Hydrophobic antireflective barrier film for perovskite thin film solar cells and method of making same

Abstract

The application belongs to the technical field of thin film packaging, and particularly relates to a hydrophobic, anti-reflection and barrier film for perovskite thin film solar cells and a preparation method thereof. The hydrophobic, anti-reflection and barrier film is a sandwich structure, comprising a flexible substrate, a water vapor barrier layer and a micro-nano structure hydrophobic and anti-reflection layer, wherein the water vapor barrier layer and the micro-nano structure hydrophobic and anti-reflection layer are arranged on two sides of the flexible substrate. The barrier film can not only improve the water vapor barrier property of the perovskite thin film solar cell after packaging, that is, the service life of the perovskite thin film solar cell, but also solve the efficiency loss of the solar cell caused by light reflection on one hand and has the effects of scratch resistance, hydrophobicity, anti-reflection and self-cleaning on the other hand. The micro-nano structure hydrophobic and anti-reflection layer can simultaneously replace the process of applying a fluorine-containing film on the perovskite thin film solar cell, which simplifies the process, improves the performance of the cell and improves the overall reliability of the barrier film.

Description

Technical Field

[0001] This invention belongs to the field of thin film encapsulation technology, specifically relating to a hydrophobic antireflection barrier film for perovskite thin film solar cells and its preparation method. Background Technology

[0002] Quantum dot films, organic photovoltaics, perovskite solar cells, quantum dot light-emitting devices, and organic electroluminescence devices have experienced rapid development in recent years. However, device lifespan remains a significant challenge in industrialization. In industrial applications, these devices need to be exposed to water and oxygen for extended periods. The organic functional materials and metal electrodes within these devices are extremely sensitive to water and oxygen, readily reacting with them and leading to performance degradation, lifespan reduction, and even failure. Therefore, encapsulation is essential to prevent direct physical damage and various chemical corrosions, particularly the severe impact of water and oxygen on device lifespan.

[0003] Currently, the water vapor barrier torque (WVTR) of barrier films used in high-end display packaging can reach 10. -6 g / m 2 The high-barrier film, used exclusively in future flexible OLED screens, is extremely expensive. Firstly, the equipment for manufacturing this film is costly. Secondly, the complex multi-layered structure of the barrier layer and the need for stable and reliable production result in very high manufacturing costs. Furthermore, in practical applications, the barrier film itself is not scratch-resistant, requiring an additional fluorine-containing coating or composite fluorine film to further reduce moisture condensation on its surface and improve scratch resistance. Summary of the Invention

[0004] To address the technical problems existing in the barrier membranes of the prior art, this invention provides a barrier membrane that is scratch-resistant, hydrophobic, anti-reflective, and self-cleaning. It combines the advantages of both barrier membranes and fluorine membranes, while also reducing light reflection and solar energy efficiency loss. Furthermore, the process is simple, the production cost is low, and the reliability is high.

[0005] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0006] This invention provides a hydrophobic anti-reflection barrier membrane, which has a sandwich structure, comprising a micro / nano structured hydrophobic anti-reflection layer, a flexible substrate, and a water vapor barrier layer.

[0007] The micro-nano structure hydrophobic antireflective layer is an array of convex hydrophobic structures, which is formed by roll-to-roll template transfer process.

[0008] The micro / nano structured hydrophobic antireflective layer uses a superhydrophobic polymer material. The advantages of this material and structure are twofold: firstly, it addresses the efficiency loss in solar cells caused by light reflection; secondly, it offers scratch resistance, hydrophobicity, antireflection, and self-cleaning properties. It can simultaneously replace the process of applying a fluorinated film to the outer layer of the solar cell encapsulation film, simplifying the process, improving cell performance, and enhancing reliability.

[0009] Flexible substrates include at least one of organic polymer materials such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI). Flexible substrates have the advantages of being lightweight, thin, and flexible, and are more suitable for encapsulating flexible solar cells.

[0010] The water vapor barrier layer is a blend of organic and inorganic nanomaterials;

[0011] The inorganic nanomaterial is at least one of silicon oxide (SiOx), silicon nitride (SiNx), and aluminum oxide (Al2O3). The organic material is SiCxHyO. Z At least one of Parylene.

[0012] The advantage of this barrier layer is that the multi-layered organic / inorganic water vapor barrier film not only has the characteristics of dense structure, chemical inertness and high chemical stability of inorganic barrier films, but also has the characteristics of flexibility and stretchability. Therefore, this water vapor barrier layer is suitable for the encapsulation of flexible solar cells, which can enable the cells to be used for a long time under bending and flexing conditions, and can ensure low water vapor and oxygen permeability.

[0013] This barrier film has a unique sandwich structure with a light transmittance of over 88% and a haze of less than 5%. It combines the advantages of hydrophobicity, anti-reflection, high barrier properties, and flexibility, which can improve the optical performance of solar cells while enhancing their stability and extending their service life.

[0014] This invention also provides a method for preparing a hydrophobic anti-reflection barrier membrane, the method comprising:

[0015] Step 1: Prepare a water vapor barrier layer. An organic layer with a thickness of 1 μm and an inorganic layer with a thickness of 30 nm-100 nm are prepared on the surface of a flexible substrate using chemical vapor deposition. Through organic / inorganic multilayer cycling, at least three organic / inorganic stacked water vapor barrier layers are obtained. The advantage of the organic layer is that it provides flexibility to the barrier film and compensates for the internal defects of the inorganic layer. However, the water vapor barrier performance of the organic layer is relatively poor (>1 g / m³). 2 / day), the thickness needs to be controlled within 1μm to eliminate the influence of moisture seepage from the side of the barrier layer. The advantage of the inorganic layer is that it provides high barrier properties for the barrier film; an inorganic layer larger than 30nm can achieve a thickness of less than 10. -2 g / m2 While the inorganic layer provides good water vapor barrier properties, the internal stress of the inorganic membrane increases with the thickness of the inorganic layer. Furthermore, some lattice and pore defects formed during the growth of the inorganic membrane do not disappear with increasing thickness. Especially when the inorganic layer thickness exceeds 100 nm, the increase in barrier properties is not significant, but the membrane becomes more prone to cracking and lacks flexibility. Therefore, an organic / inorganic laminated structure must be used. A certain thickness of organic layer can compensate for the internal defects of the inorganic layer, extend the water vapor permeation path, and further improve barrier properties and flexibility.

[0016] Step 2: Fabrication of an imprinting template for a micro / nano-structured hydrophobic antireflective layer

[0017] First, a photoresist mask layer is uniformly coated on the surface of the glass slide. The photoresist mask layer is then exposed and developed to form a photoresist mask pattern structure.

[0018] Secondly, the photolithographic mask pattern is thermally melted to form a spherical microlens structure from cylindrical photoresist pillars, which are closely arranged, forming the first-level structure. Helium ion beams are then used to locally implant the formed microstructure, creating cylindrical nanoscale papillary structures on the microlens surface, which are sparsely arranged, forming the second-level structure. This is a micro-nano hierarchical structure similar to the compound eye structure of insects, possessing scratch resistance, hydrophobicity, anti-reflection properties, and self-cleaning effects. Subsequently, high-temperature curing continues to form the photoresist micro-nano hierarchical structure pattern on the surface of the glass substrate.

[0019] Finally, through surface sensitization, silver mirror reaction and electroplating processes, the micro-nano hierarchical structure pattern on the glass substrate surface is transferred to the surface of a hard nickel plate. By splicing the nickel plates, a large-area micro-nano structure imprinted nickel template can be obtained.

[0020] Step 3: Prepare a micro-nano structure hydrophobic antireflective layer on the other side of the flexible substrate with a water vapor barrier layer. Wrap the large-area micro-nano structure imprinted nickel template obtained in Step 2 onto the surface of the imprinting machine's coating roller. Transfer the micro-nano structure to the other side of the flexible substrate with a water vapor barrier layer obtained in Step 1 through a nanoimprinting process using a superhydrophobic polymer material for surface curing to obtain a hydrophobic antireflective barrier film. The advantage of this step is that it is suitable for large-area, roll-to-roll, and mass production.

[0021] The preparation methods of superhydrophobic polymer materials include:

[0022] Mechanical blending involves mechanically mixing the hydrophobic material to be modified with the polymer material, adding a catalyst, and reacting to obtain a superhydrophobic polymer material that can be directly used in roll-to-roll nanoimprinting to obtain a micro / nano structured hydrophobic antireflective layer.

[0023] Alternatively: Surface modification, after obtaining micro-nano structures directly from polymer materials by nanoimprinting, hydrophobic materials are applied to the surface of the micro-nano structures by at least one of wet impregnation, spraying, thermal evaporation, and chemical vapor deposition.

[0024] Its advantage lies in the fact that the formation of hydrophobic micro-nano structures can prevent water vapor from adhering to and condensing on the surface of the packaged device.

[0025] The superhydrophobic polymer material is made of one of the following: hydrophobic silica, silane coupling agent, hydroxyl silicone oil, fluorosilane, or parylene; the polymer is one of the following: epoxy resin, polyurethane, or polyacrylate; and the catalyst is one of the following: dibutyltin dilaurate, stannous octoate, or monobutyltin oxide. The introduction of the catalyst can promote the hydrophobic modification of the polymer.

[0026] The mechanical blending method uses a molar ratio of hydrophobic material, polymer, and catalyst of 0.2–1.5:1:0.005–0.05.

[0027] The surface modification method involves creating a hydrophobic layer of 0.05 μm to 2 μm thickness on the surface of the micro / nano structure. This formulation allows for hydrophobic modification of the polymer without affecting its transfer performance, while the addition of a catalyst increases the reaction rate.

[0028] The structure is a micro-nano hierarchical structure, in which the diameter of the first-level micron-sized hemispherical close-packed structure is between 10 μm and 50 μm, and the diameter and height of the second-level nanopapillary structures are between 100 nm and 500 nm, with a distribution spacing between 20 nm and 1 μm. The advantage of this structure is that it is a micro-nano hierarchical structure similar to the compound eye structure of insects, and it has the effects of scratch resistance, hydrophobicity, anti-reflection and self-cleaning.

[0029] A hydrophobic antireflective barrier film structure is used to encapsulate perovskite thin-film solar cells. The encapsulated perovskite thin-film solar cell structure includes: substrate / EVA / aluminum film / POE / perovskite solar cell / POE / hydrophobic antireflective barrier film, which are integrally formed after lamination to achieve encapsulation of perovskite thin-film solar cells.

[0030] The beneficial effects of this invention are as follows: This invention introduces a hydrophobic anti-reflection layer into the barrier film, which can further and effectively prevent water vapor from condensing on the surface of the barrier film or penetrating into the inner layer of the barrier film, thereby improving the barrier performance of the barrier film; at the same time, the micro-nano structure protrusions reduce the light reflectivity of the barrier film surface, thereby increasing the light transmittance and improving the efficiency of encapsulating solar cells. On the other hand, it also increases the scratch resistance and self-cleaning effect of the barrier film, which can replace the process of applying a fluorine film to the barrier layer of perovskite thin film solar cells, simplifying the process flow. Attached Figure Description

[0031] Figure 1This is a schematic diagram of the structure of the hydrophobic antipermeability barrier membrane of Embodiment 1 of the present invention;

[0032] Figure 2 This is a top view of the structural arrangement in the micro / nano structure hydrophobic antireflective layer of Embodiment 1 of the present invention;

[0033] Figure 3 This is a flowchart of the method for manufacturing the hydrophobic anti-reflection barrier membrane according to Embodiment 2 of the present invention;

[0034] Figure 4 This is a schematic diagram of the method for manufacturing the hydrophobic anti-reflection barrier membrane according to Embodiment 2 of the present invention;

[0035] Figure 5 This is a method for encapsulating perovskite thin-film solar cells using the hydrophobic antireflection barrier film of Example 1 in Embodiment 3 of the present invention. Detailed Implementation

[0036] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention can be implemented in many different forms, and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the various embodiments of the invention and various modifications suitable for particular intended applications. In the drawings, for clarity, the shape and size of elements may be exaggerated, and the same reference numerals will always be used to denote the same or similar elements.

[0037] It will be understood that although the terms “first,” “second,” etc., may be used here to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another.

[0038] Example 1

[0039] Figure 1 This is a schematic diagram of the structure of the hydrophobic anti-reflection barrier membrane according to Embodiment 1 of the present invention.

[0040] Reference Figure 1 The first embodiment of the present invention discloses a hydrophobic anti-reflection barrier membrane structure. Specifically, the hydrophobic anti-reflection barrier membrane includes: a flexible substrate, a water vapor barrier layer disposed on one side of the flexible substrate, and a micro / nano structured hydrophobic anti-reflection layer disposed on the other side of the flexible substrate.

[0041] In one embodiment of the present invention, the water vapor barrier layer comprises an inorganic layer and an organic layer in a stacked structure, and / or a blended layer of organic polymer and inorganic nanomaterials. The inorganic and organic layers in the water vapor barrier layer are stacked on a flexible substrate, thereby ensuring the waterproof and moisture-proof properties of the water vapor barrier layer structure.

[0042] In one embodiment of the present invention, the number of moisture barrier layer groups is N, and N encapsulation layer groups are stacked. For example, the number of encapsulation layer groups is 2, and the 2 encapsulation layer groups are stacked. From bottom to top, they include a first organic layer, a first inorganic layer, a second organic layer, and a second inorganic layer. The first organic layer is disposed on the surface of the flexible substrate. A smoothing layer can be disposed between the organic layer and the flexible substrate to flatten the surface of the flexible substrate. An organic layer is disposed outside the second inorganic layer as the outermost layer of the encapsulation layer group. The organic layer provides flexibility and is also conducive to the application of an adhesive layer, resulting in better adhesion to the POE adhesive layer.

[0043] As one embodiment of the present invention, the micro-nano structure hydrophobic anti-reflective layer is composed of a micro-nano hierarchical structure similar to the compound eye structure of insects, which has the effects of scratch resistance, hydrophobicity, anti-reflective properties and self-cleaning.

[0044] In one embodiment of the present invention, the micro-nano structure hydrophobic anti-reflective layer is prepared by an imprinting template of a micro-nano structure hydrophobic anti-reflective layer.

[0045] As one embodiment of the present invention, the material used in the micro-nano structure hydrophobic anti-reflective layer is a modified hydrophobic material, and its preparation method includes mechanical blending and surface modification. This process is suitable for roll-to-roll, mass production, and large-area production.

[0046] In one embodiment of the present invention, the hydrophobic anti-reflection barrier film is made by coating a large-area micro-nano structure imprinted nickel template onto the surface of the imprinting machine coating roller, and transferring the micro-nano structure to the other side of the flexible substrate with a water vapor barrier layer through a nano-imprinting process using a superhydrophobic polymer material and then curing it to obtain the hydrophobic anti-reflection barrier film.

[0047] The hydrophobic antireflective barrier membrane of the present invention has a water vapor barrier layer that improves the barrier properties and stability of the barrier membrane. The introduction of the hydrophobic antireflective layer reduces the ability of water vapor to adhere to the surface of the barrier membrane, thereby improving the hydrophobic and anti-fogging performance. At the same time, the microstructure on the surface of the hydrophobic antireflective layer reduces the reflection of sunlight, thereby improving the efficiency of encapsulating solar cells. Therefore, it can have the effects of hydrophobicity, antireflection, high barrier properties and scratch resistance.

[0048] Example 2

[0049] In one embodiment of the present invention, the flexible substrate is made of PET.

[0050] As one embodiment of the present invention, the water vapor barrier layer is formed on the PET surface by sequentially forming an organic layer and an inorganic layer using an inductively coupled plasma-enhanced chemical vapor deposition (ICP-PECVD) device. This greatly simplifies the operation steps of the water vapor barrier layer, reduces equipment costs and shortens the processing cycle, effectively saving production costs. Furthermore, the process is carried out at low temperature (<100°C), which will not damage the substrate.

[0051] As one embodiment of the present invention, the specific method for forming the organic layer is as follows: under oxygen- and nitrogen-free conditions, 10 SCCM of hexamethyldisiloxane (HMDSO) and 20 SCCM of Ar are introduced into ICP-PECVD, wherein the ICP power is 800W and the time is 10 minutes. The organic layer SiC is formed through the pyrolysis and polymerization of the silicon precursor and the auxiliary ionization gas. x H y O Z The WVTR of the monolayer organic layer was measured to be 2.4 g / m³. 2 / day.

[0052] In one embodiment of the present invention, the specific method for fabricating the inorganic layer is as follows: O2 is introduced into the ICP-PECVD process, wherein HMDSO is 10 SCCM, Ar is 10 SCCM, O2 is 100 SCCM, the ICP power is 800 W, and the deposition time is 20 min. The inorganic layer SiOx is formed on the organic layer by utilizing the reaction between HMDSO and O2. The WVTR of the single inorganic layer is measured to be 0.038 g / m³. 2 / day.

[0053] In one embodiment of the present invention, the water vapor barrier layer structure comprises five layers of alternating organic / inorganic layers, and its WVTR is measured to be 5.7 × 10⁻⁶. -5 g / m 2 / day.

[0054] As one embodiment of the present invention, the imprint template for preparing the micro / nano structured hydrophobic antireflective layer is prepared through the following specific steps:

[0055] (1) Spin coating: Place the cleaned glass substrate into the spin coater and spin coat AZ6130 photoresist onto the glass substrate. The spin coating speed is 2000 rpm and the spin coating time is 30 s. The thickness of the photoresist layer is measured to be 3.5 μm. Then place the glass substrate coated with photoresist on a hot plate and bake at 100°C for 3 min.

[0056] (2) Exposure is performed after passing through a photomask at 100mJ / cm². 2 Exposure is performed using the appropriate exposure dose;

[0057] (3) Development: Develop the exposed substrate with Anzhi TMAH developer for 2 minutes. Finally, rinse the substrate with running deionized water for 10 seconds and then dry it with nitrogen.

[0058] (4) Hot melting: The hot melting temperature is 130℃ and the hot melting time is 2min, so as to form a photoresist microlens array structure with an aperture of 10μm and a height of 5μm, which is a primary structure.

[0059] (5) Helium plasma treatment: The photoresist plate with the primary structure is placed in a helium ion microscope. According to the shape, size, and arrangement of the microlens structure to be processed, the processing pattern is drawn in the designated area, and the corresponding parameters are set: helium ion beam energy 3keV, helium ion irradiation dose 2000 ions / nm. 2 The single-unit helium ion implantation region is a circular region with a diameter of 100 nm and a distribution spacing of 20 nm. Spherical protrusions are formed in the implantation region, creating a cylindrical nanoscale papillary structure, which is a secondary structure.

[0060] (6) Post-curing continues at 150°C to form a photoresist micro-nano structure pattern on the surface of the glass substrate;

[0061] (7) Sensitization preparation: Add 1g of stannous chloride and 1mL of hydrochloric acid to 200mL of deionized water. After pretreating the photoresist with micro-nano structure with oxygen plasma, rinse with deionized water. Then spray the prepared sensitizer on the whole surface and rinse with deionized water. Repeat the cycle three times. After that, put the photoresist in a container and add a small amount of water to cover the photoresist.

[0062] (8) Silver mirror reaction: Prepare 200 mL of 0.2 mol / L silver nitrate solution and 200 mL of 0.2 mol / L glucose solution respectively. Add ammonia solution to silver nitrate solution to form silver hydroxide precipitate first. Continue to add until the precipitation is complete. At the same time, add 20 mL of ethanol to glucose solution. Pour the treated silver nitrate solution and glucose solution into the container holding the photoresist plate and shake continuously. After reacting for 1 minute, a uniform silver mirror is formed on the photoresist plate.

[0063] (9) Electroplating: The silver-plated photoresist was placed in the electroplating solution as the cathode for electroplating. The electroplating temperature was 40℃, the electroplating current was 110A, and the electroplating time was 20min. During the electroplating process, a nickel plate was used as the anode. The electroplating solution contained nickel sulfate with a mass concentration of 330g / L, boric acid with a mass concentration of 60g / L, nickel chloride with a mass concentration of 60g / L, and a wetting agent with a volume concentration of 0.2%. Finally, an imprinted nickel template with a micro / nano structure hydrophobic antireflective layer was obtained.

[0064] In one embodiment of the present invention, the micro / nano structured hydrophobic antireflective layer uses a modified hydrophobic material, and its preparation method is mechanical blending, specifically including the following steps:

[0065] (1) Mechanically stir epoxy resin and nano-silica, and then ultrasonically disperse them evenly after stirring.

[0066] (2) After uniform dispersion, the temperature is raised to 80°C, and a catalyst (dibutyltin dilaurate) is added. The reaction is carried out at a constant temperature for 3 hours. The ratio of hydrophobic material, polymer material and catalyst is 0.2:1:0.005.

[0067] (3) After the reaction is complete, the mixture is ultrasonically dispersed for 15 minutes to obtain the modified hydrophobic material.

[0068] (4) The superhydrophobic polymer material was transferred in the form of a micro-nano structure on the imprinting template to the other side of the flexible substrate with a water vapor barrier layer by UV imprinting process, and then surface cured to obtain a hydrophobic antireflection barrier film. Its WVTR was measured to be 3.2 × 10⁻⁶. -5 g / m 2 / day;

[0069] The hydrophobic antireflective barrier membrane of the present invention has a water vapor barrier layer that improves the barrier properties and stability of the barrier membrane. The introduction of the hydrophobic antireflective layer reduces the ability of water vapor to adhere to the surface of the barrier membrane, thereby improving the hydrophobic and anti-fogging performance. At the same time, the microstructure on the surface of the hydrophobic antireflective layer reduces the reflection of sunlight, thereby improving the efficiency of encapsulating solar cells. Therefore, it can have the effects of hydrophobicity, antireflection, high barrier properties and scratch resistance.

[0070] Example 3

[0071] In one embodiment of the present invention, the flexible substrate is made of PET, the material and preparation method of the water vapor barrier layer are the same as in Example 2, and the imprinted nickel template is the same as in Example 2.

[0072] In one embodiment of the present invention, the micro / nano structure hydrophobic antireflective layer is made of epoxy resin, and its hydrophobic modification method is surface modification, specifically including the following steps:

[0073] (1) A large-area barrier film with micro-nano structure is made on the other side of PET with barrier film by UV imprinting process using epoxy resin material.

[0074] (2) Place the barrier membrane in the deposition chamber of the chemical vapor deposition equipment, put 2g of parylene C into the evaporation furnace, and sublimate Parylene C into gas at 80°C. Then, pyrolyze the gaseous raw material at 680°C to decompose it into reactive monomers.

[0075] (3) Gas monomers were deposited at nanoscale rates at room temperature and polymerized on a barrier film with micro-nano structures, with a thickness of 1 μm, ultimately yielding a hydrophobic anti-reflection barrier film with a measured WVTR of 3.0 × 10⁻⁶. -5 g / m 2 / day.

[0076] Example 4

[0077] In one embodiment of the present invention, the flexible substrate is made of PEN.

[0078] Reference Figure 3 As shown, the fourth embodiment of the present invention proposes another method for manufacturing a water vapor barrier layer, the method comprising the following steps:

[0079] Step 1: Chemical vapor deposition of a 1 μm thick layer of parylene C on the surface of a flexible PEN substrate, with a water vapor transmission rate (WVTR) of 0.1 g / m. 2 / day;

[0080] Step 2: On top of the organic layer, prepare a 30 nm thick Al2O3 layer using the ALD process at a growth temperature of 80 °C and a water vapor transmission rate (WVTR) of 10. -3 g / m 2 / day;

[0081] Step 3: A 1 μm thick layer of parylene C is deposited on top of the inorganic layer using chemical vapor deposition. Steps 1 and 2 are repeated three times in sequence to finally obtain the water vapor barrier layer. Its water vapor transmission rate (WVTR) is measured to be approximately 5 × 10⁻⁶. -5 g / m 2 / day;

[0082] In one embodiment of the present invention, the material and preparation method of the micro / nano-structured hydrophobic antireflective layer are the same as in Example 2. Finally, the superhydrophobic polymer material obtained by mechanically blending the micro / nano structure is transferred to the other side of a flexible substrate with a water vapor barrier layer and surface cured to obtain a hydrophobic antireflective barrier film. Its WVTR was measured to be 2.8 × 10⁻⁶. -5 g / m 2 / day.

[0083] Example 5

[0084] In one embodiment of the present invention, the flexible substrate is made of PET.

[0085] As one embodiment of the present invention, the material of the micro / nano structure hydrophobic anti-reflective layer is the same as that in Example 2. The ratio of hydrophobic material, polymer material and catalyst in the preparation method is 0.2:1:0.005, and the rest of the preparation method is the same.

[0086] In one embodiment of the present invention, the material and preparation method of the water vapor barrier layer are the same as in Example 4. Finally, the superhydrophobic polymer material prepared by surface modification of the micro / nano structure is transferred to the other side of the flexible substrate with the water vapor barrier layer and surface cured to obtain a hydrophobic antireflection barrier film, with a measured WVTR of 3.0 × 10⁻⁶. -5 g / m2 / day.

[0087] Example 6

[0088] Figure 5 This is a method for encapsulating perovskite solar cells using the hydrophobic antireflection barrier film of Example 2 according to Embodiment 6 of the present invention.

[0089] Reference Figure 5 As shown, the sixth embodiment of the present invention proposes a method for encapsulating a solar cell using the above-described hydrophobic antireflection barrier film. The method includes the following steps:

[0090] 1. Material preparation: flexible substrate, hydrophobic anti-reflective barrier film, and EVA film in 5×5cm increments. 2 Size cutting;

[0091] 2. Battery fabrication, using a diameter of 2.5 × 1.6 cm. 2 Using FTO conductive glass as the substrate, the perovskite solar cell was ultrasonically cleaned with deionized water, ethanol, and acetone. Then, a SnO2 electron transport layer was prepared using the sol-gel method, followed by a perovskite film fabricated using spin-coating. Spiro-OMeTAD was then used as the hole transport layer, and finally, silver evaporation was completed to fabricate the perovskite solar cell. The perovskite solar cell was then fixed to the electrodes using wires and conductive adhesive.

[0092] 3. Lamination: The aluminum-plastic film, EVA film, perovskite solar cell, EVA film, and hydrophobic anti-reflection barrier film are laid in sequence. After the wires are moved to both sides of the cell, the laminator is used for lamination.

[0093] 4. Cutting: After lamination, cut off the scraps around the battery to obtain the final product.

[0094] As one embodiment of the present invention, a hydrophobic antireflection barrier film is used to encapsulate a perovskite solar cell. The hydrophobic antireflection barrier film can simultaneously function as a commonly used water-blocking film and a fluorine film, simplifying the process and related materials, and improving the performance of the solar cell at the same time.

[0095] Comparative Example 1

[0096] Unlike Example 4, the prepared barrier membrane is only a single layer of organic parylene C water vapor barrier layer, wherein the thickness of parylene C is increased to 3 μm, and the WVTR test result is 0.16 g / m. 2 / day;

[0097] Comparative Example 2

[0098] Unlike Example 4, the barrier film obtained was only a single layer of inorganic Al2O3 water vapor barrier layer, with Al2O3 thicknesses of 20 nm, 30 nm, 50 nm, and 100 nm, and WVTR test results of 6.7 × 10⁻⁶. -3 g / m 2 / day,0.8×10 - 3 g / m 2 / day,1.6×10 -3 g / m 2 / day and 6.4×10 -3 g / m 2 / day;

[0099] Comparative Example 3

[0100] Unlike Example 2, the barrier film obtained only contains a flexible substrate and the water vapor barrier layer of Example 2, while no hydrophobic anti-reflection barrier layer is applied to the other side, and its water vapor permeability is 5.7 × 10⁻⁶. -5 g / m 2 / day, the structure and process of encapsulating the solar cell are the same as in Example 6;

[0101] Comparative Example 4

[0102] Unlike Example 2, the barrier film obtained only contains a flexible substrate and the water vapor barrier layer of Example 2, while no hydrophobic anti-reflection barrier layer is applied to the other side, and its water vapor permeability is 5.7 × 10⁻⁶. -5 g / m 2 / day, and at the same time, during the process of encapsulating solar cells, an additional 0.2mm thick EVA adhesive layer and a 20μm thick ETFE fluorine film are applied to the outer layer of the barrier film before lamination in a laminator.

[0103] Table 1. Water contact angle, permeability, water absorption, and abrasion resistance of the barrier membrane.

[0104] Water contact angle Transmission rate water absorption abrasion resistance Example 2 128 95.96％ ＜10％ ＜10％ Example 3 125 95.55％ ＜10％ ＜10％ Example 4 123 94.25％ ＜10％ ＜10％ Example 5 121 94.40％ ＜10％ ＜10％ Comparative Example 3 117 88.86％ 30％-35％ 15％-20％ Comparative Example 4 117 88.86％ 30％-35％ 15％-20％

[0105] Abrasion resistance test: The change rate of hydrophobic angle after rubbing the coated glass back and forth for 40,000 times with a load of 1N under a fully wetted sponge.

[0106] Self-cleaning test: Using the hydrophobic and anti-reflective barrier membranes of Examples 2, 3, 4, and 5, fingerprints were pressed onto them, and the fingerprints disappeared on their own after a short while.

[0107] The water vapor barrier layers in Comparative Examples 1 and 2 demonstrate that simply increasing the thickness of the organic and inorganic layers cannot further improve the water vapor barrier performance. Therefore, the water vapor barrier layer structure requires alternating organic and inorganic layers to reduce the water vapor barrier performance of the membrane to 10. -5 g / m2 / day.

[0108] In Example 2, the water vapor permeability of the barrier membrane was 3.2 × 10⁻⁶. -5 g / m 2 / day, the water vapor permeability of the barrier membranes in Comparative Examples 3 and 4 was 5.7 × 10⁻⁶. -5 g / m 2 Therefore, the water vapor barrier properties of the hydrophobic anti-reflective layer in Example 2 are better than those of the non-hydrophobic anti-reflective layers in Comparative Examples 3 and 4. Furthermore, the light transmittance of the barrier film in Example 2 is 95%, and the haze is 2%, while the light transmittance of the barrier films in Comparative Examples 3 and 4 is 88%, and the haze is 3%. Therefore, the hydrophobic anti-reflective structure in Example 2 has higher light transmittance and lower haze than the non-hydrophobic anti-reflective structures in Comparative Examples 3 and 4. Thus, the barrier film method in Example 2 of the present invention enables the encapsulated solar cell to have higher water vapor barrier properties and higher light transmittance after encapsulation.

[0109] The performance of the completed solar cells was characterized. The initial efficiencies of the laminated cells in Example 2, Comparative Example 3, and Comparative Example 4 were measured to be 22.6%, 21.68%, and 21.73%, respectively. There was no significant difference in performance between Comparative Example 3 and Comparative Example 4, while the efficiency of the cell in Example 2 was significantly higher than that in the comparative examples. This is mainly attributed to the special hydrophobic antireflective layer structure, which reduces the reflection of sunlight and increases the transmittance of sunlight, thus improving the cell's performance. Aging tests were then conducted on the three groups of laminated cells, specifically 360 hours of high temperature and humidity, 48 hours of high and low temperature shock, or 15 kWh of ultraviolet irradiation to test their power decay. After the tests, it was found that after 48 hours of high and low temperature shock, the efficiency of Example 2 decreased by 10.3%, Comparative Example 3 by 28.8%, and Comparative Example 4 by 25.5%. This indicates that the hydrophobic antireflective barrier film in Example 2 can effectively improve the performance and lifespan of the solar cell.

[0110] The hydrophobic antireflective barrier membrane of the present invention has a water vapor barrier layer that improves the barrier properties and stability of the barrier membrane; the introduction of the hydrophobic antireflective layer reduces the ability of water vapor to adhere to the surface of the barrier membrane, thereby improving the hydrophobic and anti-fogging performance. At the same time, the microstructure on the surface of the hydrophobic antireflective layer reduces the reflection of sunlight, thereby improving the efficiency of encapsulating solar cells. Therefore, it can have the effects of scratch resistance, hydrophobicity, antireflection and self-cleaning.

[0111] Although the invention has been shown and described with reference to specific embodiments, those skilled in the art will understand that various changes in form and detail may be made herein without departing from the spirit and scope of the invention as defined by the claims and their equivalents.

Claims

1. A hydrophobic, permeability-enhancing, barrier film, characterized in that: The hydrophobic permeability barrier film is a sandwich structure, comprising a micro-nano structure hydrophobic permeability layer, a flexible substrate and a water vapor barrier layer; The micro-nano structure hydrophobic permeability layer is made of super-hydrophobic polymer material and is an array of convex hydrophobic structures, which is formed by a roll-to-roll stencil transfer process; The water vapor barrier layer is a blended layer of organic and inorganic nanomaterials; The flexible substrate is at least one of polyethylene terephthalate PET, polyethylene naphthalate PEN, polyimide PI; the inorganic nanomaterial is at least one of silicon oxide SiO x , silicon nitride SiN x , aluminum oxide Al2O3, and the organic matter is at least one of SiCxHyO Z , Parylene; the super-hydrophobic polymer material is at least one of polyurethane, polyacrylate, epoxy resin, and Parylene. The preparation method of the super-hydrophobic polymer material is as follows: Mechanical blending, mechanical stirring of the hydrophobic material for modification and the polymer material, addition of a catalyst, and reaction to obtain the super-hydrophobic polymer material which can be directly used in a roll-to-roll nano-imprinting process to obtain the micro-nano structure hydrophobic permeability layer; Alternatively, after obtaining the micro-nano structure of the polymer material by nano-imprinting, at least one of wet immersion, spraying, thermal evaporation and chemical vapor deposition is used to perform hydrophobic treatment on the micro-nano structure surface.

2. The method of claim 1, wherein: The preparation method comprises the following steps: Step 1: preparation of the water vapor barrier layer An organic layer with a thickness of 1 μm and an inorganic layer with a thickness of 30 nm-100 nm are prepared on the surface of the flexible substrate by a chemical vapor deposition method, and at least three organic / inorganic stacked structure water vapor barrier layers are obtained by organic / inorganic multilayer circulation; Step 2: preparation of the nano-imprinting template of the micro-nano structure hydrophobic permeability layer First, a photoresist mask layer is uniformly coated on the surface of a glass sheet, and the photoresist mask layer is exposed and developed to form a photoetching mask pattern structure; Second, the photoetching mask pattern structure is heat-fused to make the cylindrical photoresist columns form a spherical microlens structure and closely arrange, which is a first-level structure; the microstructure is locally implanted by a helium ion beam to form a cylindrical nano-level papilla structure on the surface of the microlens, which is sparsely arranged and is a second-level structure; then, high-temperature solidification is continued to form a photoresist micro-nano hierarchical structure pattern on the surface of the glass substrate; Finally, the micro-nano hierarchical structure pattern on the surface of the glass substrate is transferred to the surface of a hard nickel plate by structure surface sensitization, silver mirror reaction and electroplating process, and a large-area micro-nano structure imprinting nickel template can be obtained by splicing the nickel plates; Step 3: preparation of the micro-nano structure hydrophobic permeability layer on the other side of the flexible substrate with the water vapor barrier layer The large-area micro-nano structure imprinting nickel template obtained in step 2 is wrapped on the surface of the imprinting machine film-coating roller, and the micro-nano structure is transferred to the surface of the flexible substrate with the water vapor barrier layer obtained in step 1 by the nano-imprinting process through the super-hydrophobic polymer material and is solidified to obtain the hydrophobic permeability barrier film.

3. The method of claim 1, wherein the superhydrophobic polymer material is prepared by the steps of: The hydrophobic material is one of hydrophobic silicon dioxide, silane coupling agent, hydroxyl silicone oil, fluorosilane and parylene, the polymer is one of epoxy resin, polyurethane and polyacrylate, and the catalyst is one of dibutyltin dilaurate, stannous octoate and monobutyl tin oxide.

4. The method of claim 1, wherein: The molar ratio of the hydrophobic material, the polymer and the catalyst is 0.2-1.5:1:0.005-0.05; and the thickness of the hydrophobic layer on the micro-nano structure surface is 0.05 μm-2 μm.

5. The method of claim 1, wherein: The caliber of the first-stage micro-hemisphere close-packed structure in step 2 is 10-50 microns, the diameter and height of the second-stage nano-papilla structure are 100-500 nm, and the distribution interval is 20-1 micron.

6. A perovskite thin film solar cell encapsulated with the hydrophobic, super- transparent, barrier film of claim 1, characterized in that, The packaged perovskite thin film solar cell structure is: substrate / EVA / aluminum film / POE / perovskite solar cell / POE / hydrophobic antireflection barrier film, which is integrated after lamination by a laminator.

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