connection part 2 refers to the transition area between adjacent sub-battery units 1. Although the connection part 2 has the same layered structure as the sub-battery unit 1, its main function is to achieve electrical connection and isolation between adjacent sub-battery units 1. In the connection part 2, some special structures such as the first etching line 9 and the conductive material 10 play a key role. The first etching line 9 is used to separate the bottom electrode layer 4 of adjacent sub-battery units 1, and the conductive material 10 is used to electrically connect the top electrode layer 8 of one sub-battery unit 1 with the bottom electrode layer 4 of the adjacent sub-battery unit 1, thereby achieving series connection.

[0087] S2, performing line etching on the connecting portion 2 in the laser processing area a to form a second etching line 11 penetrating the top electrode layer 8, the electron transport layer 7, the light absorption layer 6 and the hole transport layer 5 of the connecting portion 2, wherein the second etching line 11 is located on a side of the conductive material 10 facing away from the first etching line 9;

[0088] Specifically, this process is carried out in each laser processing area a, using precision laser equipment to perform precise linear etching on the connection part 2. The laser beam is precisely controlled to ensure that the etching depth just penetrates the top electrode layer 8, the electron transport layer 7, the light absorption layer 6 and the hole transport layer 5, but does not damage the bottom electrode layer 4 at the bottom. This precise control is essential to maintaining the overall structural integrity of the battery. The position of the second etching line 11 is precisely positioned on the side of the conductive material 10 facing away from the first etching line 9. This layout design effectively isolates the adjacent sub-battery units 1 electrically while maintaining the series connection between them through the conductive material 10. For example, in a typical perovskite cell, if the first etching line 9 is located on the left side of the connection part 2, then the second etching line 11 will be precisely positioned on the right side of the connection part 2, and the conductive material 10 is located between the two etching lines. This precise spatial layout ensures that the current can flow from one sub-battery unit 1 to the next along a predetermined path, thereby achieving an efficient series structure.

[0089] S3, performing point etching at the intersection of adjacent laser processing areas a to form an etching hole 12 penetrating the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, the hole transport layer 5 and the bottom electrode layer 4 of the connecting portion 2, wherein the diameter of the etching hole 12 is greater than or equal to the width of the connecting portion 2. Specifically, the etching hole 12 is less than twice the width of the connecting portion 2;

[0090] Among them, after step S1, the process is performed in a preset first manner or a second manner. The first manner is to perform step S3 after completing step S2 for all laser processing areas a; the second manner is to perform step S3 at the intersection of the laser processing area a and the adjacent laser processing area a after completing step S2 for the first laser processing area a, and then perform step S2 for the next laser processing area a, and then perform step S3 at the new adjacent intersection, and alternately perform steps S2 and S3 until all laser processing areas a are processed.

[0091] It can be understood that the method for manufacturing a perovskite thin film battery of the technical solution of the present invention performs point etching at the intersection of adjacent laser processing areas a to form an etching hole 12 that runs through the top electrode layer 8, electron transport layer 7, light absorption layer 6, hole transport layer 5 and bottom electrode layer 4 of the entire connecting portion 2, thereby ensuring that the top electrode layer 8 of adjacent sub-battery units 1 is completely separated at the intersection. The introduction of this point etching technology effectively avoids the possible misalignment or discontinuity of the scribing, thereby preventing the top electrode layer 8 of adjacent sub-battery units 1 from maintaining unnecessary electrical connections at certain points. Secondly, by designing the diameter of the etching hole 12 to be greater than or equal to the width of the connecting portion 2, the method further ensures that the etching hole 12 can completely cover the connecting portion 2 area and completely cut off any residual electrical connection that may exist. This design not only ensures effective isolation between the sub-battery units 1, but also improves the stability and reliability of the entire battery structure.

[0092] In addition, the flexibility of the method of the present invention is reflected in that it provides two optional manufacturing methods. The first method is suitable for large-scale batch production by first completing the line etching of all laser processing areas a, and then performing point etching; the second method adopts a strategy of alternating line etching and point etching, which is more suitable for small batch or customized production. The combination of these two methods enables the method to adapt to different production needs and equipment conditions. In particular, in the second method, point etching is performed immediately after completing the line etching of each laser processing area a. This instant processing method can better control the accuracy of each processing step, and can promptly discover and correct possible problems. In this way, the method not only solves the problem of discontinuous scribing, but also improves the controllability of the entire manufacturing process and the consistency of the product. In general, the method of the present invention effectively improves the manufacturing accuracy and product quality of perovskite thin film batteries through a carefully designed etching process and a flexible manufacturing strategy, and provides reliable technical support for the large-scale production of large-area, high-performance perovskite thin film batteries.

[0093] In some embodiments, when the first method is adopted, S3 includes:

[0094] S31a, scanning the intersection of adjacent laser processing areas a to obtain structural information of the connecting portion 2 at the intersection, wherein the structural information includes position and size data of the first etching line 9, the conductive material 10, and the second etching line 11;

[0095] Specifically, the intersection of adjacent laser processing areas a is scanned using a multi-mode scanning technique that combines surface three-dimensional profile scanning and internal structure scanning. The surface three-dimensional profile scanning uses a high-resolution laser triangulation system that emits a laser beam and captures the reflected light through a CCD camera to accurately measure surface height changes. This method can capture micron-level surface details, including the precise position and morphology of the second etching line 11. At the same time, the internal structure scan uses optical coherence tomography (OCT) technology, which uses the interference principle of near-infrared light to non-destructively "see through" the surface structure and obtain internal structure information up to a depth of several hundred microns. OCT technology is particularly suitable for detecting the position and shape of the first etching line 9 and the conductive material 10, because these structures are often covered by upper materials.

[0096] In actual operation, the scanning process first performs a quick pre-scan of the entire intersection area to determine the approximate location of the key structure. For example, when locating the first etching line 9, the OCT system will perform a fine scan near the bottom electrode layer 4 and determine the precise position and width of the etching line by analyzing the intensity change of the reflected signal. For the conductive material 10, the three-dimensional distribution map of the conductive material 10 is accurately drawn by combining the surface profile and internal structure data. The second etching line 11 is mainly determined by surface profile scanning.

[0097] The entire scanning process is controlled by a computer, and a real-time data processing algorithm is used to complete a comprehensive scan of an intersection area within a few seconds. After filtering, calibration and 3D reconstruction, the raw data obtained by the scan forms a high-precision digital model, which includes detailed 3D spatial distribution data of the first etching line 9, the conductive material 10 and the second etching line 11.

[0098] The beneficial effects of this high-precision scanning method are mainly reflected in the following aspects: First, it provides accurate three-dimensional data of the intersection structure, which provides a reliable basis for subsequent point etching operations, ensures the accuracy of the etching position, and effectively avoids processing errors caused by inaccurate positioning. Secondly, by obtaining internal structural information, especially the precise position of the first etching line 9 and the conductive material 10, the pertinence and effectiveness of subsequent processing are greatly improved. Furthermore, this non-contact scanning method will not cause any damage to the battery structure, ensuring the integrity of the sample.

[0099] S32a, forming a mask pattern for etching holes 12 on the top electrode layer 8 based on the acquired structural information;

[0100] In this embodiment, the S32a includes:

[0101] S321a, determining the boundary of each of the connecting parts 2 on the top electrode layer 8 based on the acquired structural information;

[0102] Specifically, the process first identifies the positions of the first etching line 9 and the second etching line 11, because these two lines define the minimum boundary of the connection part 2. Specifically, by analyzing the three-dimensional data obtained by scanning, the position of the first etching line 9 on the bottom electrode layer 4 is accurately located, and then this position is projected onto the top electrode layer 8. At the same time, the second etching line 11 is directly located on the top electrode layer 8. The area between these two lines is the core area of ​​the connection part 2.

[0103] In actual operation, for example, when processing a standard perovskite thin film battery, a high-precision two-dimensional coordinate system is first established on the surface of the top electrode layer 8. Then, along the projected path of the first etching line 9 and the actual path of the second etching line 11, a series of coordinate points are marked on the top electrode layer 8. These points constitute the two parallel sides of the minimum boundary of the connecting part 2. Then, vertical lines are connected at both ends of these two lines to form a rectangular area, which accurately defines the minimum boundary of the connecting part 2 on the top electrode layer 8.

[0104] S322a, calculating the center position and diameter of the etching hole 12 within the boundary of each connecting portion 2;

[0105] Specifically, based on the previously determined boundary information of the connection part 2, the geometric center of the connection part 2 is calculated. This calculation process is completed by taking the intersection of the diagonals of the rectangular boundary of the connection part 2, which represents the geometric center of the connection part 2 area and is regarded as the initial center position of the etching hole 12.

[0106] Next, consider the specific positions and distribution of the first etching line 9, the conductive material 10 and the second etching line 11. If the distribution of these structures in the connecting portion 2 is not completely symmetrical, the initial center point needs to be adjusted to ensure that the etching hole 12 can cover all key structures to the greatest extent.

[0107] The calculation of the diameter of the etched hole 12 is directly based on the width of the connecting portion 2. Since the diameter of the etched hole 12 should be greater than or equal to the width of the connecting portion 2. Therefore, the maximum width of the connecting portion 2 is measured and this value is set as the minimum diameter of the etched hole 12. In order to ensure complete coverage, the diameter is usually set slightly larger, such as 0.2-0.5 microns more than the width of the connecting portion 2.

[0108] In actual operation, multiple possible etching hole 12 configurations are calculated and the effect of each configuration is evaluated. The evaluation criteria include the coverage of the first etching line 9, the conductive material 10 and the second etching line 11, as well as the potential impact on adjacent areas. Finally, a configuration is selected that can maximize the coverage of the critical structure while minimizing the impact on adjacent areas.

[0109] This method of accurately calculating the position and size of the etching hole 12 ensures that the etching hole 12 can completely cover all key structures of the connecting part 2, effectively isolating unnecessary electrical connections between adjacent sub-battery units 1. By precisely controlling the position and size of the etching hole 12, interference with adjacent functional areas is minimized, ensuring the overall performance of the battery. This method takes into account the slight deviations that may exist in the actual manufacturing process, improving the fault tolerance and yield rate of production. Finally, this precise calculation provides clear parameters for the subsequent laser etching process, which helps to improve the accuracy and consistency of the etching process.

[0110] S323a, marking a circular etching area on the top electrode layer 8 according to the calculated center position and diameter;

[0111] S324a, applying a local electric field around the circular etching area;

[0112] Specifically, using the previously calculated center coordinates, an accurate point is determined on the top electrode layer 8. This point becomes the center of the circular etching area. Then, with this center point as the center of the circle and half of the calculated diameter value as the radius, an accurate circle is drawn on the top electrode layer 8. This circular area is the predetermined etching area, which accurately defines the range of material to be removed in the subsequent etching process.

[0113] After marking the circular etched area, the next step is to apply a local electric field around this area. This process involves placing specially designed electrodes around the edges of the circular area. These electrodes are usually arranged in a ring, completely surrounding the circular etched area. When a voltage is applied to these electrodes, a local electric field of controllable strength is generated around the circular area.

[0114] S325a, spraying charged photosensitive material particles toward the periphery of the circular etching area, so that the photosensitive material particles are deposited on the top electrode layer 8 to form an annular distribution structure centered on the circular etching area;

[0115] In this embodiment, S325a includes: dissolving the photosensitive material in an organic solvent to prepare a precursor solution; using a piezoelectric nozzle to atomize the precursor solution into charged droplets; spraying the charged droplets around the circular etching area, and during the flight of the droplets, evaporating the solvent through an infrared heater, and at the same time using the local electric field to accelerate and orient the charged particles to form solid photosensitive material particles; by adjusting the intensity distribution of the local electric field and the spraying angle of the piezoelectric nozzle, the deposition of solid photosensitive material particles on the top electrode layer 8 is controlled to form an annular distribution structure centered on the circular etching area.

[0116] Specifically, an appropriate photosensitive material is selected, usually a positive photoresist that is sensitive to ultraviolet light, and dissolved in a specific organic solvent, such as propylene glycol methyl ether acetate. The dissolution process requires precise control of temperature and stirring speed to ensure that the photosensitive material is completely dissolved and forms a uniform solution. This solution is the so-called precursor solution, and its concentration and viscosity directly affect the subsequent atomization and deposition effects.

[0117] Next, a high-precision piezoelectric nozzle is used to atomize the precursor liquid into charged droplets. The working principle of the piezoelectric nozzle is to use the rapid deformation of piezoelectric materials under the action of voltage to produce tiny droplets. By precisely controlling the voltage waveform applied to the piezoelectric material, the droplet size and injection frequency can be precisely adjusted. This method can produce uniform droplets with a diameter of the order of micrometers, laying the foundation for subsequent precise deposition.

[0118] Spraying charged droplets around the circular etching area is a process that requires precise control. During the spraying process, the flight trajectory of the droplets is affected by multiple factors, including initial velocity, gravity, and air resistance. In order to ensure that the droplets land accurately at the target location, the position, angle, and spray parameters of the nozzle need to be precisely adjusted. At the same time, an infrared heater is used to heat the flight path during the flight of the droplets. This heating process causes the organic solvent to evaporate rapidly, converting the liquid droplets into solid photosensitive material particles. The temperature and power of the infrared heater need to be precisely controlled to ensure that the solvent evaporates completely without causing thermal damage to the photosensitive material itself.

[0119] While the droplets are flying and evaporating, a pre-applied local electric field is used to accelerate and orient the charged particles. This local electric field is generated by an annular electrode arranged around the circular etching area. The intensity and distribution of the electric field are carefully designed to exert a precise electromagnetic force on the charged particles. This force can both accelerate the movement of the particles and improve deposition efficiency, and precisely control the direction of the particles to ensure that they land exactly at the intended location.

[0120] By adjusting the intensity distribution of the local electric field and the spray angle of the piezoelectric nozzle, precise control of the deposition process of solid-state photosensitive material particles is achieved. The electric field intensity is adjusted by changing the voltage applied to the annular electrode, while the spray angle is adjusted by a precise mechanical system. The coordinated adjustment of these two parameters enables precise control of the landing point and distribution density of the particles. In this way, an annular distribution structure centered on the circular etching area is finally formed on the top electrode layer 8. The inner diameter of this annular structure is equal to the diameter of the circular etching area, while the outer diameter is adjusted as needed, usually 0.5μm to 10μm larger than the inner diameter.

[0121] This embodiment achieves highly accurate deposition of photosensitive material particles, ensuring that the formed mask pattern accurately matches the expected etching area. Secondly, by controlling the size and distribution of the particles, a mask layer with a specific thickness and edge profile can be formed, which is crucial for the subsequent etching process. Furthermore, this method is highly flexible and controllable and can adapt to etching requirements of different sizes and shapes. Finally, due to the use of precise atomization and electric field control technology, this method greatly improves material utilization efficiency, reduces waste generation, and meets the environmental protection requirements of modern manufacturing processes.

[0122] S326a, selectively exposing the deposited photosensitive material particles using an ultraviolet light source to form a solidified pattern corresponding to the circular etching area;

[0123] S327a, cleaning the uncured photosensitive material with a developer, so that the cured pattern forms a mask pattern of the etching hole 12 on the top electrode layer 8.

[0124] Specifically, a high-precision UV light source is first used, usually a mercury lamp or LED light source with a wavelength of about 365nm. This light source can provide stable and uniform UV light to ensure the consistency of the exposure process. Selective exposure is achieved by using a mask. This mask contains a pattern that exactly corresponds to the circular etching area. The mask is made of quartz glass and is covered with a precise chrome pattern. When UV light is irradiated through this mask onto the deposited photosensitive material particles, only specific areas of the photosensitive material will receive UV light.

[0125] For positive photoresists, a chemical reaction occurs in the areas exposed to UV light, causing the photosensitive material in these areas to become soluble in the developer. The areas not exposed to light remain unchanged and insoluble in the developer. This selective exposure creates a latent pattern that exactly corresponds to the circular etched area. The timing and intensity of the exposure process need to be precisely controlled. Overexposure may result in blurred edges or dimensional deviations of the pattern, while underexposure may result in some areas not being fully reacted.

[0126] After exposure, the next step is to clean the uncured photosensitive material with a developer. The choice of developer needs to match the photosensitive material used. Commonly used developers include aqueous solutions of potassium hydroxide or tetramethylammonium hydroxide. When the exposed sample is immersed in the developer, the areas that have been exposed to UV light will quickly dissolve, while the areas that have not been exposed will remain unchanged.

[0127] The time and temperature of the development process also need to be precisely controlled. If the development time is too short, some of the material that should be dissolved may remain, while if the time is too long, the pattern may be over-corroded, affecting the accuracy. Usually, the development process is carried out under constant temperature conditions, supplemented by slight mechanical agitation to ensure uniform development.

[0128] After development, the sample is rinsed thoroughly with deionized water to stop the development reaction and remove the residual developer. The sample is then dried, usually by nitrogen blowing or low-temperature drying, to avoid introducing impurities or causing pattern deformation.

[0129] The advantages of this embodiment are its high precision and repeatability. By precisely controlling the exposure and development process, submicron pattern accuracy can be achieved. At the same time, it is suitable for large-area processing, which is conducive to improving production efficiency. In addition, since the entire process does not involve high temperature or highly corrosive chemicals, the damage to the battery structure is minimal, which helps to maintain the overall performance of the perovskite thin film battery.

[0130] S33a, setting laser spot etching parameters according to the mask pattern, including laser power, pulse frequency and scanning path;

[0131] S34a, etching is performed using the set laser spot etching parameters to form an etching hole 12 that penetrates the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, the hole transport layer 5 and the bottom electrode layer 4 of the connecting portion 2.

[0132] Specifically, the setting of laser power directly affects the depth and efficiency of etching. For multi-layer structures such as perovskite thin-film cells, the laser power needs to be precisely controlled to ensure that it can penetrate all target layers without damaging the bottom transparent base layer 3. Usually, a step-by-step power setting is adopted, that is, the power is gradually increased during the etching process to adapt to the etching characteristics of different material layers.

[0133] The setting of pulse frequency affects the material removal rate and the size of the heat-affected zone. High frequency can improve processing efficiency, but may increase heat accumulation; low frequency can reduce heat effects, but will extend processing time. Therefore, it is necessary to optimize the pulse frequency according to the thermal sensitivity and thickness of each layer of material.

[0134] The design of the scanning path is the key to ensure etching uniformity and accuracy. A spiral or concentric scanning path is usually used, expanding outward from the center of the etching area. This path design helps reduce heat accumulation and ensures smoothness of the etching edge.

[0135] The actual etching is performed using the set laser spot etching parameters. This process uses a high-precision laser system, usually a femtosecond or picosecond pulsed laser. The laser beam moves along a preset scanning path, removing material layer by layer. The etching process starts from the top electrode layer 8, passes through the electron transport layer 7, the light absorption layer 6, the hole transport layer 5, and finally reaches the bottom electrode layer 4.

[0136] The entire etching process needs to be precisely controlled to ensure consistent etching depth. Real-time monitoring systems, such as optical interferometers or plasma emission spectrometers, are usually used to monitor the etching depth. These systems can detect the interface of different material layers to accurately control the etching endpoint.

[0137] During the etching process, the uniformity of material removal also needs to be considered. Different material layers may have different laser absorption characteristics and etching thresholds, so it may be necessary to dynamically adjust the laser parameters during the etching process to ensure that each layer is removed uniformly.

[0138] The finally formed etching hole 12 penetrates all functional layers of the connecting part 2, namely, the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, the hole transport layer 5 and the bottom electrode layer 4. The shape and size of the etching hole 12 are highly consistent with the mask pattern, and are usually cylindrical or slightly conical.

[0139] In the above embodiment, preferably, the photosensitive material is a positive photoresist, and the organic solvent is propylene glycol methyl ether acetate.

[0140] The piezoelectric nozzle has a spraying frequency of 1 kHz to 100 kHz, and a sprayed charged droplet has a diameter of 1 μm to 50 μm.

[0141] The temperature of the infrared heater is 50°C to 200°C.

[0142] The intensity of the local electric field is 0.1 kV / cm to 10 kV / cm.

[0143] The inner diameter of the annular distribution structure is equal to the diameter of the circular etching area, and the outer diameter of the annular distribution structure is 0.5 μm to 10 μm greater than the inner diameter of the annular distribution structure.

[0144] In some other embodiments, when the second method is adopted, S3 includes:

[0145] S31b, calculating the optimal etching hole 12 position and size based on the end position of the second etching line 11 of the laser processing area a where the line etching has been completed, the position of the first etching line 9, the position of the conductive material 10, and the expected second etching line 11 position of the next laser processing area a;

[0146] Specifically, a two-dimensional coordinate system is established based on the acquired precise position data of the end of the second etching line 11, the first etching line 9 and the conductive material 10. In this system, the end of the second etching line 11 of the current laser processing area a is used as a reference point, and its coordinates are set to (0, 0). Then, the edge contours of the first etching line 9 and the conductive material 10 are fitted using the least squares method to obtain their precise mathematical expressions in the coordinate system. Next, the starting position of the second etching line 11 of the next laser processing area a is predicted by an extrapolation algorithm, which is usually based on the linear extrapolation of the current processing area and the overall battery design parameters. With these basic data, an iterative optimization algorithm is started. The algorithm first sets the center of the initial etching hole 12 at the midpoint between the end of the current second etching line 11 and the predicted starting point of the next second etching line 11. Then, the position of this center point is gradually adjusted, and a coverage index is calculated after each adjustment, which reflects the degree of coverage of the etching hole 12 on the first etching line 9, the conductive material 10 and the second etching lines 11 at both ends. At the same time, considering the manufacturing tolerance, an error range is added to the calculation, usually ±5 microns. The optimization process continues until a position is found that maximizes the coverage index. For the calculation of the size of the etched hole 12, the width of the connecting portion 2 is first taken as the minimum diameter, and then the diameter is gradually increased, while evaluating the impact of the increased size on the surrounding structure. This process uses the Monte Carlo simulation method to simulate thousands of different manufacturing scenarios to ensure that the selected size remains effective under various possible manufacturing errors. Ultimately, a diameter value is selected that minimizes the impact on the surrounding structure while ensuring full coverage of the necessary area. This calculation method not only ensures the precise positioning and appropriate size of the etched hole 12, but also improves the robustness and reliability of the entire manufacturing process by considering multiple factors and possible changes.

[0147] S32b, performing point etching at the calculated optimal etching hole 12 position to form a main etching hole 12 that penetrates the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, the hole transport layer 5 and the bottom electrode layer 4 of the connecting portion 2;

[0148] Specifically, the laser is focused on the calculated optimal position. Then, by controlling the power, pulse width and repetition frequency of the laser, each layer of the connecting part 2 is etched layer by layer. The etching process starts from the top electrode layer 8, passes through the electron transport layer 7, the light absorption layer 6, the hole transport layer 5, and finally reaches the bottom electrode layer 4. During the whole process, the laser parameters are dynamically adjusted according to the material properties of different layers to ensure the accuracy and uniformity of etching. At the same time, a real-time monitoring system, such as an optical interferometer, is used to control the etching depth to ensure that the etching hole 12 completely penetrates all target layers without damaging the transparent base layer 3 at the bottom.

[0149] S33b. Local etching is performed on the peripheral wall of the main etching hole 12 on the side adjacent to the next laser processing area a to form a secondary etching hole 12. The secondary etching hole 12 penetrates the top electrode layer 8, the electron transport layer 7 and the light absorption layer 6. The central axis of the secondary etching hole 12 intersects with the central axis of the expected second etching line 11 of the next laser processing area a.

[0150] In this embodiment, the S33b includes:

[0151] S331b, based on the direction of the completed second etching line 11, extending the track of the completed second etching line 11 in the main etching hole 12;

[0152] Specifically, computer-aided design (CAD) software is used to analyze the direction of the completed second etching line 11. By accurately positioning the end point of the second etching line 11 and calculating the direction vector, the trajectory of the second etching line 11 is extended to the inside of the main etching hole 12 in the virtual environment. This extension process takes into account the curvature and direction of the second etching line 11 to ensure that the extended trajectory remains consistent with the original trajectory.

[0153] S332b, determining the intersection point between the track and the peripheral wall of the main etching hole 12, and taking the intersection point as the center of the auxiliary etching hole 12;

[0154] A geometric calculation algorithm is used to determine the precise intersection of the extended trajectory with the peripheral wall of the main etching hole 12. This involves solving the intersection equation of a straight line (or curve) and a circle. The calculated intersection coordinates are recorded and set as the center position of the secondary etching hole 12.

[0155] S333b, forming a secondary etching hole 12 on the peripheral wall of the main etching hole 12 with the center of the secondary etching hole 12 as a reference.

[0156] Based on the determined center of the secondary etching hole 12, a precision laser system is used to perform local etching on the peripheral wall of the main etching hole 12. This process usually uses a femtosecond laser to accurately form the secondary etching hole 12 on the peripheral wall by controlling the laser power, pulse width and repetition frequency. The laser parameters are optimized and adjusted according to the material properties and the required etching depth.

[0157] The auxiliary etching hole 12 provides a precise starting point for the second etching line 11 of the next laser processing area a, ensuring seamless connection between adjacent processing areas and greatly improving connection accuracy.

[0158] In some embodiments, the diameter of the etching hole 12 is less than 1 mm. This tiny size design ensures that the etching hole 12 can accurately cover the area of ​​the connecting portion 2, effectively isolating adjacent sub-battery units 1, while minimizing the impact on the overall battery structure. Since perovskite thin-film batteries are usually composed of multiple sub-battery units 1 connected in series, the width of each unit is usually in the range of several millimeters to several centimeters, and the etching hole 12 less than 1 mm is extremely small relative to the area of ​​the entire sub-battery unit 1. This means that the effective power generation area occupied by the etching hole 12 is negligible, and the overall photoelectric conversion efficiency of the battery is minimal.

[0159] In addition, such tiny etched holes 12 help maintain the mechanical strength and structural integrity of the battery. Larger holes may cause local weakening of the film structure and increase the risk of cracks or delamination, especially in flexible battery applications. Etched holes 12 smaller than 1 mm can maximize the continuity and strength of the film. At the same time, etched holes 12 of this size are also beneficial in reducing the penetration of moisture and oxygen, improving the long-term stability and service life of the battery.

[0160] From a manufacturing perspective, the size of the etching hole 12 less than 1 mm provides greater room for error tolerance in the manufacturing process. Even if there is a slight position deviation during the processing, it will not significantly affect the function and performance of the battery. This design increases the robustness of the manufacturing process and is conducive to improving the yield and consistency of the product.

[0161] The present invention also provides a perovskite thin film battery, which is prepared by the above-mentioned method for manufacturing a perovskite thin film battery, wherein the perovskite thin film battery comprises a perovskite battery, wherein the perovskite battery comprises a plurality of laser processing regions a sequentially connected in its length direction, wherein the perovskite battery comprises a plurality of sub-battery units 1 arranged at intervals in its width direction, wherein any two adjacent sub-battery units 1 are connected by a connecting portion 2, and each of the sub-battery units 1 and each of the connecting portions 2 comprises a transparent base layer 3, a bottom electrode layer 4, a hole transport layer 5, a light absorption layer 6, an electron transport layer 7 and a top electrode layer 8 which are stacked;

[0162] A first etching line 9 is formed on the bottom electrode layer 4 of the connecting portion 2, and the first etching line 9 is used to separate the bottom electrode layers 4 of two adjacent sub-battery units 1. A conductive material 10 is also provided on the connecting portion 2, and the position of the conductive material 10 and the position of the first etching line 9 are offset in the width direction of the perovskite battery. The conductive material 10 penetrates the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, and the hole transport layer 5 of the connecting portion 2, and the conductive material 10 is used to electrically connect the top electrode layer 8 of one of the two adjacent sub-battery units 1 and the bottom electrode layer 4 of the other;

[0163] A second etching line 11 is formed on the connecting portion 2 and passes through the top electrode layer 8, the electron transport layer 7, the light absorption layer 6 and the hole transport layer 5 of the connecting portion 2. An etching hole 12 is formed at the intersection of any two adjacent laser processing areas a and passes through the top electrode layer 8, the electron transport layer 7, the light absorption layer 6, the hole transport layer 5 and the bottom electrode layer 4 of the connecting portion 2. The etching holes 12 are respectively connected to the second etching lines 11 of the two adjacent laser processing areas a.

[0164] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification and drawings under the inventive concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for manufacturing a perovskite thin film battery, characterized in that: include: S1. Provide a perovskite cell, wherein the perovskite cell comprises a plurality of laser processing areas sequentially connected in the length direction thereof, wherein the laser processing area is a range that can be processed by the laser device in one operation, and wherein the perovskite cell comprises a plurality of sub-cells spaced apart in the width direction thereof, wherein any two adjacent sub-cells are connected by a connecting portion, and each of the sub-cells and each of the connecting portions comprises a transparent base layer, a bottom electrode layer, a hole transport layer, a light absorption layer, an electron transport layer and a top electrode layer that are stacked; A first etching line is formed on the bottom electrode layer of the connecting portion, and the first etching line is used to separate the bottom electrode layers of two adjacent sub-battery units. A conductive material is also provided on the connecting portion, and the location of the conductive material and the location of the first etching line are offset in the width direction of the perovskite battery. The conductive material penetrates the top electrode layer, the electron transport layer, the light absorption layer, and the hole transport layer of the connecting portion, and the conductive material is used to electrically connect the top electrode layer of one of the two adjacent sub-battery units and the bottom electrode layer of the other; S2, performing line etching on the connecting portion in the laser processing area to form a second etching line that penetrates the top electrode layer, the electron transport layer, the light absorption layer and the hole transport layer of the connecting portion, wherein the second etching line is located on a side of the conductive material that is away from the first etching line; S3, performing point etching at the intersection of adjacent laser processing areas to form an etching hole that penetrates the top electrode layer, the electron transport layer, the light absorption layer, the hole transport layer and the bottom electrode layer of the connecting portion, wherein the diameter of the etching hole is greater than or equal to the width of the connecting portion; Among them, after step S1, the process is performed in a preset first manner or a second manner. The first manner is to perform step S3 after completing step S2 for all laser processing areas. The second manner is to perform step S3 at the intersection of the laser processing area and the adjacent laser processing area after completing step S2 for the first laser processing area, and then perform step S2 for the next laser processing area, and then perform step S3 at the new adjacent intersection, and alternately perform steps S2 and S3 until all laser processing areas are processed.

2. The method for manufacturing a perovskite thin film battery according to claim 1, characterized in that: When the first method is adopted, S3 includes: S31a, scanning the intersection of adjacent laser processing areas to obtain structural information of the connection portion of the intersection, wherein the structural information includes position and size data of the first etching line, the conductive material, and the second etching line; S32a, forming a mask pattern for etching holes on the top electrode layer based on the acquired structural information; S33a, setting laser spot etching parameters according to the mask pattern, including laser power, pulse frequency and scanning path; S34a, performing etching using set laser spot etching parameters to form etching holes that penetrate the top electrode layer, the electron transport layer, the light absorption layer, the hole transport layer and the bottom electrode layer of the connecting portion.

3. The method for manufacturing a perovskite thin film battery according to claim 2, characterized in that: The S32a includes: S321a, determining the boundary of each of the connecting parts on the top electrode layer based on the acquired structural information; S322a, calculating the center position and diameter of the etching hole within the boundary of each connecting portion; S323a, marking a circular etching area on the top electrode layer according to the calculated center position and diameter; S324a, applying a local electric field around the circular etching area; S325a, spraying charged photosensitive material particles toward the periphery of the circular etching area, so that the photosensitive material particles are deposited on the top electrode layer to form an annular distribution structure centered on the circular etching area; S326a, selectively exposing the deposited photosensitive material particles using an ultraviolet light source to form a solidified pattern corresponding to the circular etching area; S327a, cleaning the uncured photosensitive material with a developer, so that the cured pattern forms a mask pattern of etching holes on the top electrode layer.

4. The method for manufacturing a perovskite thin film battery according to claim 3, characterized in that: The S325a includes: Dissolving a photosensitive material in an organic solvent to prepare a precursor solution; Atomizing the precursor liquid into charged droplets using a piezoelectric nozzle; The charged droplets are sprayed around the circular etching area, and during the flight of the droplets, the solvent is evaporated by an infrared heater, and the charged particles are accelerated and oriented by the local electric field to form solid photosensitive material particles; By adjusting the intensity distribution of the local electric field and the spray angle of the piezoelectric nozzle, the solid photosensitive material particles are controlled to be deposited on the top electrode layer to form an annular distribution structure centered on the circular etching area.

5. The method for manufacturing a perovskite thin film battery according to claim 4, characterized in that: The photosensitive material is a positive photoresist, and the organic solvent is propylene glycol methyl ether acetate; and / or, The piezoelectric nozzle has a spraying frequency of 1 kHz to 100 kHz, and a diameter of the sprayed charged droplets is 1 μm to 50 μm; and / or, The temperature of the infrared heater is 50°C to 200°C; and / or, The intensity of the local electric field is 0.1 kV / cm to 10 kV / cm; and / or, The inner diameter of the annular distribution structure is equal to the diameter of the circular etching area, and the outer diameter of the annular distribution structure is 0.5 μm to 10 μm greater than the inner diameter of the annular distribution structure.

6. The method for manufacturing a perovskite thin film battery according to claim 1, characterized in that: When the second method is adopted, S3 includes: S31b, calculating the optimal etching hole position and size based on the second etching line end position of the laser processing area where the line etching has been completed, the first etching line position, the conductive material position, and the expected second etching line position of the next laser processing area; S32b, performing point etching at the calculated optimal etching hole position to form a main etching hole that penetrates the top electrode layer, the electron transport layer, the light absorption layer, the hole transport layer and the bottom electrode layer of the connecting portion; S33b. Perform local etching on the peripheral wall of the main etching hole on a side adjacent to the next laser processing area to form a secondary etching hole, wherein the secondary etching hole penetrates the top electrode layer, the electron transport layer and the light absorbing layer, and the central axis of the secondary etching hole intersects with the central axis of the expected second etching line of the next laser processing area.

7. The method for manufacturing a perovskite thin film battery according to claim 6, characterized in that: The S33b includes: S331b, based on the direction of the completed second etching line, extending the track of the completed second etching line in the main etching hole; S332b, determining the intersection point between the track and the peripheral wall of the main etching hole, and taking the intersection point as the center of the auxiliary etching hole; S333b, taking the center of the secondary etching hole as a reference, forming a secondary etching hole on the peripheral wall of the main etching hole.

8. The method for manufacturing a perovskite thin film battery according to claim 1, characterized in that: The diameter of the etching hole is less than 1 mm.

9. A perovskite thin film battery, characterized in that: The perovskite thin film battery is manufactured by the manufacturing method of any one of claims 1 to 8, wherein the perovskite thin film battery comprises a perovskite battery, the perovskite battery comprises a plurality of laser processing regions sequentially connected in its length direction, the perovskite battery comprises a plurality of sub-battery units spaced apart in its width direction, any two adjacent sub-battery units are connected by a connecting portion, and each of the sub-battery units and each of the connecting portions comprises a transparent base layer, a bottom electrode layer, a hole transport layer, a light absorption layer, an electron transport layer and a top electrode layer which are stacked; A first etching line is formed on the bottom electrode layer of the connecting portion, and the first etching line is used to separate the bottom electrode layers of two adjacent sub-battery units. A conductive material is also provided on the connecting portion, and the location of the conductive material and the location of the first etching line are offset in the width direction of the perovskite battery. The conductive material penetrates the top electrode layer, the electron transport layer, the light absorption layer, and the hole transport layer of the connecting portion, and the conductive material is used to electrically connect the top electrode layer of one of the two adjacent sub-battery units and the bottom electrode layer of the other; A second etching line is formed on the connecting portion, which passes through the top electrode layer, electron transport layer, light absorption layer and hole transport layer of the connecting portion. An etching hole is formed at the intersection of any two adjacent laser processing areas, which passes through the top electrode layer, electron transport layer, light absorption layer, hole transport layer and bottom electrode layer of the connecting portion. The etching holes are respectively connected to the second etching lines of the two adjacent laser processing areas.

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