Glass substrate, manufacturing method thereof and photovoltaic module

Abstract

The invention discloses a glass substrate, a manufacturing method thereof and a photovoltaic module, relates to the technical field of photovoltaics, and aims to enable a first surface of the glass substrate to have higher light transmittance for a long time under the condition that the glass substrate is exposed in an external environment, and the manufacturing cost of the glass substrate can be reduced. The manufacturing method of the glass substrate comprises the following steps: providing the glass substrate; the glass substrate has a first surface and a second surface opposite to each other. Forming a mask layer doped with solid particles on the first surface of the glass substrate; in all the solid particles, the size of the solid particle with the smallest size is greater than the thickness of the mask layer; the material of the solid particles is different from that of the mask layer, and the bottoms of the solid particles are in contact with the first surface. And selectively removing the solid particles to form a mask pattern penetrating through the mask layer. And next, under the mask effect of the mask layer, etching the first surface of the glass substrate by adopting a wet etching process, so that the first surface of the glass substrate forms a textured surface. And then, removing the mask layer.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic technology, and in particular to a glass substrate, a manufacturing method thereof, and a photovoltaic module. Background Art

[0002] Solar cell encapsulation is a crucial step in the manufacturing of photovoltaic modules. Photovoltaic glass, a key raw material in the solar cell manufacturing process, directly impacts the solar cell's photoelectric conversion efficiency. Currently, the main methods for reducing the reflectivity of photovoltaic glass are coating and photolithography.

[0003] However, when coated glass is exposed to external environments such as humidity, heat, freezing, ultraviolet radiation, and salt spray for a long time, its transmittance decreases and the film layer is easy to fall off; and the tools required for photolithography technology are relatively expensive, which greatly increases the cost of photovoltaic modules and is not conducive to the mass production of photovoltaic modules. Summary of the Invention

[0004] The object of the present invention is to provide a glass substrate, a manufacturing method thereof, and a photovoltaic module, so that when the glass substrate is exposed to the external environment, the first surface thereof has a high light transmittance for a long time, and the manufacturing cost of the glass substrate can be reduced, which is conducive to the mass production of photovoltaic modules including the glass substrate.

[0005] To achieve the above-mentioned objectives, in a first aspect, the present invention provides a method for manufacturing a glass substrate, comprising: first, providing a glass substrate; the glass substrate having a first surface and a second surface relative to each other. Next, forming a mask layer doped with solid particles on the first surface of the glass substrate; the size of the smallest solid particles among all the solid particles is greater than the thickness of the mask layer; the material of the solid particles is different from the material of the mask layer, and the bottom of the solid particles is in contact with the first surface. Next, selectively removing the solid particles to form a mask pattern that penetrates the mask layer. Next, under the masking action of the mask layer and using a wet etching process, etching the first surface of the glass substrate so that a velvet surface is formed on the first surface of the glass substrate. Then, removing the mask layer.

[0006] In the technical solution, after the glass substrate is provided, a mask layer doped with solid particles is formed on the first surface of the glass substrate. The size of the smallest solid particle among all the solid particles is greater than the thickness of the mask layer, so that at least the top region of the smallest solid particle is exposed outside the mask layer. Meanwhile, the material of the solid particle is different from the material of the mask layer. Therefore, an etchant that only has etching effect on the solid particle and has little effect on the mask layer can be selected to selectively remove the solid particle. Secondly, the bottom of the solid particle is in contact with the first surface of the glass substrate. Therefore, after the solid particle doped in the mask layer is selectively removed, the position originally occupied by the solid particle forms a mask pattern penetrating through the mask layer, so that the mask layer with the mask pattern is manufactured by pre-occupying the solid particle, without using the expensive photolithography technology to manufacture the mask layer, thereby reducing the manufacturing cost of the glass substrate and the photovoltaic module including the glass substrate, and further facilitating mass production of the photovoltaic module.

[0007] In addition, after the mask layer with the mask pattern is obtained, the first surface of the glass substrate is etched under the mask effect of the mask layer by using a wet etching process, so that the first surface of the glass substrate forms a rough surface. Therefore, compared with a flat surface, the rough surface has a larger specific surface area, so that it has good light trapping effect and helps to reduce the reflectivity of the first surface of the glass substrate. In this case, if the photovoltaic module includes the above glass substrate and the first surface of the glass substrate is the light-receiving surface, more light can be transmitted from the first surface of the glass substrate to the solar cell included in the photovoltaic module and utilized by the solar cell, thereby improving the working efficiency of the photovoltaic module. Secondly, the rough surface with the light trapping effect is obtained by processing the first surface of the glass substrate, i.e., the rough surface is part of the glass substrate itself, rather than forming a coating on the light-receiving surface of the glass substrate that does not belong to the structure of the glass substrate itself in the prior art. Therefore, the problems of the light transmittance of the light-receiving surface of the glass substrate decreasing over time and the coating layer easily falling off due to low hardness, poor wear resistance, and low bonding force between the coating layer and the glass substrate can be prevented, so that the first surface of the glass substrate has a high light transmittance for a long time, thereby helping to make the photovoltaic module including the glass substrate have stable working performance.

[0008] As a possible implementation, the mask layer doped with solid particles on the first surface of the glass substrate includes: forming a dispersion liquid arranged in an integral layer on the first surface; the dispersion liquid includes a mask liquid and solid particles dispersed in the mask liquid. Next, the dispersion liquid is subjected to a solidification treatment to form the mask layer doped with solid particles.

[0009] When the above-described technical solution is employed, after a full layer of dispersion is formed on the first surface, the dispersion can, by virtue of its own fluidity, flow toward the areas on the first surface where the dispersion has a lesser thickness. Therefore, after the dispersion is solidified to form a mask layer doped with solid particles, the thickness of the mask layer on each area of ​​the first surface of the glass substrate is substantially uniform, ensuring that each area of ​​the first surface of the mask layer has a good masking effect, thereby improving etching accuracy. Furthermore, the dispersion's fluidity facilitates uniform distribution of the solid particles within each area of ​​the mask layer, thereby ensuring that the different mask holes included in the mask pattern are evenly distributed after removal of the solid particles. This further facilitates uniform distribution of the velvet structure of the velvet surface obtained under the masking effect of the mask layer and after wet etching, ensuring that each area of ​​the first surface has a low reflectivity.

[0010] As a possible implementation solution, the concentration of the solid particles in the dispersion is greater than or equal to 1 mg / mL and less than or equal to 10 mg / mL.

[0011] In the case of adopting the above technical solution, it can be understood that the greater the concentration of solid particles in the dispersion, the greater the number of solid particles in the dispersion, and the greater the number of solid particles doped in the mask layer formed based on the dispersion; after selectively removing the solid particles, the density of the mask pattern on the mask layer is higher, and the distribution density of the velvet structure in the velvet formed under the masking action of the mask layer is also larger. On the contrary, the smaller the concentration of solid particles in the dispersion, the smaller the distribution density of the velvet structure in the velvet formed under the masking action of the mask layer. It can be seen that the distribution density of the velvet structure in the velvet can be adjusted by adjusting the concentration of solid particles in the dispersion. Based on this, the concentration of solid particles in the dispersion is within the above range, which can prevent the reflectivity of the velvet from being reduced to a lesser extent due to the smaller concentration of solid particles in the dispersion, thereby ensuring that the first surface of the glass substrate has a good light trapping effect, and thus ensuring that the photovoltaic module including the glass substrate has a high light utilization rate. In addition, it can also prevent the first side of the glass substrate from easily accumulating dust when it is in the external environment for a long time due to the high concentration of solid particles in the dispersion liquid, which makes the distribution of the velvet structure in the velvet too dense. It further ensures that when the glass substrate is exposed to the external environment, the first side itself has a high light transmittance for a long time.

[0012] As a possible implementation solution, the masking liquid includes a resin solution.

[0013] In the technical solution, the mask layer formed based on the resin solution is easy to be large-sized, and can be more suitable for large-sized glass substrates, thereby facilitating the large-sized photovoltaic module. In addition, compared with other hard mask layers, the mask layer formed based on the resin solution has low rigidity, and the material etching selectivity between the resin mask layer and the glass substrate is large, thereby facilitating removal and preventing damage to the first surface of the glass substrate, and ensuring high yield of the glass substrate.

[0014] As a possible implementation, the solid particles are spherical solid particles.

[0015] In the technical solution, compared with polyhedral solid particles, the spherical solid particles have smooth outer surfaces, and have certain rollability. In the case of forming the mask layer by forming a dispersion liquid arranged in an integral layer on the first surface and curing the dispersion liquid, the solid particles are uniformly distributed in each region of the mask layer. In addition, the spherical solid particles have good symmetry, and the corresponding region shape in the mask layer is substantially the same regardless of the angle of the spherical solid particles in the mask layer. Therefore, the morphology of the mask pattern formed in the mask layer by the solid particles pre-occupying is substantially the same, which improves the mask precision of the mask layer, and facilitates the size and morphology of the textured structure formed on each region of the textured surface to be substantially the same, thereby ensuring the light trapping effect of each region of the textured surface to be substantially the same.

[0016] As a possible implementation, the solid particles are silica particles.

[0017] In the technical solution, the main component of the glass substrate is silica, and therefore, when the solid particles are silica glass, the formation of the mask layer doped with the solid particles on the first surface of the glass substrate and the selective removal of the solid particles can prevent chemical influence on the surface of the glass substrate and introduce new variables, thereby ensuring high yield of the glass substrate. In addition, when the solid particles are silica glass, the same etchant can be used to etch the first surface of the glass substrate while selectively removing the solid particles doped in the mask layer, and different etchants are not required to selectively remove the solid particles and to texturize the first surface, thereby improving the manufacturing efficiency of the glass substrate.

[0018] As a possible implementation, the size of the solid particles is greater than or equal to 1 μm and less than or equal to 10 μm.

[0019] In the technical solution, it can be understood that the larger the size of the solid particles is, the larger the size of the mask hole in the mask pattern formed in the mask layer by the pre-occupying of the solid particles is, and the larger the area of the first surface of the glass substrate exposed outside through the mask hole is, so that after the first surface is processed by the mask layer and the wet etching process, the size of the surface structure of the surface is larger. On the contrary, the smaller the size of the solid particles is, the smaller the size of the surface structure of the surface is. Therefore, the size of the surface structure of the surface can be adjusted by adjusting the size of the solid particles. Therefore, the size of the solid particles is in the above range, which can prevent the size of the surface structure from being too small due to the small size of the solid particles, so that the specific surface area of the surface is small, and the light trapping effect of the surface is ensured. In addition, it can also prevent the size of the surface structure from being too large due to the large size of the solid particles, so that the surface (i.e. the first surface of the glass substrate) is prone to accumulate dust in the external environment for a long time, and further ensure that the first surface of the glass substrate has a high light transmittance for a long time when exposed to the external environment.

[0020] As a possible implementation, the different solid particles are uniformly distributed. In this case, it is beneficial to uniformly distribute the different mask holes included in the mask pattern after the solid particles are removed, and further beneficial to uniformly distribute the surface structure of the surface obtained after the mask layer is masked and processed by the wet etching process, so as to ensure that each region of the first surface has a low reflectivity.

[0021] As a possible implementation, in the case of the solid particles being spherical solid particles, the thickness of the mask layer is equal to one half of the average size of all solid particles. In this case, the top of the mask layer is approximately located at the maximum radius of the spherical solid particles. Based on this, after the selective removal of the solid particles, the opening of each mask hole included in the mask pattern is large, which is beneficial to the contact and reaction of the wet etching solution with the first surface of the glass substrate through the mask hole, and also facilitates the discharge of reaction by-products through the mask hole with a large opening. At the same time, the part of the solid particles exposed outside the mask layer is approximately hemispherical, i.e. the volume of the part of the solid particles exposed outside the mask layer is large, which can improve the efficiency of the selective removal of the solid particles.

[0022] As a possible implementation, the surface structure of the surface is a semi-spherical concave structure recessed into the glass substrate.

[0023] In the technical solution, the semi-spherical concave structure recessed into the glass substrate has a rough surface characteristic, which is beneficial to increase the specific surface area of the surface and ensure that the first surface of the glass substrate has a high light transmittance.

[0024] As a possible implementation, the size of the surface structure of the above-mentioned surface is micron level. In this case, the size of the surface structure is small, which is conducive to increasing the specific surface area of the surface, ensuring that the first surface of the glass substrate has high light transmittance, and preventing dust accumulation and other problems caused by the uneven topography of the surface when exposed to the external environment for a long time, thereby ensuring that the first surface of the glass substrate has high light transmittance for a long time when exposed to the external environment.

[0025] As a possible implementation, the first surface of the glass substrate is etched under the masking effect of the mask layer and by using a hydrogen fluoride solution. The concentration of the hydrogen fluoride solution is greater than or equal to 4% and less than or equal to 12%. And / or, the etching time is greater than or equal to 10 min and less than or equal to 30 min.

[0026] In the above technical solution, within a certain range, the concentration of the hydrogen fluoride solution and the etching time are respectively proportional to the degree of etching of the first surface of the glass substrate. Based on this, the concentration of the hydrogen fluoride solution within the above range can prevent the first surface of the glass substrate from having poor light trapping effect due to the small size of the surface structure formed on the first surface of the glass substrate after the texturing treatment, and ensure that the first surface of the glass substrate has high light transmittance. In addition, it can also prevent the first surface of the glass substrate from easily accumulating dust and other problems when exposed to the external environment for a long time due to the large size of the surface structure formed on the first surface of the glass substrate after the texturing treatment, thereby ensuring that the first surface of the glass substrate has high light transmittance for a long time when exposed to the external environment.

[0027] As a possible implementation, before the first surface of the glass substrate is etched under the masking effect of the mask layer and by using a wet etching process, the manufacturing method of the glass substrate further comprises: forming a protective layer arranged on the second surface of the glass substrate. In this case, the presence of the protective layer can prevent the second surface of the glass substrate from being affected by the wet etching solution when the texturing treatment is performed on the first surface of the glass substrate, thereby facilitating the second surface of the glass substrate to have high flatness.

[0028] In a second aspect, the present application provides a glass substrate manufactured by the manufacturing method of the glass substrate provided in the first aspect and any of its various implementation manners.

[0029] In a third aspect, the present application provides a photovoltaic module, which comprises: the glass substrate provided in the third aspect and any of its various implementation manners, a back sheet arranged opposite to the glass substrate, and a cell structure arranged between the glass substrate and the back sheet. The second surface of the glass substrate faces the cell structure.

[0030] The beneficial effects of the second and third aspects of the present invention and their various implementations can be analyzed with reference to the beneficial effects of the first aspect and its various implementations, and will not be repeated here. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0032] Figure 1 A flow chart of a method for manufacturing a glass substrate provided by an embodiment of the present invention;

[0033] Figure 2 Schematic diagram of the structure of the glass substrate formed by the manufacturing method provided by the embodiment of the present invention during the manufacturing process Figure 1 ;

[0034] Figure 3 Schematic diagram of the structure of the glass substrate formed by the manufacturing method provided by the embodiment of the present invention during the manufacturing process Figure 2 ;

[0035] Figure 4 Schematic diagram of the structure of the glass substrate formed by the manufacturing method provided by the embodiment of the present invention during the manufacturing process Figure 3 ;

[0036] Figure 4 Schematic diagram of the structure of the glass substrate formed by the manufacturing method provided by the embodiment of the present invention during the manufacturing process Figure 6 ;

[0037] Figure 5 Schematic diagram of the structure of the glass substrate formed by the manufacturing method provided by the embodiment of the present invention during the manufacturing process Figure 7 ;

[0038] Figure 6 Schematic diagram of the structure of the glass substrate formed by the manufacturing method provided by the embodiment of the present invention during the manufacturing process Figure 8 ;

[0039] Figure 9 A scanning electron microscope image of the first surface of a glass substrate formed by the manufacturing method provided by an embodiment of the present invention;

[0040] Figure 1 This is a comparison diagram of light transmission between a glass substrate (corresponding to a textured surface) formed by the manufacturing method provided by an embodiment of the present invention and conventional flat glass (corresponding to a flat surface).

[0041] Reference numerals: 11 is a glass substrate, 12 is a first surface, 13 is a second surface, 14 is solid particles, 15 is a mask layer, 16 is a mask pattern, 17 is a velvet structure, and 18 is a protective layer. DETAILED DESCRIPTION

[0042] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are merely illustrative and are not intended to limit the scope of the present disclosure. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present disclosure.

[0043] The accompanying drawings illustrate various schematic diagrams of structures according to embodiments of the present disclosure. These figures are not drawn to scale, and for the purpose of clarity, certain details are exaggerated and certain details may be omitted. The shapes of the various regions and layers shown in the figures, as well as their relative sizes and positional relationships, are merely exemplary and may deviate in practice due to manufacturing tolerances or technical limitations. Those skilled in the art may design regions / layers with different shapes, sizes, and relative positions as needed.

[0044] In the context of this disclosure, when a layer / element is referred to as being "on" another layer / element, the layer / element may be directly on the other layer / element, or there may be an intervening layer / element between them. Furthermore, if a layer / element is "on" another layer / element in one orientation, it may be "below" the other layer / element when the orientation is reversed. To further clarify the technical problems, technical solutions, and beneficial effects to be solved by the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are intended solely to explain the present invention and are not intended to limit the present invention.

[0045] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be understood to indicate or imply relative importance or implicitly specify the number of the technical features indicated. Thus, a feature specified as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, "plurality" means two or more, unless otherwise specifically defined. "Several" means one or more, unless otherwise specifically defined.

[0046] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they may refer to fixed, detachable, or integral connections; mechanical or electrical connections; direct or indirect connections through an intermediate medium; and may encompass internal communication between two components or interaction between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention based on specific circumstances.

[0047] Currently, due to energy shortages and environmental concerns, new energy sources such as photovoltaic power generation are attracting increasing attention. Furthermore, my country's photovoltaic industry has also seen significant growth in recent years. Domestic companies have consistently increased the production of photovoltaic modules and installed capacity, making it the world's largest photovoltaic market. Specifically, in 2021, my country's newly installed photovoltaic capacity reached 54.88 GW, and photovoltaic product exports exceeded US$28 billion. In this context, improving the cost-effectiveness of photovoltaic modules, thereby further enhancing their competitiveness against other energy sources, is of vital practical significance to the healthy and sustainable development of the photovoltaic market and the achievement of carbon reduction goals. Improving the cost-effectiveness of photovoltaic modules can be achieved, on the one hand, by reducing material costs and optimizing various production processes, thereby lowering module costs; on the other hand, by improving the modules' photoelectric conversion performance. In actual applications, compared with the former, which has already low raw material costs and mature processes, the latter offers greater potential and opportunities.

[0048] The encapsulation of solar cells is a crucial step. Photovoltaic glass, a key raw material in photovoltaic modules, is a crucial raw material in the solar cell manufacturing process. Its solar light transmittance directly impacts the solar cell's photoelectric conversion efficiency. In addition to the influence of iron content on glass transmittance, the patterned structure of the glass surface also significantly impacts transmittance. If improperly designed, when sunlight strikes the photovoltaic glass, some of the light may be reflected, significantly impacting the surrounding environment. Sunlight incident on the cover plate may not be properly refracted back, affecting light transmittance and, in turn, the conversion of light energy into electrical energy.

[0049] At present, there are two main ways to achieve the effect of anti-reflection and anti-transmission of glass:

[0050] The first method involves coating the glass surface, which is also the most common surface treatment method. Specifically, by coating the glass surface with one or more layers of metal, metal compounds, or organic films, this reduces light reflection and improves the transmittance of photovoltaic glass. Currently, the main glass surface coating processes include chemical vapor deposition, magnetron sputtering, and sol-gel methods.

[0051] The second method is to use physical etching, that is, to prepare a light-trapping structure on the glass surface through photolithography technology, thereby reducing the Fresnel reflection caused by the sudden change in the refractive index coefficient of the medium in the glass when the light enters from the air, effectively reducing the reflectivity of the glass surface and increasing the transmittance.

[0052] While both of the aforementioned methods can reduce the reflectivity of the glass surface, the first method, after coating the glass, results in most functional films with a lower hardness than the glass itself, resulting in poor wear resistance. Furthermore, due to the significant difference in composition between the film material and the glass, the interfacial bonding strength is low. Consequently, prolonged exposure to heat, humidity, freezing, UV radiation, and salt fog can lead to decreased light transmittance, the appearance of rainbow patterns on the surface, and the film easily falling off. The second method, which uses photolithography to create a light-trapping structure on the glass surface to increase light transmittance, can avoid these issues. However, the tools required for photolithography are relatively expensive, significantly increasing the cost of photovoltaic modules and hindering mass production.

[0053] In order to solve the above technical problems, firstly, Figures 2 to 7 As shown, the embodiment of the present invention provides a method for manufacturing a glass substrate. Figure 2 The manufacturing process is described with reference to the cross-sectional view of the operation shown in FIG. Specifically, the manufacturing method of the glass substrate includes the following steps:

[0054] First, if Figure 3 As shown in FIG. 1 , a glass substrate 11 is provided; the glass substrate 11 has a first surface 12 and a second surface 13 opposite to each other. Figure 5 As shown, a mask layer 15 doped with solid particles 14 is formed on the first surface of the glass substrate 11; among all the solid particles 14, the size of the smallest solid particle 14 is larger than the thickness of the mask layer 15; the material of the solid particles 14 is different from that of the mask layer 15, and the bottom of the solid particles 14 is in contact with the first surface. Figure 6 As shown, the solid particles are selectively removed to form a mask pattern 16 that penetrates the mask layer 15. Next, as shown Figure 7 As shown, under the masking effect of the mask layer 15, the first surface of the glass substrate 11 is etched by a wet etching process so that the first surface of the glass substrate 11 forms a textured surface. Figure 3 As shown, the mask layer is removed.

[0055] When the above technical solution is adopted, Figure 5As shown, after providing a glass substrate 11, a mask layer 15 doped with solid particles 14 is first formed on the first surface of the glass substrate 11. Moreover, among all the solid particles 14, the size of the smallest solid particle 14 is larger than the thickness of the mask layer 15. This arrangement allows at least the top area of ​​the smallest solid particle 14 to be exposed outside the mask layer 15. At the same time, the material of the solid particle 14 is different from that of the mask layer 15. Based on this, as Figure 6 As shown, an etchant that only etches the solid particles without affecting or having minimal impact on the mask layer 15 can be selected to achieve selective removal of the solid particles. Secondly, the bottom of the solid particles contacts the first surface of the glass substrate 11. Therefore, after selectively removing the solid particles doped in the mask layer 15, a mask pattern 16 that penetrates the mask layer 15 is formed at the location where the solid particles originally were. This allows the mask layer 15 having the mask pattern 16 to be manufactured by pre-occupying the solid particles, eliminating the need to use expensive photolithography technology to manufacture the mask layer 15. This helps reduce the manufacturing cost of the glass substrate 11 and the photovoltaic module including the glass substrate 11, thereby facilitating mass production of photovoltaic modules.

[0056] In addition, if Figure 8 As shown, after obtaining the mask layer 15 having the mask pattern 16, the first surface of the glass substrate 11 is etched under the masking effect of the mask layer 15 and a wet etching process is adopted, so that the first surface of the glass substrate 11 forms a textured surface. Figure 9 and Figure 3 As shown, because the velvet surface has a larger specific surface area than a flat surface, it has an excellent light-trapping effect, which helps reduce the reflectivity of the first surface of the glass substrate. In this case, if a photovoltaic module includes the above-mentioned glass substrate and the first surface of the glass substrate is the light-facing surface, more light is transmitted from the first surface of the glass substrate to the solar cells included in the photovoltaic module and utilized by the solar cells, thereby improving the operating efficiency of the photovoltaic module. Secondly, the velvet surface with light-trapping effect is obtained by treating the first surface of the glass substrate. That is, the velvet surface is a part of the glass substrate itself, rather than being an additional coating formed on the light-facing side of the glass substrate as in the prior art. This prevents the light transmittance of the light-facing side of the glass substrate from decreasing over time due to factors such as low coating hardness, poor wear resistance, and weak bonding strength with the glass substrate, as well as the problem of film layer easily falling off. This helps to ensure that the first surface of the glass substrate has a high light transmittance over a long period of time, thereby ensuring stable operating performance of the photovoltaic module including the glass substrate.

[0057] In actual applications, the present invention does not impose any specific restrictions on the thickness of the glass substrate. Secondly, before forming the mask layer doped with solid particles on the first surface of the glass substrate, the glass substrate can be cleaned to remove impurities such as grease on the surface of the glass substrate. This prevents the presence of impurities from affecting the manufacturing accuracy of the mask layer, thereby improving the yield of the subsequent texturing process on the first surface of the glass substrate based on the mask layer.

[0058] For example, a glass substrate can be scrubbed with a detergent. Then, ultrasonic cleaning can be performed using ethanol, acetone, isopropyl alcohol, and ethanol for 20 minutes each to remove any remaining impurities. After cleaning, the substrate can be dried and used for later use.

[0059] Next, if Figure 3 As shown, the mask layer 15 doped with solid particles 14 is formed on the first surface of the glass substrate 11. For example, a dispersion liquid can be formed as a whole layer on the first surface; the dispersion liquid includes a mask liquid and solid particles 14 dispersed in the mask liquid. Next, the dispersion liquid is solidified to form the mask layer 15 doped with solid particles 14. In this case, after the dispersion liquid is formed as a whole layer on the first surface by spraying, spin coating, or doctoring, the dispersion liquid can flow to the area with less thickness on the first surface by virtue of its own fluidity. Therefore, after the dispersion liquid is solidified to form the mask layer 15 doped with solid particles 14, the thickness of the mask layer 15 on each area of ​​the first surface of the glass substrate 11 is made substantially the same, ensuring that each area of ​​the first surface of the mask layer 15 has a good masking effect, thereby improving the etching accuracy. In addition, the dispersion has a certain fluidity, which is also conducive to the uniform distribution of the solid particles 14 in each area of ​​the mask layer 15, so that after removing the solid particles 14, the different mask holes included in the mask pattern are evenly distributed, which is conducive to the uniform distribution of the velvet structure of the velvet obtained under the masking action of the mask layer 15 and after wet etching treatment, ensuring that each area of ​​the first surface has a lower reflectivity.

[0060] Alternatively, a layer of solid particles may be deposited on the first surface of the glass substrate. Next, a layer of masking liquid may be deposited on the first surface by spraying, spin coating, or doctor blade coating to obtain a dispersion of solid particles and masking liquid. The dispersion is then solidified to form a masking layer doped with solid particles.

[0061] Specifically, for the above-mentioned dispersion, the type of masking liquid included in the dispersion determines the material of the mask layer. Therefore, the type of masking liquid can be determined according to the material requirements of the mask layer in actual application scenarios.

[0062] Exemplarily, the masking liquid may include a resin solution. The specific type of the resin solution may be determined according to the actual application scenario. For example, the resin solution may include at least one of a polydimethylsiloxane solution, an epoxy resin solution, a phenolic resin solution, a polyaramid resin solution, a polyurethane resin solution, and an acrylic solution. In this case, the mask layer formed based on the resin solution is easy to achieve large-scale, can be more adaptable to large-size glass substrates, and is conducive to the large-scale photovoltaic module. In addition, compared with other hard mask layers, the mask layer formed based on the resin solution has lower rigidity, and the material etching selection between the resin mask layer and the glass substrate is relatively large, which is easy to remove, prevents damage to the first side of the glass substrate, and ensures that the glass substrate has a high yield.

[0063] In addition to the masking fluid and solid particles, the dispersion may also include a diluent to adjust the fluidity of the dispersion and the position of the solid particles within the dispersion. The type of diluent can be determined based on the type of masking fluid and the material of the solid particles and is not specifically limited here. For example, the diluent may be acetone.

[0064] For the above-mentioned solid particles, it can be understood that the greater the concentration of solid particles in the dispersion, the greater the number of solid particles in the dispersion, and the greater the number of solid particles doped in the mask layer formed based on the dispersion; after the selective removal of the solid particles, the density of the mask pattern on the mask layer is higher, and the distribution density of the velvet structure in the velvet formed under the masking action of the mask layer is also larger. On the contrary, the smaller the concentration of solid particles in the dispersion, the smaller the distribution density of the velvet structure in the velvet formed subsequently under the masking action of the mask layer. It can be seen from this that the distribution density of the velvet structure in the velvet can be adjusted by adjusting the concentration of solid particles in the dispersion. Based on this, the concentration of solid particles in the dispersion can be determined according to the distribution density of the velvet structure in the actual application scenario.

[0065] Exemplarily, the concentration of the above-mentioned solid particles in the dispersion can be greater than or equal to 1 mg / mL and less than or equal to 10 mg / mL. For example, the concentration of the solid particles in the dispersion can be 1 mg / mL, 2 mg / mL, 4 mg / mL, 6 mg / mL, 8 mg / mL or 10 mg / mL, etc. In this case, the concentration of the solid particles in the dispersion is within the above-mentioned range, which can prevent the reflectivity of the velvet from being reduced to a lesser extent due to the smaller concentration of the solid particles in the dispersion, which makes the distribution density of the velvet structure in the velvet smaller, thereby ensuring that the first surface of the glass substrate has a good light trapping effect, and further ensuring that the photovoltaic module including the glass substrate has a higher light utilization rate. In addition, it can also prevent the first surface of the glass substrate from being easily accumulated with dust when it is in the external environment for a long time due to the large concentration of the solid particles in the dispersion, which makes the distribution of the velvet structure in the velvet too dense, further ensuring that when the glass substrate is exposed to the external environment, the first surface itself has a higher light transmittance for a long time.

[0066] In addition, it can be understood that the larger the size of the solid particles, the larger the size of the mask holes in the mask pattern formed in the mask layer by pre-occupying the solid particles, and the larger the area of ​​the first surface of the corresponding glass substrate exposed to the outside through the mask holes, so that under the masking action of the mask layer and after the first surface is processed by a wet etching process, the size of the velvet structure of the velvet is larger. On the contrary, the smaller the size of the solid particles, the smaller the size of the velvet structure of the velvet. It can be seen from this that the size of the velvet structure in the velvet can be adjusted by adjusting the size of the solid particles. Based on this, the size of the solid particles can be determined according to the size requirements of the velvet structure in the actual application scenario.

[0067] Exemplarily, the size of the above-mentioned solid particles can be greater than or equal to 1μm and less than or equal to 10μm. For example, the size of the solid particles can be 1μm, 2μm, 4μm, 6μm, 8μm or 10μm, etc. In this case, based on this, the size of the solid particles is within the above-mentioned range, which can prevent the velvet structure from being smaller due to the smaller size of the solid particles, resulting in a smaller specific surface area of ​​the velvet, and ensure that the velvet has a higher light-trapping effect. In addition, it can also prevent the velvet (i.e., the first side of the glass substrate) from being easily accumulated with dust in the external environment for a long time due to the larger size of the solid particles, further ensuring that when the glass substrate is exposed to the external environment, the first side itself has a higher light transmittance for a long time.

[0068] Specifically, the sizes of different solid particles can be the same or different. The embodiment of the present invention does not impose any specific limitation on the size relationship between different solid particles, as long as the transmittance of the suede formed by the mask layer doped with solid particles meets the working requirements.

[0069] As for the material of the solid particles, it can be any material different from the material of the mask layer, as long as it can be applied to the method for manufacturing the glass substrate provided in the embodiment of the present invention.

[0070] Exemplarily, the solid particles may be silica particles. In this case, the main component of the glass substrate is silica. Therefore, when the solid particles are silica glass, it is possible to prevent the formation of a mask layer doped with solid particles on the first side of the glass substrate, and to prevent chemical effects on the surface of the glass substrate during the selective removal of the solid particles, thereby introducing new variables, thereby ensuring a high yield of the glass substrate. In addition, when the solid particles are silica glass, when selectively removing the solid particles doped in the mask layer, the first side of the glass substrate can be etched simultaneously using the same etchant, eliminating the need to use different etchants for the selective removal of solid particles and the texturing of the first side, thereby improving the manufacturing efficiency of the glass substrate.

[0071] As for the shape of the solid particles, it can be determined according to the size and material of the solid particles, as well as the actual application scenario, and is not specifically limited here.

[0072] For example, the solid particles may be quasi-spherical solid particles; alternatively, the solid particles may have a polyhedral or irregular morphology, as long as they are applicable to the glass substrate manufacturing method provided in the embodiments of the present invention. It should be noted that the quasi-spherical solid particles may be strictly spherical solid particles or approximately spherical solid particles, i.e., some minor deformation due to tolerances may be permitted.

[0073] It is worth noting that compared with three-dimensional shapes such as polyhedrons, the outer surface of spherical solid particles is relatively smooth, which makes them have a certain degree of rollability, and facilitates the uniform distribution of solid particles in various areas of the mask layer when a mask layer is formed by forming a whole layer of dispersion on the first surface and curing the dispersion. In addition, the spherical solid particles have good symmetry. No matter at which angle the spherical solid particles are in the mask layer, the shape of the corresponding area in the mask layer is roughly the same, which is conducive to making the morphology of the mask pattern formed in the mask layer by pre-occupying solid particles basically the same, while improving the mask accuracy of the mask layer, it is conducive to improving the size and morphology of the velvet structure formed in each area of ​​the velvet surface to be roughly the same, thereby ensuring that the light trapping effect of each area of ​​the velvet surface is roughly the same.

[0074] As for the distribution of the solid particles, their positions within the dispersion can be randomly arranged. Preferably, the different solid particles are evenly distributed. In this case, after removing the solid particles, the different mask holes included in the mask pattern are evenly distributed. This further facilitates the uniform distribution of the velvet structure of the velvet surface obtained after wet etching under the masking effect of the mask layer, ensuring that each area of ​​the first surface has a low reflectivity.

[0075] In addition, in actual applications, the dispersion can be cured by allowing the glass substrate, on which the entire layer of dispersion is formed, to stand at room temperature to allow the solvent in the dispersion to evaporate. Alternatively, the dispersion can be cured at a relatively high temperature. The curing temperature can be determined based on the actual application scenario and is not specifically limited here.

[0076] After curing, a mask layer doped with solid particles is obtained. To facilitate removal of the solid particles from the mask layer, the thickness of the mask layer is smaller than the smallest solid particle. Specifically, the thickness of the mask layer, and the difference between the thickness of the mask layer and the size of the solid particles, can be determined based on the shape of the solid particles, the opening size of the mask holes in the mask pattern to be formed within the mask layer, and the actual application scenario.

[0077] For example, Figure 5 As shown, in the case where the solid particles 14 are spherical solid particles, the thickness of the mask layer 15 can be equal to half of the average size of all the solid particles 14. In this case, the top of the mask layer 15 is roughly located at the point where the radius of the spherical solid particles is the largest. Based on this, Figure 5 As shown, after selectively removing solid particles, each mask hole in mask pattern 16 has a relatively large opening, which facilitates the wet etching solution to contact and react with the first surface of glass substrate 11 through the mask holes and also facilitates the discharge of reaction byproducts through the relatively large mask holes. Furthermore, the portion of the solid particle exposed outside mask layer 15 is roughly hemispherical, meaning that the portion of the solid particle exposed outside mask layer 15 is larger, thereby improving the efficiency of selective removal of solid particles.

[0078] Of course, when the solid particles are spherical solid particles, the size of the solid particles is large and the size of the velvet structure to be formed is small, the thickness of the mask layer is also less than half of the average size of all solid particles, or greater than half of the average size of all solid particles and less than the average size of all solid particles.

[0079] like Figure 6As shown, after forming the mask layer 15 doped with solid particles, the solid particles can be selectively removed by dry etching or wet etching, thereby forming mask holes included in the mask pattern 16 at the locations where the solid particles originally existed.

[0080] The type of etchant used to selectively remove solid particles and the specific etching conditions can be determined based on the material and size of the solid particles and are not specifically limited herein. For example, if the solid particles are silicon dioxide particles, the solid particles can be removed using a hydrogen fluoride solution.

[0081] After the selective removal, the mask layer has a through mask pattern. Figure 6 As shown, under the masking effect of the mask layer 15, a wet etching process is used to texture the first surface of the glass substrate 11. The etching solution used in the texture treatment and the specific etching conditions can be determined according to the morphology requirements of the texture structure in the actual application scenario.

[0082] For example, the first surface of the glass substrate can be etched using a hydrogen fluoride solution under the masking action of a mask layer. The concentration of the hydrogen fluoride solution can be greater than or equal to 4% and less than or equal to 12%; and / or the etching time can be greater than or equal to 10 minutes and less than or equal to 30 minutes. For example, when using a hydrogen fluoride solution for texturing, the concentration of the hydrogen fluoride solution can be 4%, 6%, 8%, 10%, or 12%, etc.; and the etching time can be 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, 25 minutes, or 30 minutes, etc. In this case, within a certain range, the concentration of the hydrogen fluoride solution and the etching time are respectively proportional to the extent of etching of the first surface of the glass substrate. Therefore, when the concentration of the hydrogen fluoride solution is within the above range, it can prevent the first surface of the glass substrate from having a smaller texture structure after the texturing treatment due to the lower concentration of the hydrogen fluoride solution, resulting in poor light trapping, thereby ensuring that the first surface of the glass substrate has a higher light transmittance. In addition, it can also prevent the velvet structure formed on the first surface of the glass substrate after the velvet treatment from being larger in size due to the high concentration of the hydrogen fluoride solution, which may cause the velvet surface (i.e., the first surface of the glass substrate) to be easily accumulated with dust when it is exposed to the external environment for a long time. It further ensures that when the glass substrate is exposed to the external environment, the first surface itself has a high light transmittance for a long time.

[0083] Specifically, after the texturing treatment, a velvet surface is formed on the first surface of the glass substrate. The morphology, size, spacing between adjacent velvet structures, and dimensional uniformity of different velvet structures of the velvet surface can be determined according to the transmittance requirements for the first surface of the glass substrate in the actual application scenario.

[0084] For example, Figure 7 As shown, the velvet structure 17 of the velvet surface can be a semi-spherical concave structure recessed into the glass substrate 11. In this case, the semi-spherical concave structure recessed into the glass substrate 11 has an uneven surface characteristic, which is beneficial for increasing the specific surface area of ​​the velvet surface and ensuring that the first surface of the glass substrate 11 has a high light transmittance.

[0085] Exemplarily, the size of the velvet structure of the velvet surface is in the micron range. For example, the size of the velvet structure can be greater than or equal to 1 μm and less than or equal to 10 μm (such as 1 μm, 2 μm, 4 μm, 6 μm, 8 μm or 10 μm, etc.). In this case, the size of the velvet structure is relatively small, which is conducive to increasing the specific surface area of ​​the velvet surface, ensuring that the first surface of the glass substrate has a high light transmittance, and also helps prevent the velvet surface from having uneven morphological features and easily causing dust accumulation when in the external environment for a long time. This further ensures that when the glass substrate is exposed to the external environment, the first surface itself has a high light transmittance for a long time.

[0086] Exemplarily, the spacing between two adjacent velvet structures can be greater than or equal to 0.5 μm and less than or equal to 5 μm. For example, the spacing between two adjacent velvet structures can be 0.5 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm, etc. In this case, in the actual manufacturing process, since the ratio between the spacing between two adjacent velvet structures and the diameter of the solid particles is approximately 0.5:1, the spacing between two adjacent velvet structures is within the above range, which is beneficial to prevent the surface roughness of the velvet formed based on the mask pattern from being smaller due to the smaller size of the solid particles due to the smaller spacing between the two adjacent velvet structures, and the greater difficulty in forming the velvet. It is also beneficial to prevent the velvet from having a poor light trapping effect due to the smaller distribution density of the velvet structure due to the larger spacing between the two adjacent velvet structures, thereby ensuring that the first surface of the glass substrate has a higher light transmittance.

[0087] For example, the dimensional uniformity between different velvet structures can be less than 1. The dimensional uniformity refers to the difference between the largest and smallest velvet structures among all velvet structures, divided by the average size of all velvet structures. Therefore, when the dimensional uniformity between different velvet structures is less than 1, the sizes of the different velvet structures are relatively small, which helps ensure that the surface roughness of different regions of the first surface of the glass substrate is roughly the same, and helps ensure that different regions of the first surface of the glass substrate have high light transmittance.

[0088] like Figure 4As shown, after the texturing treatment, the mask layer needs to be removed. The process for removing the mask layer, the type of etchant, and the specific process conditions can be determined according to the material of the mask layer, and are not specifically limited here. For example, the type of etchant used to remove the mask layer includes but is not limited to acetone, acetic acid, toluene, and other organic solvents.

[0089] In addition, after the glass substrate is provided, and under the masking effect of the mask layer, before etching the first surface of the glass substrate using a wet etching process, the manufacturing method of the glass substrate according to the embodiments of the present application further includes the step of: Figure 4 As shown, the protective layer 18 is formed on the second surface side of the glass substrate 11. In this case, the presence of the protective layer 18 can prevent the second surface of the glass substrate 11 from being affected by the wet etching solution when the texturing treatment is performed on the first surface of the glass substrate 11, thereby facilitating the second surface of the glass substrate 11 to have higher flatness.

[0090] Specifically, the material and thickness of the protective layer are not specifically limited in the embodiments of the present application, as long as the second surface of the glass substrate can be protected from being affected by the wet etching solution during the texturing treatment. For example, the protective layer can be a paraffin layer or the like. The thickness of the protective layer can be greater than or equal to 0.5 mm.

[0091] As for the formation sequence of the protective layer, the protective layer can be formed on the second surface of the glass substrate after the glass substrate is provided and before the mask layer doped with solid particles is formed on the first surface of the glass substrate. Alternatively, as shown in Figure 7 As shown, the protective layer 18 can also be formed on the second surface of the glass substrate 11 after the mask layer 15 doped with solid particles 14 is formed on the first surface of the glass substrate 11 and before the solid particles 14 are selectively removed. Alternatively, the protective layer can also be formed on the second surface of the glass substrate after the solid particles are selectively removed and before the texturing treatment is performed on the first surface of the glass substrate.

[0092] The second aspect, as shown in Figure 8 and ​ The embodiments of the present application provide a glass substrate 11, which is manufactured by using the manufacturing method of the glass substrate provided in any one of the first aspect and various implementation manners thereof.

[0093] The third aspect, the embodiments of the present application provide a photovoltaic module, which includes: the glass substrate provided in the third aspect and various implementation manners thereof, a backsheet arranged opposite to the glass substrate, and a cell structure arranged between the glass substrate and the backsheet. The second surface of the glass substrate faces the cell structure.

[0094] The beneficial effects of the second aspect and the third aspect and various implementation manners thereof in the embodiments of the present application can be analyzed with reference to the beneficial effects in the first aspect and various implementation manners thereof, which will not be described herein.

[0095] In the above description, the technical details of the patterning, etching, etc. of each layer are not described in detail. However, it should be understood by those skilled in the art that the layers, regions, etc. of the required shape can be formed by various technical means. In addition, those skilled in the art can also design methods that are not exactly the same as the methods described above in order to form the same structure. In addition, although each embodiment is described above separately, this does not mean that the measures in each embodiment cannot be used advantageously in combination.

[0096] The embodiments of the present disclosure are described above. However, these embodiments are only for illustrative purposes, and are not intended to limit the scope of the present disclosure. The scope of the present disclosure is defined by the appended claims and their equivalents. Without departing from the scope of the present disclosure, those skilled in the art can make various substitutions and modifications, which should all fall within the scope of the present disclosure.

Claims

1. A method for manufacturing a glass substrate, characterized in that: include: providing a glass substrate; The glass substrate has a first side and a second side opposite to each other; A mask layer doped with solid particles is formed on the first surface of the glass substrate; among all the solid particles, the smallest solid particle has a size greater than the thickness of the mask layer; the material of the solid particles is different from the material of the mask layer, and the bottom of the solid particles is in contact with the first surface; selectively removing the solid particles to form a mask pattern penetrating the mask layer; Under the masking action of the mask layer, the first surface of the glass substrate is etched by a wet etching process, so that a textured surface is formed on the first surface of the glass substrate; The mask layer is removed.

2. The method for manufacturing a glass substrate according to claim 1, wherein: The step of forming a mask layer doped with solid particles on the first surface of the glass substrate comprises: forming a whole layer of dispersion liquid on the first surface; the dispersion liquid includes a masking liquid and the solid particles dispersed in the masking liquid; The dispersion is solidified to form the mask layer doped with solid particles.

3. The method for manufacturing a glass substrate according to claim 2, wherein: The concentration of the solid particles in the dispersion is greater than or equal to 1 mg / mL and less than or equal to 10 mg / mL.

4. The method for manufacturing a glass substrate according to claim 2, wherein: The masking fluid includes a resin solution.

5. The method for manufacturing a glass substrate according to claim 2, wherein: The solid particles are spherical solid particles; and / or, The solid particles are silicon dioxide particles; and / or, The size of the solid particles is greater than or equal to 1 μm and less than or equal to 10 μm; and / or, Different solid particles are evenly distributed.

6. The method for manufacturing a glass substrate according to claim 1, wherein: In the case that the solid particles are spherical solid particles, the thickness of the mask layer is equal to half of the average size of all the solid particles.

7. The method for manufacturing a glass substrate according to claim 1, wherein: The velvet surface has a velvet surface structure that is a hemispherical concave structure that is concave into the glass substrate; and / or, The velvet surface has a velvet structure with a size of micron order.

8. The method for manufacturing a glass substrate according to any one of claims 1 to 7, wherein: Under the masking action of the mask layer and through the hydrogen fluoride solution, the first surface of the glass substrate is etched; wherein, The concentration of the hydrogen fluoride solution is greater than or equal to 4% and less than or equal to 12%; and / or the etching time is greater than or equal to 10 minutes and less than or equal to 30 minutes.

9. The method for manufacturing a glass substrate according to any one of claims 1 to 7, wherein: After providing a glass substrate, before etching the first surface of the glass substrate using a wet etching process under the masking action of the mask layer, the method for manufacturing the glass substrate further includes: A protective layer is formed on one side of the second surface of the glass substrate.

10. A glass substrate, characterized in that: The glass substrate is manufactured by the method for manufacturing a glass substrate according to any one of claims 1 to 9.

11. A photovoltaic module, characterized in that: include: The glass substrate according to claim 10, a back plate disposed opposite to the glass substrate; and a battery structure arranged between the glass substrate and the back plate; the second surface of the glass substrate faces the battery structure.

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