Perovskite solar cell based on ground glass substrate and preparation method thereof

Abstract

The application discloses a kind of perovskite solar cells based on frosted glass substrate and preparation method thereof, belong to perovskite solar cell technical field.The perovskite solar cell includes frosted glass substrate and cell function layer module;Frosted glass substrate light entrance surface is the frosted surface with continuous gradient composite concave-convex structure, surface roughness Ra is 50-200 nm;In this case, frosted surface can form gradient refractive index transition at air-glass interface to reduce Fresnel reflection loss, diffuse and angle reform to direct light to extend the propagation path of photon in perovskite layer, and direction modulation to scattered light in weak light environment to improve utilization rate;In addition, the frosted surface of frosted glass substrate can produce soft diffuse reflection to shield internal structure, inhibit glare, smooth to ensure uniform deposition of non-light entrance surface function layer, while ensuring efficiency and stability, and widen BIPV application scenario.

Description

Technical Field

[0001] This invention belongs to the field of perovskite solar cell technology, and relates to a perovskite solar cell based on a frosted glass substrate and its fabrication method. Background Technology

[0002] The high power generation capacity of perovskite solar cells under indoor lighting has made them an ideal power supply solution for low-power devices such as IoT sensors and electronic tags. They also have broad application prospects in the field of building-integrated photovoltaics (BIPV).

[0003] Currently, perovskite solar cells used in BIPV devices all use glass with high light transmittance and a smooth light-receiving surface as the substrate. However, their practical application faces the following key technical bottlenecks: First, under direct sunlight conditions such as early morning, late afternoon, and high-latitude regions, the reflectivity of the air-glass interface increases dramatically, and some light passes through or escapes without being absorbed. In contrast, under weak light scattering conditions such as cloudy days or building backlighting, the light is mainly scattered light at random angles. Smooth glass has limited ability to capture this scattered light, allowing only small-angle scattered light to enter the cell with low reflectivity. Most large-angle, randomly oriented scattered light is reflected and escapes through the smooth surface, significantly reducing power generation efficiency. Second, the high light transmittance of smooth glass makes internal structures, such as laser-etched lines, visible, affecting the aesthetics of the building facade. Furthermore, specular reflection can easily cause glare pollution, limiting its application in BIPV scenarios.

[0004] To address these issues, existing technologies texturize the non-light-incident surface of the glass substrate, which can improve light absorption, but excessive surface roughness can affect the deposition of upper functional thin films and reduce battery stability and efficiency. In addition, chemical etching of the light-incident surface of smooth glass can reduce specular reflection and shield internal structures, but it significantly sacrifices light transmittance and weakens the battery's power generation advantage. Furthermore, some studies have explored attaching anti-reflective films to the light-incident surface of smooth glass, but these films rely on complex processes such as nanofabrication and photolithography, which are lengthy and costly, making them unsuitable for large-scale production.

[0005] In summary, existing technologies cannot effectively solve the core problems caused by smooth glass substrates, such as low light utilization and limited application scenarios. Therefore, it is urgent to develop a perovskite solar cell with a novel glass substrate structure and its preparation method to promote the industrialization of perovskite solar cells for use in BIPV devices. Summary of the Invention

[0006] To address the technical problems of existing perovskite solar cells, such as low light absorption and utilization efficiency and insufficient light capture capacity due to smooth glass substrates, as well as the visibility of internal structures and glare pollution during application, this invention provides a perovskite solar cell based on a frosted glass substrate and its fabrication method. By setting the light-incident surface of the perovskite solar cell as a frosted surface with micro-nano-level uneven structures, the problems of severe interface reflection, insufficient absorption of direct light, and poor light capture capacity of weak light scattered light on smooth glass substrates are effectively improved. At the same time, the internal structure can be shielded and specular reflection glare can be reduced. While ensuring the photoelectric conversion efficiency of the cell, its application adaptability in the BIPV field is significantly improved.

[0007] This invention is achieved through the following technical solution: A perovskite solar cell based on a frosted glass substrate, comprising: A frosted glass substrate and a battery functional layer module located on one side of the frosted glass substrate; The frosted glass substrate has a first surface and a second surface disposed opposite to each other; the first surface is a frosted surface formed by frosting treatment, the frosted surface has a micro-nano-level concave-convex structure, and the frosted surface is the light-incident surface of the perovskite solar cell; The battery functional layer module is disposed on the second surface of the frosted glass substrate. The battery functional layer module includes a conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer stacked sequentially.

[0008] Preferably, the surface roughness Ra of the frosted surface is 50 nm-200 nm.

[0009] Preferably, the micro-nano-level concave-convex structure is a continuous gradient composite concave-convex structure formed by sandblasting with sand particles of multiple sizes.

[0010] Preferably, the continuous gradient composite concave-convex structure includes: a base concave-convex structure, a transition concave-convex structure, and a surface concave-convex structure, and the base concave-convex structure, the transition concave-convex structure, and the surface concave-convex structure together constitute the surface morphology of the frosted surface. Wherein, the structural feature size of the substrate concave-convex structure is larger than the structural feature size of the transition concave-convex structure, and the structural feature size of the transition concave-convex structure is larger than the structural feature size of the surface concave-convex structure.

[0011] Preferably, the base uneven structure constitutes the basic morphology of the frosted surface, the transition uneven structure is formed on the surface of the base uneven structure, and the surface uneven structure is formed on the surface of the base uneven structure and / or the surface of the transition uneven structure. The three elements are superimposed on each other to form the continuous gradient composite concave-convex structure.

[0012] Preferably, the substrate uneven structure is formed by sandblasting with sand particles of a first diameter, the transition uneven structure is formed by sandblasting with sand particles of a second diameter, and the surface uneven structure is formed by sandblasting with sand particles of a third diameter. The first particle size of the sand is 80-120 mesh, the second particle size of the sand is 300-500 mesh, and the third particle size of the sand is 700-1000 mesh.

[0013] A method for fabricating a perovskite solar cell based on a frosted glass substrate includes the following steps: S1. A smooth glass substrate is provided, the smooth glass substrate having two surfaces arranged opposite to each other; one surface of the smooth glass substrate is frosted to form a frosted surface with a micro-nano-level uneven structure, thus obtaining the frosted glass substrate; the frosted surface is the light-incident surface of the perovskite solar cell; S2. A conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer are sequentially prepared on the side of the frosted glass substrate opposite to the frosted surface to obtain a perovskite solar cell based on the frosted glass substrate.

[0014] Preferably, the frosting treatment of one side surface of the smooth glass substrate in step S1 includes: The smooth glass substrate is subjected to a first-stage sandblasting treatment on one side surface using abrasive grains of the first size, forming a substrate concave-convex structure on one side surface of the smooth glass substrate, thus obtaining a first substrate with a substrate concave-convex structure. A second-stage sandblasting process is performed on the surface after the first-stage sandblasting treatment using sand particles of the second size, forming a transitional uneven structure on the uneven surface of the substrate to obtain a second substrate. A third-stage sandblasting process is performed on the surface after the second-stage sandblasting, using a third-size abrasive grain to form a surface concave-convex structure on the surface of the substrate and / or the transition concave-convex structure, thereby forming a frosted surface with a continuous gradient composite concave-convex structure, thus obtaining the frosted glass substrate.

[0015] Preferably, the materials of the first-size sand particles, the second-size sand particles, and the third-size sand particles are selected from any one or more of corundum, silicon carbide, quartz sand, or glass beads.

[0016] Preferably, prior to step S1, the method further includes: The smooth glass substrate is cleaned using any one or more of ultrapure water, ethanol, and deionized water. The smooth glass substrate is preheated to 50-70°C and held for 20-40 minutes.

[0017] Compared with the prior art, the present invention has the following beneficial technical effects: This invention provides a perovskite solar cell based on a frosted glass substrate, where the light-incident surface of the perovskite solar cell is configured as a frosted surface with a micro-nano-scale uneven structure. The frosted surface is formed by sandblasting with multi-level particle sizes, creating a continuous gradient composite uneven structure composed of nested, superimposed, and fused substrate uneven structures, transition uneven structures, and surface uneven structures. The surface roughness Ra of the frosted surface is ultimately controlled to be 50-200 nm. This frosted surface can form a gradient refractive index transition at the air-glass interface, significantly reducing Fresnel reflection loss; simultaneously, it effectively diffuses and reshapes direct light, extending the propagation path of photons within the perovskite layer, increasing the photon absorption probability, and reducing the phenomenon of light directly penetrating and escaping without being absorbed. For large-angle scattered light in low-light environments such as cloudy days and building backlighting, it can modulate large-angle scattered light, which would otherwise easily escape due to reflection from a smooth glass surface, into effective light that meets the incident conditions. At the same time, it directionally calibrates small-angle scattered light that can be incident, significantly improving the capture and utilization efficiency of scattered light.

[0018] Meanwhile, the frosted surface can create a soft diffuse reflection effect, which can effectively shield the internal structure and functional layer edges of the battery, significantly suppressing mirror glare pollution, without reducing light incident efficiency due to excessive roughness, thus balancing photovoltaic performance and architectural aesthetics. Furthermore, the non-light-incident surface of the frosted glass substrate maintains its smooth characteristics, which is conducive to the uniform and dense film formation of functional layers such as conductive oxides and charge carrier transport layers, reducing interface defects and charge carrier recombination, further ensuring the photoelectric conversion efficiency and long-term working stability of the battery, and greatly expanding the practical application scenarios of perovskite solar cells in the BIPV field. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a schematic diagram of the structure of a perovskite solar cell based on a frosted glass substrate provided in an embodiment of the present invention; Figure 2 A flowchart illustrating a method for fabricating a perovskite solar cell based on a frosted glass substrate, provided by this invention; Figure 3 A flowchart illustrating another method for fabricating a perovskite solar cell based on a frosted glass substrate provided by the present invention; Figure 4 The integrated sphere transmittance spectra of the frosted glass substrate of Embodiment 1 and the smooth glass substrate of Comparative Example 1 are shown. Figure 5 The current density-voltage curves of the perovskite solar cell based on a frosted glass substrate in Example 1 of the present invention and the perovskite solar cells of Comparative Examples 1-4 were obtained under a light irradiation condition of 300 lux. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0022] The present invention provides a perovskite solar cell based on a frosted glass substrate, comprising: a frosted glass substrate and a cell functional layer module located on one side of the frosted glass substrate.

[0023] The frosted glass substrate has a first surface and a second surface arranged opposite to each other. Here, the first surface is a frosted surface formed by a frosting process, and the frosted surface is the light-incident surface of the perovskite solar cell. That is, when external light enters the perovskite solar cell, it first passes through the frosted surface, and then enters the interior of the cell's functional layer module through the frosted surface.

[0024] In this application, the battery functional layer module is disposed on the second surface of the frosted glass substrate. The battery functional layer module includes a conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer stacked sequentially.

[0025] In this case, the second surface can be a smooth surface, which facilitates the uniform and dense deposition of each functional layer in the battery functional layer module, reduces interface defects and carrier recombination, and thus ensures that the battery has high photoelectric conversion efficiency and good stability.

[0026] In this embodiment, the frosted surface has a micro-nano-level uneven structure, which is preferably a continuous gradient composite uneven structure formed by sandblasting with multi-sized abrasive particles. The continuous gradient composite uneven structure may include: a substrate uneven structure, a transition uneven structure, and a surface uneven structure.

[0027] It should be noted that the base concave-convex structure, the transition concave-convex structure, and the surface concave-convex structure are all irregular concave-convex structures with non-periodic distribution. That is, the continuous gradient composite concave-convex structure is not composed of concave-convex units of a single size, but is a continuously changing gradient composite concave-convex structure formed by concave-convex units of multiple sizes nesting and superimposing with each other to achieve a smooth transition.

[0028] Specifically, the uneven structure of the substrate can be formed by sandblasting with sand particles of a first particle size, where the mesh size of the first particle size can be 80-120 mesh. Here, the uneven structure of the substrate can constitute the basic morphology of the frosted surface.

[0029] For example, a smooth glass substrate can be sandblasted with 100-mesh abrasive to create a textured surface. The structural feature size of this textured surface is larger than that of the transition texture and also larger than that of the surface texture. For example, the structural feature size of the textured surface ranges from 0.8 to 2.0 μm.

[0030] It should be noted that the structural feature size refers to the statistical average peak and valley depth of the irregular concave and convex structure along the thickness direction of the frosted glass substrate. In other words, the structural feature size is the average longitudinal feature scale obtained based on the overall surface morphology statistics, rather than the individual size of a single concave and convex structure.

[0031] Here, the surface roughness Ra of the glass after sandblasting with sand of the first particle size is greater than 500 nm.

[0032] In this way, since the glass surface with the formed uneven structure contains countless local slopes, each with a different local normal direction, when light is incident at a large angle and not perpendicular, a large-angle incident light beam can be decomposed into multiple local light beams with small angles relative to the local slopes. This allows more than 95% of the local light rays to successfully enter the interior of the glass substrate with low reflection and high refraction, significantly reducing the reflection loss before incident in this scenario and increasing the effective incident light intensity.

[0033] Specifically, the transitional uneven structure can be an uneven structure formed by sandblasting with a second-diameter abrasive grain, the mesh size of which can be 300-500 mesh. Here, the transitional uneven structure can be formed on the overall surface of the base uneven structure; that is, the second-diameter abrasive grain can act on the glass surface after sandblasting with the first-diameter abrasive grain. Because the structural undulations of the base uneven structure are relatively severe, the transitional uneven structure can smooth, blunt, and homogenize the undulating contours of the base uneven structure. The two are nested, superimposed, and fused together to form a continuously transitioning composite morphology, thereby achieving homogenization and adjustment of the surface roughness of the glass after the first-stage sandblasting treatment.

[0034] For example, a second sandblasting treatment can be performed on the glass surface with an already formed base uneven structure using 400-mesh abrasive to create a transition uneven structure. The structural feature size of the transition uneven structure is smaller than that of the base uneven structure but larger than that of the surface uneven structure. For example, the range of the structural feature size of the transition uneven structure is 0.3-0.8 μm.

[0035] Here, the surface roughness Ra of the glass after sandblasting with second-diameter sand particles is 150 nm-300 nm.

[0036] In this way, after the light is initially deflected by the uneven structure of the substrate, the uneven structure can make its diffusion direction distribution more uniform, allowing the light to enter the battery functional layer module at a more uniform and suitable angle.

[0037] Specifically, the surface unevenness structure can be formed by sandblasting with a third-diameter abrasive grains, with the third-diameter abrasive grains having a mesh size of 700-1000. Here, the surface unevenness structure can be formed on the surface of the base unevenness structure and / or the surface of the transition unevenness structure. That is, the third-diameter abrasive grains can act on the glass surface after the second-stage sandblasting treatment, smoothing the overall morphological undulations and allowing the surface unevenness structure to be nested, superimposed, and fused with the base unevenness structure and the transition unevenness structure. These three elements fuse and superimpose to form a continuous gradient composite unevenness structure.

[0038] For example, 800-mesh abrasive can be used to perform a third sandblasting treatment on the composite morphology surface formed by the first two sandblasting processes to create a surface texture.

[0039] The range of the structural feature dimensions of the surface uneven structure is 0.1-0.3 μm.

[0040] Here, the surface roughness Ra of the glass after sandblasting with sand of the third particle size is 50 nm-200 nm.

[0041] In this way, small-angle direct light can be finely diffused at the air-glass incident light interface, modulating the unidirectional direct light into diffuse light that propagates at multiple angles. This allows the light to pass through the glass substrate and then enter the perovskite layer in a non-linear direction, effectively extending the propagation path and residence time of photons within the perovskite layer, increasing the probability of photon absorption, and reducing the situation where light passes through directly without being absorbed. Furthermore, large-angle scattered light that is easily reflected and escapes by smooth glass is transformed into small-angle light that meets the incident conditions. The propagation direction of the originally incident small-angle scattered light is further calibrated, significantly improving the capture and utilization efficiency of weak light scattered light.

[0042] In this application, the substrate uneven structure, the transition uneven structure, and the surface uneven structure together constitute the surface morphology of the frosted surface. The final surface roughness Ra of the frosted surface is 50 nm-200 nm.

[0043] Within this roughness range, the frosted glass substrate can form a continuous gradient refractive index distribution at the air-glass interface under direct light, with the refractive index smoothly transitioning from air to glass, significantly reducing Fresnel reflection loss. Multi-angle diffusion and incident angle reshaping of direct light transform large-angle direct light into small-angle incident light that is easier to enter the perovskite layer, increasing the propagation path length and absorption probability of light in the perovskite layer, and reducing the probability of light directly penetrating and escaping.

[0044] Meanwhile, in low-light environments, the direction of large-angle scattered light is redistributed to an angle that is easier to enter the interior of the battery functional layer module, and the propagation direction of small-angle scattered light is calibrated, so that the incident light can illuminate the entire perovskite layer with a more uniform light intensity distribution, which greatly improves the capture and utilization efficiency of weak light scattered light, thereby significantly enhancing the light absorption and utilization rate of perovskite solar cells under full incident angle, all weather and low light conditions.

[0045] In addition, the frosted surface in the frosted glass substrate can form a soft diffuse reflection effect, which can effectively shield the internal structure such as laser engraving marks and functional layer edges inside the cell, suppress glare pollution and specular reflection, and will not affect the light incident efficiency due to excessive roughness. While ensuring the high photoelectric conversion efficiency of perovskite solar cells, it greatly improves their appearance adaptability and scenario applicability in the field of building-integrated photovoltaics.

[0046] It should be understood that the present invention does not impose any particular restrictions on the material selection, thickness, and fabrication process of the transparent conductive oxide layer, the first carrier transport layer, the perovskite layer, the second carrier transport layer, the top electrode layer, and the encapsulation layer, as long as the purpose of the present invention can be achieved.

[0047] Secondly, see Figure 2 The present invention also provides a method for fabricating a perovskite solar cell based on a frosted glass substrate, comprising the following steps: S1. Provide a smooth glass substrate with two surfaces arranged opposite each other; perform frosting treatment on one side of the smooth glass substrate to form a frosted surface with micro-nano-level uneven structure, thus obtaining a frosted glass substrate; the frosted surface is the light-incident surface of the perovskite solar cell.

[0048] S2. A conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer are sequentially fabricated on the side of the frosted glass substrate opposite to the frosted surface to obtain a perovskite solar cell based on the frosted glass substrate.

[0049] In this application, the frosting treatment is preferably a multi-level particle size sandblasting treatment; that is, a smooth glass surface is sandblasted stepwise with sand particles of progressively increasing mesh size to form a base concave-convex structure, a transition concave-convex structure and a surface concave-convex structure in sequence, so that the three structures are nested, superimposed and fused together to form a frosted surface with a continuous gradient composite morphology.

[0050] join Figure 3 This invention provides another method for fabricating perovskite solar cells based on a frosted glass substrate, comprising the following steps: S11. Pre-treat the smooth glass substrate; In this embodiment, the smooth glass substrate can be cleaned using any one or more of ultrapure water, ethanol, and deionized water, followed by drying with nitrogen gas. The cleaned smooth glass substrate is then placed in an oven, preheated to 50-70°C for 20-40 minutes, and finally purged with an ionizer to remove residual particles. This reduces localized coating differences caused by temperature gradients during sandblasting, resulting in more uniform abrasive particle coating.

[0051] S12. The first-stage sandblasting treatment is performed on one side surface of the smooth glass substrate using sand particles of the first size to obtain a first substrate with a substrate concave-convex structure. In this application, a first-stage sandblasting treatment can be performed on one side surface of a smooth glass substrate using a first-particle-size abrasive grains of 80-120 mesh to obtain a first substrate with a substrate uneven structure.

[0052] The process parameters for the first stage of sandblasting are as follows: sandblasting pressure: 0.18 MPa - 0.25 MPa, nozzle distance: 150 mm - 200 mm, scanning speed: 5 mm / s - 8 mm / s, sandblasting time: 12 s - 15 s, and sand flow rate: 8 kg / min - 10 kg / min.

[0053] Here, after the first stage of sandblasting, the first substrate needs to be ultrasonically cleaned with ultrapure water. For example, the ultrasonic frequency is 80 kHz, the cleaning time is 30 min, and the temperature is 40°C, in order to remove the floating dust and abrasive residue after the first stage of sandblasting.

[0054] S13. The surface after the first-stage sandblasting is treated with second-size sand particles to form a transitional uneven structure on the uneven surface of the substrate, thus obtaining the second substrate.

[0055] In this application, a second-stage sandblasting treatment can be performed on the surface after the first-stage sandblasting treatment using 300-500 mesh abrasive particles to form a transitional uneven structure on the uneven surface of the substrate, thereby obtaining a second substrate.

[0056] The process parameters for the second-stage sandblasting treatment are as follows: sandblasting pressure: 0.12 MPa - 0.18 MPa, nozzle distance: 200 mm - 250 mm, scanning speed: 8 mm / s - 10 mm / s, sandblasting time: 8 s - 10 s, and sand flow rate: 6 kg / min - 8 kg / min.

[0057] Here, after the second-stage sandblasting, the light-receiving surface of the glass is ultrasonically cleaned with ultrapure water. For example, the ultrasonic frequency is 80 kHz, the cleaning time is 30 min, and the temperature is 40℃, to remove the floating dust and abrasive residue after the second-stage sandblasting.

[0058] S14. The surface after the second-stage sandblasting is treated with third-stage sand particles to form a surface concave-convex structure on the concave-convex structure surface and / or the transition concave-convex structure surface, so as to form a frosted surface with a continuous gradient composite concave-convex structure, and obtain a frosted glass substrate.

[0059] In this application, a third-stage sandblasting treatment can be performed on the surface after the second-stage sandblasting treatment using 700-1000 mesh third-stage sandblasting particles to form a surface concave-convex structure on the substrate concave-convex structure surface and / or the transition concave-convex structure surface, so as to form a frosted surface with a continuous gradient composite concave-convex structure, thereby obtaining a frosted glass substrate.

[0060] The process parameters for the third-stage sandblasting treatment are as follows: sandblasting pressure: 0.08 MPa-0.12 MPa, nozzle distance: 250 mm-300 mm, scanning speed: 10 mm / s-12 mm / s, sandblasting time: 5 s-7 s, and sand flow rate: 4 kg / min-6 kg / min.

[0061] Here, after the third-stage sandblasting, the frosted glass substrate needs to be finally cleaned. For example, firstly, ultrasonic cleaning is performed using ultrapure water: the ultrasonic frequency is 80 kHz, the cleaning time is 30 min, and the temperature is 40℃, to remove surface dust and abrasive residue; then, chelation cleaning is used: the substrate is immersed in a 0.5 mol / L ammonium citrate solution for 15 min to complex and remove trace metal ions (such as Fe) remaining from the abrasive residue. 3+ Na + The detection limit for metal ions is ≤0.1 ppm; finally, plasma cleaning is performed: under an argon atmosphere, the power is 100 W and the time is 5 min to remove surface organic contaminants and hydroxyl groups.

[0062] In addition, the cleaned frosted glass substrate should be immediately placed in a nitrogen cabinet for storage to prevent recontamination by dust and moisture in the air.

[0063] In the embodiments of this application, the materials of the first-size sand grains, the second-size sand grains, and the third-size sand grains are selected from any one or more combinations of corundum (Al2O3), silicon carbide (SiC), quartz sand, or glass beads, wherein the sand grains have a Mohs hardness ≥9.0 and a purity ≥99%; thus, they can effectively etch smooth glass substrates and have stable chemical properties, making it difficult to introduce impurities.

[0064] S21. A conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer are sequentially fabricated on the side of the frosted glass substrate opposite to the frosted surface to obtain a perovskite solar cell based on the frosted glass substrate.

[0065] In this application, the side of the frosted glass substrate opposite to the frosted surface refers to the second surface. That is, a conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer are sequentially prepared on the second surface of the frosted glass substrate to obtain a perovskite solar cell based on the frosted glass substrate.

[0066] It should be noted that if the first carrier transport layer is one of the hole transport layer and the electron transport layer, then the second carrier transport layer is the other of the hole transport layer and the electron transport layer. This application does not limit this, and the following is an example of the first carrier transport layer being the hole transport layer and the second carrier transport layer being the electron transport layer.

[0067] The material of the conductive oxide layer is not particularly limited and can be any material or combination thereof known to those skilled in the art. For example, it can be made of any one or more of indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO), fluorine-doped tin oxide (FTO), indium tungsten oxide (IWO), indium cerium oxide (ICO), and Ag nanowires. The conductive oxide layer can be prepared by magnetron sputtering, and the thickness of the conductive oxide layer can be in the range of 100 nm to 150 nm.

[0068] Specifically, the material of the first carrier transport layer is not particularly limited and can be a material or combination thereof known to those skilled in the art, such as NiOx, MoS, MoO, CuS, CuSCN, PTAA, PEDOT, or Spiro. In any one or at least two combinations of MeOTAD, the first carrier transport layer can be prepared by reactive sputtering, and the thickness of the first carrier transport layer can be in the range of 15 nm - 20 nm.

[0069] Specifically, the material of the perovskite layer is not particularly limited and can be a material or combination thereof known to those skilled in the art. For example, the perovskite precursor solution system can be Cs. x FA 1-x PbI y Br 3-y The system has x ranging from 0 to 0.3 and y ranging from 1.5 to 3. The solvent for the perovskite precursor solution is a mixture of N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP), with a volume ratio of DMF to NMP of 4:1 to 8:1. The concentration of the perovskite precursor solution is 0.8 mol / L to 1.4 mol / L. The perovskite layer can be formed by coating the perovskite precursor solution onto the first carrier transport layer using any of the following methods: spin coating, blade coating, slot coating, or screen printing. The perovskite precursor solution is then annealed at 100℃ to 170℃ for 10 min to 60 min.

[0070] Specifically, the material of the second carrier transport layer is not particularly limited and can be a material or combination thereof known to those skilled in the art, such as SnO2, TiO2, WO3, Nb2O5, C 60 Or any one or a combination of at least two of the PCBMs. The second carrier transport layer can be formed by vapor deposition, and the thickness of the second carrier transport layer can range from 15 nm to 30 nm.

[0071] Specifically, the material of the top electrode layer is not particularly limited and can be any material or combination thereof known to those skilled in the art. For example, it can be any one or a combination of at least two of Au, Ag, Cu, Al, Cr, Mo, carbon, fluorine-doped tin oxide, indium-doped tin oxide, aluminum-doped zinc oxide, boron-doped zinc oxide, or aluminum-doped tin oxide. The top electrode layer can be formed by vapor deposition, and the thickness of the top electrode layer can range from 70 nm to 120 nm.

[0072] Specifically, an encapsulation layer can be provided on the side of the top electrode layer facing away from the frosted glass substrate to protect the battery from the corrosion of moisture and oxygen in the environment. The encapsulation layer has a multi-layer stacked structure, which includes a first inorganic encapsulation layer, an organic encapsulation layer and a second inorganic encapsulation layer from bottom to top. The first inorganic encapsulation layer and the second inorganic encapsulation layer are both composed of oxide films or nitride films with a thickness of 1μm-3μm, and are prepared by at least one of the following processes: chemical vapor deposition, plasma-enhanced chemical vapor deposition, sputtering or sublimation. The organic encapsulation layer is made of acrylic resin, epoxy acrylic resin or epoxy resin with a thickness of 5μm-15μm. The ink composition is coated onto the substrate by any one of the following methods: inkjet printing, spraying, roller coating, blade coating or spin coating, and cured by heating or ultraviolet exposure to form a polymer film.

[0073] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0074] Example 1 See Figure 1 This embodiment discloses a schematic diagram of a perovskite solar cell based on a frosted glass substrate. The perovskite solar cell based on the frosted glass substrate includes: a frosted glass substrate, a conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer.

[0075] Here, the method for preparing the frosted glass substrate is as follows: A smooth glass substrate was pretreated using a 3.2 mm thick, Mohs hardness of 6.8, and flexural strength of 100 MPa ultra-white smooth photovoltaic glass as the substrate. The ultra-white smooth photovoltaic glass was ultrasonically cleaned sequentially with acetone, ethanol, and deionized water, each cleaning session lasting 15 minutes, followed by drying with nitrogen. The cleaned glass was then placed in an oven and preheated at 60°C for 30 minutes. After preheating, an ionization air gun was used to clean the surface of the ultra-white smooth photovoltaic glass to remove any remaining microparticles.

[0076] The first stage of sandblasting was performed on one side of the pretreated smooth glass substrate: a CNC multi-gun sandblasting system was used, with 100-mesh white corundum (Al2O3, Mohs hardness 9.0, purity 99.5%) as the first particle size. The process parameters were set as follows: sandblasting pressure 0.20 MPa, nozzle distance 180 mm, robotic arm scanning speed 6 mm / s, sandblasting time 13 s, and abrasive flow rate 9 kg / min. After the first stage of sandblasting, the substrate was immediately ultrasonically cleaned with 40℃ ultrapure water at 80 kHz for 30 min, and then dried with nitrogen.

[0077] Second-stage sandblasting: 400-mesh silicon carbide (SiC, Mohs hardness 9.5, purity 99%) was used as the second particle size. Process parameters were set as follows: sandblasting pressure 0.15 MPa, nozzle distance 220 mm, scanning speed 9 mm / s, sandblasting time 9 s, and abrasive flow rate 7 kg / min. After the second-stage sandblasting, the sample was ultrasonically cleaned with 40℃ ultrapure water at 80 kHz for 30 min, and then dried with nitrogen.

[0078] The third stage of sandblasting: 800-mesh quartz sand (SiO2, Mohs hardness 9.0, purity 99.9%) was used as the third particle size. Process parameters were set as follows: sandblasting pressure 0.10 MPa, nozzle distance 280 mm, scanning speed 11 mm / s, sandblasting time 6 s, and sand flow rate 5 kg / min. After the third stage of sandblasting, the sand was ultrasonically cleaned with 40℃ ultrapure water for 30 min, and then immersed in a 0.5 mol / L ammonium citrate solution for 15 min to complex and remove residual trace metal ions (such as Fe). 3+ Na + ).

[0079] Finally, the substrate was rinsed three times with deionized water and then subjected to plasma cleaning (100W power, 5min) under an argon atmosphere to remove organic contaminants and activate the surface. The cleaned frosted glass substrate was immediately placed in a nitrogen cabinet for storage. The resulting frosted surface had a surface roughness Ra of approximately 80 nm and exhibited a continuous gradient composite uneven structure formed by multi-level particle size blasting.

[0080] Specifically, the fabrication method of perovskite solar cells is as follows: On the second surface of the prepared frosted glass substrate, that is, the side opposite to the frosted surface, the functional layers are deposited sequentially: Conductive oxide layer: A 120 nm thick ITO thin film is deposited on the second surface using a magnetron sputtering process to serve as a transparent conductive electrode.

[0081] First carrier transport layer: A NiO layer with a thickness of 18 nm is deposited on the conductive oxide layer using reactive sputtering. X film.

[0082] Perovskite layer: Prepare a perovskite precursor solution; the solution system is Cs 0.1 FA 0.9 PbI 2.7 Br 0.3 The solvent was N,N-dimethylformamide (DMF):N-methylpyrrolidone (NMP) = 4:1 (volume ratio), and the concentration of the perovskite precursor solution was 1.2 mol / L. The perovskite precursor solution was coated onto the first carrier transport layer using a blade coating method, and then annealed at 150 °C for 30 min to form the perovskite layer.

[0083] Second carrier transport layer: C is sequentially deposited on the perovskite layer. 60 The BCP serves as the electron transport layer, and the CCP as the cathode buffer layer. 60 The vapor deposition thickness of the first type is 25 nm, and the vapor deposition rate is 0.3 Å / s; the vapor deposition thickness of the second type is 5 nm, and the vapor deposition rate is 0.1 Å / s.

[0084] Top electrode layer: A Cu metal electrode layer with a thickness of 100 nm is deposited on the second carrier transport layer as the top electrode layer; Encapsulation layer: A 2 μm thick silicon nitride (SiN) layer is deposited on the side of the top electrode layer away from the glass using plasma-enhanced chemical vapor deposition (PECVD). x A 10 μm thick acrylic resin precursor was deposited using inkjet printing, followed by UV irradiation for 3 minutes to form a polymer film. A 2 μm thick silicon nitride (SiN) film was then deposited using plasma-enhanced chemical vapor deposition (PECVD). x )film.

[0085] Through the above steps, a complete perovskite solar cell based on a frosted glass substrate is obtained.

[0086] Comparative Example 1 The only difference between this comparative example and Example 1 is the glass substrate. All other preparation processes (including the materials, thicknesses, and deposition conditions of the conductive oxide layer, the first carrier transport layer, the perovskite layer, the second carrier transport layer, the top electrode layer, and the encapsulation layer) are exactly the same as those in Example 1.

[0087] The glass substrate used in this comparative example is a smooth glass substrate, and its preparation method is as follows: A piece of ultra-white, smooth photovoltaic glass (3.2 mm thick, Mohs hardness 6.8, flexural strength 100 MPa) of the same specifications as in Example 1 was used as the smooth glass substrate. The smooth glass substrate was ultrasonically cleaned sequentially with acetone, ethanol, and deionized water, each cleaning session lasting 15 minutes, followed by drying with nitrogen. The cleaned glass was placed in an oven and preheated at 60°C for 30 minutes. After preheating, the glass surface was swept with an ion gun to remove any remaining microparticles. No sandblasting treatment was performed, and subsequent fabrication processes were the same as in Example 1, resulting in a perovskite solar cell.

[0088] Comparative Example 2 The only difference between this comparative example and Example 1 is the frosting process of the glass substrate. All other preparation processes (including the materials, thicknesses, and deposition conditions of the conductive oxide layer, the first carrier transport layer, the perovskite layer, the second carrier transport layer, the top electrode layer, and the encapsulation layer) are exactly the same as those in Example 1.

[0089] The frosted glass substrate in this comparative example is prepared using the following method: Pretreatment of the smooth glass substrate: Take the same ultra-white smooth photovoltaic glass of the same specifications as in Example 1 (thickness 3.2 mm, Mohs hardness 6.8, bending strength 100 MPa), and clean it with acetone, ethanol and deionized water for 15 min each. After drying with nitrogen, put it in an oven and preheat it at 60°C for 30 min. Then, clean the surface with an ion air gun.

[0090] One side of the pretreated smooth glass substrate was subjected to a single sandblasting treatment: the process parameters were exactly the same as the first-stage sandblasting in Example 1, using 100-mesh white corundum (Al2O3, Mohs hardness 9.0, purity 99.5%) as abrasive; the sandblasting pressure was 0.20 MPa, the nozzle distance was 180 mm, the robotic arm scanning speed was 6 mm / s, the sandblasting time was 13 s, and the abrasive flow rate was 9 kg / min. After treatment, the substrate was ultrasonically cleaned for 30 min with ultrapure water at 40°C and 80 kHz, and then dried with nitrogen to remove all abrasive residue and debris. The subsequent steps for fabricating the functional layer on the opposite side of the sandblasted surface were the same as in Example 1, resulting in a perovskite solar cell.

[0091] Comparative Example 3 The difference between this comparative example and Example 1 is that the frosting process of the glass substrate is different. The rest of the preparation process (including the materials, thickness, deposition conditions, etc. of the conductive oxide layer, the first carrier transport layer, the perovskite layer, the second carrier transport layer, the top electrode layer and the encapsulation layer) are exactly the same as those of Example 1.

[0092] The frosted glass substrate in this comparative example is prepared using the following method: Pretreatment of the smooth glass substrate: Take the same ultra-white smooth photovoltaic glass of the same specifications as in Example 1 (thickness 3.2 mm, Mohs hardness 6.8, bending strength 100 MPa), and clean it with acetone, ethanol and deionized water for 15 min each. After drying with nitrogen, put it in an oven and preheat it at 60°C for 30 min. Then, clean the surface with an ion air gun.

[0093] One side surface of the pretreated smooth glass substrate was subjected to a single sandblasting treatment: the process parameters were exactly the same as the second-stage sandblasting in Example 1, using 400-mesh silicon carbide (SiC, Mohs hardness 9.5, purity 99%) as abrasive; the sandblasting pressure was 0.15 MPa, the nozzle distance was 220 mm, the scanning speed was 9 mm / s, the sandblasting time was 9 seconds, and the abrasive flow rate was 7 kg / min. After treatment, the substrate was ultrasonically cleaned for 30 min with ultrapure water at 40°C and a frequency of 80 kHz using a cleaning machine, and then dried with nitrogen to remove all abrasive residues and debris. The subsequent steps for fabricating the functional layer on the opposite side of the sandblasted surface were the same as in Example 1, resulting in a perovskite solar cell. Comparative Example 4 The difference between this comparative example and Example 1 is that the frosting process of the glass substrate is different. The rest of the preparation process (including the materials, thickness, deposition conditions, etc. of the conductive oxide layer, the first carrier transport layer, the perovskite layer, the second carrier transport layer, the top electrode layer and the encapsulation layer) are exactly the same as those of Example 1.

[0094] The frosted glass substrate in this comparative example is prepared using the following method: Pretreatment of the smooth glass substrate: Take the same ultra-white smooth photovoltaic glass of the same specifications as in Example 1 (thickness 3.2 mm, Mohs hardness 6.8, bending strength 100 MPa), and clean it with acetone, ethanol and deionized water for 15 min each. After drying with nitrogen, put it in an oven and preheat it at 60°C for 30 min. Then, clean the surface with an ion air gun.

[0095] One side of the pretreated smooth glass substrate was subjected to a single sandblasting treatment: the process parameters were exactly the same as those for the third-stage sandblasting in Example 1, using 800-mesh quartz sand (SiO2, Mohs hardness 9.0, purity 99.9%) as the abrasive particles; the sandblasting pressure was 0.10 MPa, the nozzle distance was 280 mm, the scanning speed was 11 mm / s, the sandblasting time was 6 seconds, and the abrasive flow rate was 5 kg / min. After treatment, the substrate was ultrasonically cleaned for 30 min with ultrapure water at 40°C and 80 kHz, and then dried with nitrogen to remove all abrasive residues and debris. The subsequent steps for fabricating the functional layer on the opposite side of the sandblasted surface were the same as in Example 1, resulting in a perovskite solar cell.

[0096] Performance Testing and Results Analysis The performance of the perovskite solar cells prepared in Example 1 and Comparative Examples 1-4 was tested under two conditions: 1. Low-light performance test: Illumination intensity was 300 lux. Test data are shown in Table 1; Table 1 shows the photovoltaic performance test results of the perovskite solar cells provided in Example 1 and Comparative Examples 1-4 under illumination of 300 lux;

[0097] In the table, Voc is the open-circuit voltage, Jsc is the short-circuit current density, FF is the fill factor, and PCE is the photoelectric conversion efficiency. (See Table 1 and...) Figure 5 As can be seen, the perovskite solar cell based on a frosted glass substrate prepared in this embodiment exhibits significantly improved open-circuit voltage Voc, short-circuit current density Jsc, and fill factor FF under 300 lux illumination, with a photoelectric conversion efficiency reaching 32.48%.

[0098] 2. The test conditions were direct light incident at a large angle (1 Sun), and the test data are shown in Table 2; Table 2 shows the photovoltaic performance test results of the perovskite solar cells provided in Example 1 and Comparative Examples 1-4 under direct light with a large incident angle (1 Sun).

[0099] As shown in Table 2, the perovskite solar cell based on a frosted glass substrate prepared in this embodiment can achieve a photoelectric conversion efficiency of 14.92% under 1 Sun illumination. Regardless of whether under weak light or direct light conditions, all performance parameters of Example 1 (open-circuit voltage Voc, short-circuit current density Jsc, fill factor FF, and photoelectric conversion efficiency PCE) are superior to those of Comparative Examples 1-4, perfectly meeting the all-weather, wide-angle light environment requirements of BIPV, and providing core support for efficient absorption under weak light conditions.

[0100] Figure 4 The integral sphere transmittance spectra of the frosted glass substrate of Example 1 and the smooth glass substrate of Comparative Example 1 show that the overall transmittance of the frosted glass substrate in Example 1 is higher than that of the smooth glass substrate in Comparative Example 1. The frosted glass substrate maintains a high transmittance of 85%-90% in the visible light band (>400 nm).

[0101] In summary, this invention prepares a frosted glass substrate with a micro-nano-level uneven structure through a frosting process and applies it to perovskite solar cells. This significantly improves the device's performance under incident light from all angles without sacrificing transmittance or affecting the quality of the upper thin film, providing a practical and feasible technical solution for the large-scale production of perovskite cells for high-performance BIPV.

[0102] Unless otherwise specified, all the technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0103] In this invention, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0104] Unless otherwise specified, the components or preferred components involved in this invention can be combined with each other to form new technical solutions.

[0105] In this invention, unless otherwise specified, the numerical range "a~b" represents an abbreviation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "6~22" means that all real numbers between "6~22" have been listed in this document, and "6~22" is simply an abbreviation of these numerical combinations.

[0106] The "scope" disclosed in this invention can be in the form of a lower limit and an upper limit, and can be one or more lower limits and one or more upper limits, respectively.

[0107] In this invention, the term "and / or" as used herein refers to any combination of one or more of the associated listed items, as well as all possible combinations, and includes such combinations.

[0108] In this invention, unless otherwise stated, the various reaction or operation steps may be performed sequentially or in a particular order. Preferably, the reaction methods described herein are performed sequentially.

[0109] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this invention.

[0110] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Those skilled in the art can readily implement the present invention based on the accompanying drawings and the above description. However, any modifications, alterations, or variations made by those skilled in the art without departing from the scope of the present invention, utilizing the disclosed technical content, are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, or variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A perovskite solar cell based on a frosted glass substrate, characterized in that, include: A frosted glass substrate and a battery functional layer module located on one side of the frosted glass substrate; The frosted glass substrate has a first surface and a second surface disposed opposite to each other; The first surface is a frosted surface formed by a frosting process. The frosted surface has a micro-nano-level uneven structure and is the light-incident surface of the perovskite solar cell. The battery functional layer module is disposed on the second surface of the frosted glass substrate. The battery functional layer module includes a conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer stacked sequentially.

2. The perovskite solar cell based on a frosted glass substrate according to claim 1, characterized in that, The surface roughness Ra of the frosted surface is 50 nm-200 nm.

3. The perovskite solar cell based on a frosted glass substrate according to claim 1, characterized in that, The micro-nano-level concave-convex structure is a continuous gradient composite concave-convex structure formed by sandblasting with sand particles of multiple sizes.

4. The perovskite solar cell based on a frosted glass substrate according to claim 3, characterized in that, The continuous gradient composite concave-convex structure includes: a base concave-convex structure, a transition concave-convex structure, and a surface concave-convex structure, and the base concave-convex structure, the transition concave-convex structure, and the surface concave-convex structure together constitute the surface morphology of the frosted surface. Wherein, the structural feature size of the substrate concave-convex structure is larger than the structural feature size of the transition concave-convex structure, and the structural feature size of the transition concave-convex structure is larger than the structural feature size of the surface concave-convex structure.

5. The perovskite solar cell based on a frosted glass substrate according to claim 4, characterized in that, The base uneven structure constitutes the basic morphology of the frosted surface, the transition uneven structure is formed on the surface of the base uneven structure, and the surface uneven structure is formed on the surface of the base uneven structure and / or the surface of the transition uneven structure. The three elements are superimposed on each other to form the continuous gradient composite concave-convex structure.

6. The perovskite solar cell based on a frosted glass substrate according to claim 4, characterized in that, The base uneven structure is formed by sandblasting with sand particles of the first particle size, the transition uneven structure is formed by sandblasting with sand particles of the second particle size, and the surface uneven structure is formed by sandblasting with sand particles of the third particle size. The first particle size of the sand is 80-120 mesh, the second particle size of the sand is 300-500 mesh, and the third particle size of the sand is 700-1000 mesh.

7. A method for fabricating a perovskite solar cell based on a frosted glass substrate as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. A smooth glass substrate is provided, the smooth glass substrate having two surfaces arranged opposite to each other; one surface of the smooth glass substrate is frosted to form a frosted surface with a micro-nano-level uneven structure, thus obtaining the frosted glass substrate; the frosted surface is the light-incident surface of the perovskite solar cell; S2. A conductive oxide layer, a first carrier transport layer, a perovskite layer, a second carrier transport layer, a top electrode layer, and an encapsulation layer are sequentially prepared on the side of the frosted glass substrate opposite to the frosted surface to obtain a perovskite solar cell based on the frosted glass substrate.

8. The method for fabricating a perovskite solar cell based on a frosted glass substrate according to claim 7, characterized in that, The frosting treatment of one side surface of the smooth glass substrate in step S1 includes: The smooth glass substrate is subjected to a first-stage sandblasting treatment on one side surface using abrasive grains of the first size, forming a substrate concave-convex structure on one side surface of the smooth glass substrate, thus obtaining a first substrate with a substrate concave-convex structure. A second-stage sandblasting process is performed on the surface after the first-stage sandblasting treatment using sand particles of the second size, forming a transitional uneven structure on the uneven surface of the substrate to obtain a second substrate. A third-stage sandblasting process is performed on the surface after the second-stage sandblasting, using a third-size abrasive grain to form a surface concave-convex structure on the surface of the substrate and / or the transition concave-convex structure, thereby forming a frosted surface with a continuous gradient composite concave-convex structure, thus obtaining the frosted glass substrate.

9. The method for fabricating a perovskite solar cell based on a frosted glass substrate according to claim 8, characterized in that, The materials of the first-sized sand grains, the second-sized sand grains, and the third-sized sand grains are selected from any one or more of corundum, silicon carbide, quartz sand, or glass beads.

10. The method for fabricating a perovskite solar cell based on a frosted glass substrate according to claim 7, characterized in that, Prior to S1, the method further includes: The smooth glass substrate is cleaned using any one or more of ultrapure water, ethanol, and deionized water. The smooth glass substrate is preheated to 50-70°C and held for 20-40 minutes.

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