Perovskite cell with low-temperature evaporation antireflection film and preparation method thereof

Abstract

The invention relates to a perovskite cell with a low-temperature evaporation antireflection film and a preparation method of the perovskite cell. The perovskite cell comprises a transparent substrate, an anode layer, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a hole barrier layer, a cathode layer and an antireflection optical coating layer, the anode layer is arranged on the transparent substrate, the hole transport layer is arranged on the anode layer, the perovskite light absorption layer is arranged on the hole transport layer, the electron transport layer is arranged on the perovskite light absorption layer, the hole barrier layer is arranged on the electron transport layer, and the cathode layer is arranged on the hole barrier layer. Wherein the antireflection optical coating layer is arranged below the transparent substrate, and the material of the antireflection optical coating layer is cryolite. Through the arrangement, the problems that decomposition and performance degradation of a perovskite material are easily caused in a high-temperature environment, meanwhile, the internal stress of the glass is increased, the brittle rupture risk is increased, and efficient and stable production of a battery is not facilitated can be solved.

Description

Technical Field

[0001] This invention relates to the field of perovskite technology, and in particular to a perovskite solar cell with a low-temperature evaporation antireflective film and its preparation method. Background Technology

[0002] The industrial application of perovskite photovoltaic technology urgently requires high repeatability and low-cost manufacturing at the cell level, and large-scale assembly line production is the key path to achieving this goal. Against this backdrop, perovskite photovoltaic cells must maintain high performance while meeting the requirements of continuous, stable, and rapid fabrication processes.

[0003] Currently, the main methods for preparing antireflective coatings for perovskite photovoltaic cells include solution coating and high-temperature evaporation. However, both methods are carried out in a high-temperature environment, which easily causes the decomposition and performance degradation of perovskite materials, while also increasing the internal stress of the glass and raising the risk of brittle fracture, which is detrimental to the efficient and stable production of cells. Summary of the Invention

[0004] In view of this, this application provides a perovskite solar cell with a low-temperature evaporation antireflective coating, comprising a transparent substrate, an anode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a hole blocking layer, a cathode layer, and an antireflective optical coating layer; the anode layer is disposed on the transparent substrate, the hole transport layer is disposed on the anode layer, the perovskite light-absorbing layer is disposed on the hole transport layer, the electron transport layer is disposed on the perovskite light-absorbing layer, the hole blocking layer is disposed on the electron transport layer, and the cathode layer is disposed on the hole blocking layer; wherein, the antireflective optical coating layer is disposed on the underside of the transparent substrate, and the material of the antireflective optical coating layer is cryolite.

[0005] In one possible implementation, the transparent substrate is made of glass, the anode layer is made of fluorine-doped tin oxide, the hole transport layer is made of nickel oxide, and the electron transport layer is made of C. 60 The hole blocking layer is made of copper bath, and the cathode layer is made of copper.

[0006] In one possible implementation, the chemical structural formula of the perovskite material of the perovskite light-absorbing layer is: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3.

[0007] In one possible implementation, the solvent for dissolving the perovskite precursor in the perovskite light-absorbing layer is N,N-dimethylformamide and dimethyl sulfoxide.

[0008] A method for preparing a perovskite solar cell with a low-temperature evaporation antireflection film, using the aforementioned materials, comprises the following steps: S1: fluorine-doped tin oxide is magnetron sputtered onto the glass surface to form the anode layer; the glass and the anode layer constitute a fluorine-doped tin oxide substrate; S2: The fluorine-doped tin oxide substrate is cleaned in a cleaning machine; S3: Nickel oxide is magnetron sputtered onto the cleaned fluorine-doped tin oxide substrate to form a hole transport layer; the hole transport layer and the cleaned fluorine-doped tin oxide substrate constitute a nickel oxide substrate; S4: The perovskite precursor for the perovskite light-absorbing layer is prepared according to the chemical formula to obtain Cs. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3 Precursor solution; S5: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. The precursor solution is slit-coated onto a nickel oxide substrate to obtain a perovskite light-absorbing layer. The perovskite light-absorbing layer and the nickel oxide substrate constitute the perovskite substrate. The slit width is 70 μm and the coating speed is 15 mm / s during the slit coating process; S6: C is deposited on the surface of the perovskite substrate by vapor deposition under vacuum. 60 An electron transport layer is obtained, and the electron transport layer and the perovskite substrate constitute C. 60 Substrate; S7: In a vacuum environment, at C 60 Copper oxide is deposited on the surface of the substrate by vapor deposition to obtain a hole blocking layer, and C 60 The substrate is a copper bath substrate; S8: Copper is magnetron sputtered onto the copper bath substrate to obtain a cathode layer and form a perovskite cell; S9: Cryolite is vapor-deposited under the glass to form an anti-reflection optical coating layer, and finally a perovskite cell with a low-temperature vapor-deposited anti-reflection film is formed.

[0009] In one possible implementation, in S9: the pressure of the vapor deposition chamber needs to be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite photovoltaic cell in the vapor deposition chamber is 80 mm / s.

[0010] In one possible implementation, in S9: the temperature of the cryolite evaporation source is 1100 degrees, the crystal oscillator monitoring rate is 5 Å / s, and the thickness of the resulting Na3AlF6 film is 90 nm.

[0011] In one possible implementation, in S3, the target for nickel oxide magnetron sputtering is a nickel target, and a mixture of oxygen and argon is introduced during the magnetron sputtering process to react, and the temperature of the fluorine-doped tin oxide substrate needs to be raised to 250°C before sputtering.

[0012] In one possible implementation, in S6: the pressure of the vapor deposition chamber needs to be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite substrate in the evaporation chamber is 10 mm / s, C 60 The temperature of the evaporation source is 600 degrees Celsius, and the crystal oscillator monitoring rate is 1 Å / s.

[0013] In one possible implementation, in S7: the pressure of the vapor deposition chamber is less than 5 × 10⁻⁶. -4 Pa, C 60 The substrate oscillates at a speed of 16 mm / s within the vapor deposition chamber, the temperature of the copper bath evaporation source is 150 degrees Celsius, and the crystal oscillator monitoring rate is 3 Å / s.

[0014] The beneficial effects of this invention are: by using cryolite with a low melting point as an antireflective medium material, the process temperature required for thermal evaporation is significantly reduced, thereby avoiding thermal decomposition and performance degradation of the perovskite active layer caused by a high-temperature environment. Attached Figure Description

[0015] Figure 1 This is a detailed structural diagram of the perovskite solar cell with a low-temperature evaporation antireflection film according to this application; Figure 2 This is an optical length distribution diagram of Comparative Example 1 of this application; Figure 3 This is an optical length distribution diagram of Comparative Example 2 of this application; Figure 4 This is an optical length distribution diagram of Embodiment 1 of this application; Figure 5 The exciton generation rate distribution in the perovskite light-absorbing layer of Comparative Examples 1, 2 and 1 of this application is shown. Figure 6 This is a graph showing the difference in exciton generation in the perovskite light-absorbing layer between Comparative Examples 1 and 2 and Example 1 of this application. Figure 7 The reflectance spectra of Comparative Examples 1, 2 and 1 of this application are shown. Figure 8 This is a schematic diagram of the highest temperature reached during the vapor deposition of the antireflective optical coating layer in Comparative Example 2 of this application. Figure 9 This is a schematic diagram showing the highest temperature reached during the vapor deposition of the antireflective optical coating layer in Embodiment 1 of this application. Figure 10The JV curves are for Comparative Examples 1, 2 and 1 of this application. Detailed Implementation

[0016] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0017] Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar symbols denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the invention, and should not be construed as limiting the invention.

[0018] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention or to simplify the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0019] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0020] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "joining," "fixing," "linking," "hinging," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0021] like Figure 1As shown, the perovskite solar cell with a low-temperature evaporation antireflective coating includes a transparent substrate 800, an anode layer 100, a hole transport layer 200, a perovskite light absorption layer 300, an electron transport layer 400, a hole blocking layer 500, a cathode layer 600, and an antireflective optical coating layer 700. The anode layer 100 is disposed on top of the transparent substrate 800, the hole transport layer 200 is disposed on top of the anode layer 100, the perovskite light absorption layer 300 is disposed on top of the hole transport layer 200, the electron transport layer 400 is disposed on top of the perovskite light absorption layer 300, the hole blocking layer 500 is disposed on top of the electron transport layer 400, and the cathode layer 600 is disposed on top of the hole blocking layer 500. The antireflective optical coating layer 700 is disposed below the transparent substrate 800, and the material of the antireflective optical coating layer 700 is cryolite.

[0022] Specifically, a transparent substrate 800 serves as the supporting structure for the solar cell, and a transparent conductive anode, used as the electrode material, is deposited on its surface by magnetron sputtering for subsequent charge collection and transport, i.e., the anode layer 100. Then, a hole transport layer 200 is deposited on the anode layer 100 by magnetron sputtering to facilitate the efficient transport of holes from the perovskite layer to the anode. Subsequently, a perovskite precursor material is coated on the hole transport layer 200 to form a perovskite light-absorbing layer 300. Next, an electron transport layer 400 is deposited on the perovskite light-absorbing layer 300 by evaporation to facilitate the transport of electrons from the perovskite layer to the cathode. Subsequently, a hole blocking layer 500 is deposited on the electron transport layer 400 to protect it and simultaneously suppress the recombination of holes and electrons. Finally, a cathode layer 600, the metal back electrode of the entire perovskite photovoltaic cell, is deposited on the hole blocking layer 500 by magnetron sputtering. Finally, an anti-reflection optical coating layer 700 is deposited on the lower surface of the substrate by vapor deposition to reduce the reflection loss of incident light at the air-glass interface.

[0023] It should be noted that the transparent substrate 800 is made of glass, the anode layer is made of fluorine-doped tin oxide, the hole transport layer is made of nickel oxide, and the electron transport layer is made of C. 60 The hole-blocking layer is made of copper bath, and the cathode layer is made of copper. These materials are existing technologies, so they will not be described in detail here.

[0024] In one possible implementation, the chemical structural formula of the perovskite material in the perovskite light-absorbing layer 300 is: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3. The solvent for dissolving the perovskite light-absorbing layer in the perovskite precursor is N,N-dimethylformamide and dimethyl sulfoxide.

[0025] A method for fabricating a perovskite solar cell with a low-temperature evaporation antireflection film, using the aforementioned materials, comprises the following steps: S1: Fluorine-doped tin oxide is magnetron sputtered onto a glass surface to form an anode layer; the glass and the anode layer constitute a fluorine-doped tin oxide substrate; S2: The fluorine-doped tin oxide substrate is cleaned in a cleaning machine; S3: Nickel oxide is magnetron sputtered onto the cleaned fluorine-doped tin oxide substrate to form a hole transport layer; the hole transport layer and the cleaned fluorine-doped tin oxide substrate constitute a nickel oxide substrate; S4: A perovskite precursor for the perovskite light-absorbing layer is prepared according to the chemical formula to obtain Cs. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3 Precursor solution; S5: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. The precursor solution is slit-coated onto a nickel oxide substrate to obtain a perovskite light-absorbing layer. The perovskite light-absorbing layer and the nickel oxide substrate constitute the perovskite substrate. The slit width is 70 μm and the coating speed is 15 mm / s during the slit coating process; S6: C is deposited on the surface of the perovskite substrate by vapor deposition under vacuum. 60 An electron transport layer is obtained, and the electron transport layer and the perovskite substrate constitute C. 60 Substrate; S7: In a vacuum environment, at C 60 Copper oxide is deposited on the surface of the substrate by vapor deposition to obtain a hole blocking layer, and C 60 The substrate is a copper bath substrate; S8: Copper is magnetron sputtered onto the copper bath substrate to obtain a cathode layer and form a perovskite cell; S9: Cryolite is vapor-deposited under the glass to form an anti-reflection optical coating layer, and finally a perovskite cell with a low-temperature vapor-deposited anti-reflection film is formed.

[0026] More specifically, in S9, the pressure of the vapor deposition chamber needs to be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite photovoltaic cell in the evaporation chamber is 80 mm / s, the temperature of the Na3AlF6 evaporation source is 1100 degrees, the crystal oscillator monitoring rate is 5 Å / s, and the thickness of the obtained Na3AlF6 film is 90 nm.

[0027] In S2, it is important to emphasize that the fluorine-doped tin oxide substrate is fed into the cleaning machine. First, the surface of the fluorine-doped tin oxide substrate is ultrasonically cleaned. Then, the surface of the fluorine-doped tin oxide substrate is dried by irradiation with an infrared radiation lamp. Finally, the surface of the fluorine-doped tin oxide substrate is plasma cleaned. The ultrasonic cleaning of the fluorine-doped tin oxide substrate needs to be repeated twice. The cleaning agents include active detergent, deionized water, acetone and isopropanol. The irradiation time of the fluorine-doped tin oxide substrate under the infrared radiation lamp is 3 minutes, followed by plasma cleaning for 3 minutes.

[0028] More specifically in S3, the target material for nickel oxide magnetron sputtering is a nickel target. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to react. The temperature of the fluorine-doped tin oxide substrate needs to be raised to 250°C before sputtering. The oscillation speed of the fluorine-doped tin oxide substrate in the magnetron sputtering cavity is 3.5 m / min, and the sputtering power of the target material is 20 kW.

[0029] In S4, more specifically, cesium iodide (CsI), lead iodide (PbI2), lead bromide (PbBr2), formamidinium iodide (FAI), and methylamine iodide (MAI) are dissolved in a suitable ratio in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to obtain a CsI solution with a concentration of 1.5 M. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3. Precursor solution. Further, the molar ratio of CsI, PbI2, PbBr2, FAI, and MABr was 0.05:0.60:0.40:0.61:0.10, and the volume ratio of DMF to DMSO was 4:1. The mixture was stirred with a magnetic stirrer at 60 degrees Celsius for 6 hours to obtain a thoroughly mixed CsI solution. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. Precursor solution.

[0030] Next, in S5: S5: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30)3 The precursor solution is slit-coated on a nickel oxide substrate to obtain a perovskite light absorption layer. The perovskite light absorption layer and the nickel oxide substrate constitute a perovskite substrate. The width of the slit is 70 μm and the coating speed is 15 mm / s during the slit coating process, resulting in a perovskite light absorption layer with a preferred thickness of 350 nm.

[0031] More specifically, in S6: the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite substrate in the evaporation chamber is 10 mm / s, C 60 The temperature of the evaporation source is 600 degrees Celsius, the crystal oscillator monitoring rate is 1 Å / s, and an electron transport layer is obtained. The preferred thickness of the electron transport layer is 20 nm.

[0032] In S7, it is important to emphasize that the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, C 60 The substrate oscillates at a speed of 16 mm / s within the vapor deposition chamber, the temperature of the copper bath evaporation source is 150 degrees Celsius, and the crystal oscillator monitoring rate is 3 Å / s, resulting in a hole blocking layer with a preferred thickness of 5 nm.

[0033] Specifically, in S8: during magnetron sputtering of copper, a rotating copper target is used, and a mixture of oxygen and argon is introduced during the magnetron sputtering process to facilitate the reaction. Furthermore, the oscillation speed of the BCP substrate within the magnetron sputtering cavity is 0.5 m / min, and the sputtering power of the target is 6 kW, resulting in a cathode layer with a preferred thickness of 90 nm.

[0034] This application reduces the reflectivity of perovskite photovoltaic cells by depositing a cryolite antireflective optical coating beneath a glass substrate, allowing more incident light to enter and be absorbed by the perovskite light-absorbing layer. This application exhibits high light absorption capacity and exciton generation rate.

[0035] This invention effectively avoids the negative impacts of high-temperature environments on perovskite materials, such as thermal decomposition and ion migration, by using low-melting-point cryolite instead of high-melting-point MgF2, thus preventing performance degradation and ensuring the long-term stability of the module. Simultaneously, the lower process temperature reduces the risk of glass substrate cracking due to thermal stress, which is beneficial for improving yield and reliability in large-scale production. It solves the problem of high-temperature environments easily causing perovskite material decomposition and performance degradation, while also increasing internal stress in the glass, increasing the risk of brittleness, and hindering efficient and stable battery production.

[0036] The following are embodiments and comparative examples of this application: Example 1: The specific preparation steps are as follows: S1: The fluorine-doped tin oxide is magnetron sputtered and deposited on the glass surface to form the anode layer, and the glass and the anode layer constitute a fluorine-doped tin oxide substrate; S2: The fluorine-doped tin oxide substrate is fed into a cleaning machine. First, the surface of the fluorine-doped tin oxide substrate is ultrasonically cleaned. Then, the surface is dried by irradiation with an infrared lamp. Finally, the surface of the fluorine-doped tin oxide substrate is plasma cleaned. The ultrasonic cleaning of the fluorine-doped tin oxide substrate requires two cycles. The cleaning agents include an active detergent, deionized water, acetone, and isopropanol. The ultrasonic cleaning time for each cleaning agent is 5 minutes, followed by irradiation under an infrared lamp for 3 minutes. Afterwards, it is passed through a plasma cleaner with a plasma power of 2000 watts. The working gases are compressed dry air and nitrogen, with flow rates of 6 L / min and 60 L / min, respectively. S3: Nickel oxide is magnetron sputtered onto a cleaned fluorine-doped tin oxide substrate to form a hole transport layer. The hole transport layer and the cleaned fluorine-doped tin oxide substrate constitute the nickel oxide substrate. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to react. The temperature of the fluorine-doped tin oxide substrate needs to be raised to 250°C before sputtering. The oscillation speed of the fluorine-doped tin oxide substrate in the magnetron sputtering cavity is 3.5 m / min, the sputtering power of the target is 20 kW, the process vacuum is 0.4 Pa, and the oxygen to argon flow ratio is 25%, resulting in a nickel oxide hole transport layer with a thickness of 25 nm. S4: Cesium iodide (CsI), lead iodide (PbI2), lead bromide (PbBr2), formamidinium iodide (FAI), and methylamine iodide (MAI) are dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in appropriate proportions to obtain CsI with a concentration of 1.5 M. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3. Precursor solution. Further, the molar ratio of CsI, PbI2, PbBr2, FAI, and MABr was 0.05:0.60:0.40:0.61:0.10, and the volume ratio of DMF to DMSO was 4:1. The mixture was stirred with a magnetic stirrer at 60 degrees Celsius for 6 hours to obtain a thoroughly mixed CsI solution. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. Precursor solution; S5: Cs 0.05 (FA 0.90 MA0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3 The precursor solution was slit-coated on a nickel oxide substrate to obtain a perovskite light absorption layer. The perovskite light absorption layer and the nickel oxide substrate constitute a perovskite substrate. The width of the slit during the slit coating process was 70 μm, the coating speed was 15 mm / s, and a perovskite light absorption layer with a thickness of 350 nm was obtained. S6: C is deposited on the surface of a perovskite substrate by vapor deposition in a vacuum environment. 60 An electron transport layer is obtained, and the electron transport layer and the perovskite substrate constitute C. 60 The substrate must be suitable, and the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite substrate in the evaporation chamber is 10 mm / s, C 60 The temperature of the evaporation source is 600 degrees, the crystal oscillator monitoring rate is 1 Å / s, and an electron transport layer is obtained. The preferred thickness of the electron transport layer is 20 nm. S7: In a vacuum environment, at C 60 Copper oxide is deposited on the surface of the substrate by vapor deposition to obtain a hole blocking layer, and C 60 The substrate is a copper bath substrate, and the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, C 60 The substrate oscillates at a speed of 16 mm / s in the evaporation chamber, the temperature of the copper bath evaporation source is 150 degrees, the crystal oscillator monitoring rate is 3 Å / s, and a hole blocking layer is obtained. The preferred thickness of the hole blocking layer is 5 nm. S8: Copper is magnetron sputtered onto a copper bath substrate to obtain a cathode layer, forming a perovskite solar cell. A mixture of oxygen and argon is introduced during the magnetron sputtering process to facilitate the reaction. The copper bath substrate oscillates at a speed of 0.5 m / min within the magnetron sputtering chamber, and the target sputtering power is 6 kW, resulting in a cathode layer with a preferred thickness of 90 nm. S9: Deposit cryolite under the glass to form an anti-reflective optical coating layer, ultimately forming a perovskite solar cell with a low-temperature deposited anti-reflective coating. The pressure of the deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite photovoltaic cell in the evaporation chamber is 80 mm / s, the temperature of the Na3AlF6 evaporation source is 1100 degrees, the crystal oscillator monitoring rate is 5 Å / s, and the thickness of the obtained Na3AlF6 film is 90 nm.

[0037] Comparative Example 1: This comparative example is a normal perovskite solar cell.

[0038] The specific steps are as follows: S1: The fluorine-doped tin oxide is magnetron sputtered and deposited on the glass surface to form the anode layer, and the glass and the anode layer constitute a fluorine-doped tin oxide substrate; S2: The fluorine-doped tin oxide substrate is fed into a cleaning machine. First, the surface of the fluorine-doped tin oxide substrate is ultrasonically cleaned. Then, the surface is dried by irradiation with an infrared lamp. Finally, the surface of the fluorine-doped tin oxide substrate is plasma cleaned. The ultrasonic cleaning of the fluorine-doped tin oxide substrate requires two cycles. The cleaning agents include an active detergent, deionized water, acetone, and isopropanol. The ultrasonic cleaning time in each cleaning solvent is 5 minutes, followed by irradiation under an infrared lamp for 3 minutes. Afterwards, it is passed through a plasma cleaner with a plasma power of 2000 watts. The working gases are compressed dry air and nitrogen, with flow rates of 6 L / min and 60 L / min, respectively. S3: Nickel oxide is magnetron sputtered onto a cleaned fluorine-doped tin oxide substrate to form a hole transport layer. The hole transport layer and the cleaned fluorine-doped tin oxide substrate constitute the nickel oxide substrate. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to react. The temperature of the fluorine-doped tin oxide substrate needs to be raised to 250°C before sputtering. The oscillation speed of the fluorine-doped tin oxide substrate in the magnetron sputtering cavity is 3.5 m / min, the sputtering power of the target is 20 kW, the process vacuum is 0.4 Pa, and the oxygen to argon flow ratio is 25%, resulting in a nickel oxide hole transport layer with a thickness of 25 nm. S4: Cesium iodide (CsI), lead iodide (PbI2), lead bromide (PbBr2), formamidinium iodide (FAI), and methylamine iodide (MAI) are dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in appropriate proportions to obtain CsI with a concentration of 1.5 M. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3. Precursor solution. Further, the molar ratio of CsI, PbI2, PbBr2, FAI, and MABr was 0.05:0.60:0.40:0.61:0.10, and the volume ratio of DMF to DMSO was 4:1. The mixture was stirred with a magnetic stirrer at 60 degrees Celsius for 6 hours to obtain a thoroughly mixed CsI solution. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. Precursor solution; S5: Cs 0.05 (FA 0.90 MA0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3 The precursor solution was slit-coated on a nickel oxide substrate to obtain a perovskite light absorption layer. The perovskite light absorption layer and the nickel oxide substrate constitute a perovskite substrate. The width of the slit during the slit coating process was 70 μm, the coating speed was 15 mm / s, and a perovskite light absorption layer with a thickness of 350 nm was obtained. S6: C is deposited on the surface of a perovskite substrate by vapor deposition in a vacuum environment. 60 An electron transport layer is obtained, and the electron transport layer and the perovskite substrate constitute C. 60 The substrate must be suitable, and the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite substrate in the evaporation chamber is 10 mm / s, C 60 The temperature of the evaporation source is 600 degrees, the crystal oscillator monitoring rate is 1 Å / s, and an electron transport layer is obtained. The preferred thickness of the electron transport layer is 20 nm. S7: In a vacuum environment, at C 60 Copper oxide is deposited on the surface of the substrate by vapor deposition to obtain a hole blocking layer, and C 60 The substrate is a copper bath substrate, and the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, C 60 The substrate oscillates at a speed of 16 mm / s in the evaporation chamber, the temperature of the copper bath evaporation source is 150 degrees, the crystal oscillator monitoring rate is 3 Å / s, and a hole blocking layer is obtained. The preferred thickness of the hole blocking layer is 5 nm. S8: Copper is magnetron sputtered onto a copper bath substrate. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to facilitate the reaction. The copper bath substrate oscillates at a speed of 0.5 m / min within the magnetron sputtering chamber, and the sputtering power of the target is 6 kW, resulting in a cathode layer with a preferred thickness of 90 nm, forming a perovskite solar cell.

[0039] Comparative Example 2: Comparative Example 2 is a perovskite solar cell prepared using a high-melting-point dielectric material. The difference between Comparative Example 2 and Example 1 is that MgF2 is vapor-deposited under the glass to form an anti-reflective optical coating layer, ultimately forming a perovskite solar cell with a low-temperature vapor-deposited anti-reflective film. Furthermore, the pressure of the vapor deposition chamber needs to be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite photovoltaic cell in the evaporation chamber is 70 mm / s, the temperature of the MgF2 evaporation source is 1400 degrees, the crystal oscillator monitoring rate is 4 Å / s, and the thickness of the obtained MgF2 film is 100 nm.

[0040] The specific steps are as follows: S1: The fluorine-doped tin oxide is magnetron sputtered and deposited on the glass surface to form the anode layer, and the glass and the anode layer constitute a fluorine-doped tin oxide substrate; S2: The fluorine-doped tin oxide substrate is fed into a cleaning machine. First, the surface of the fluorine-doped tin oxide substrate is ultrasonically cleaned. Then, the surface is dried by irradiation with an infrared lamp. Finally, the surface of the fluorine-doped tin oxide substrate is plasma cleaned. The ultrasonic cleaning of the fluorine-doped tin oxide substrate requires two cycles. The cleaning agents include an active detergent, deionized water, acetone, and isopropanol. The ultrasonic cleaning time in each cleaning solvent is 5 minutes, followed by irradiation under an infrared lamp for 3 minutes. Afterwards, it is passed through a plasma cleaner with a plasma power of 2000 watts. The working gases are compressed dry air and nitrogen, with flow rates of 6 L / min and 60 L / min, respectively. S3: Nickel oxide is magnetron sputtered onto a cleaned fluorine-doped tin oxide substrate to form a hole transport layer. The hole transport layer and the cleaned fluorine-doped tin oxide substrate constitute the nickel oxide substrate. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to react. The temperature of the fluorine-doped tin oxide substrate needs to be raised to 250°C before sputtering. The oscillation speed of the fluorine-doped tin oxide substrate in the magnetron sputtering cavity is 3.5 m / min, the sputtering power of the target is 20 kW, the process vacuum is 0.4 Pa, and the oxygen to argon flow ratio is 25%, resulting in a nickel oxide hole transport layer with a thickness of 25 nm. S4: Cesium iodide (CsI), lead iodide (PbI2), lead bromide (PbBr2), formamidinium iodide (FAI), and methylamine iodide (MAI) are dissolved in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in appropriate proportions to obtain CsI with a concentration of 1.5 M. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3. Precursor solution. Further, the molar ratio of CsI, PbI2, PbBr2, FAI, and MABr was 0.05:0.60:0.40:0.61:0.10, and the volume ratio of DMF to DMSO was 4:1. The mixture was stirred with a magnetic stirrer at 60 degrees Celsius for 6 hours to obtain a thoroughly mixed CsI solution. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. Precursor solution; S5: Cs 0.05 (FA 0.90 MA0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3 The precursor solution was slit-coated on a nickel oxide substrate to obtain a perovskite light absorption layer. The perovskite light absorption layer and the nickel oxide substrate constitute a perovskite substrate. The width of the slit during the slit coating process was 70 μm, the coating speed was 15 mm / s, and a perovskite light absorption layer with a thickness of 350 nm was obtained. S6: C is deposited on the surface of a perovskite substrate by vapor deposition in a vacuum environment. 60 An electron transport layer is obtained, and the electron transport layer and the perovskite substrate constitute C. 60 The substrate must be suitable, and the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite substrate in the evaporation chamber is 10 mm / s, C 60 The temperature of the evaporation source is 600 degrees, the crystal oscillator monitoring rate is 1 Å / s, and an electron transport layer is obtained. The preferred thickness of the electron transport layer is 20 nm. S7: In a vacuum environment, at C 60 Copper oxide is deposited on the surface of the substrate by vapor deposition to obtain a hole blocking layer, and C 60 The substrate is a copper bath substrate, and the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, C 60 The substrate oscillates at a speed of 16 mm / s in the evaporation chamber, the temperature of the copper bath evaporation source is 150 degrees, the crystal oscillator monitoring rate is 3 Å / s, and a hole blocking layer is obtained. The preferred thickness of the hole blocking layer is 5 nm. S8: Copper is magnetron sputtered onto a copper bath substrate. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to facilitate the reaction. The copper bath substrate oscillates at a speed of 0.5 m / min within the magnetron sputtering chamber, and the sputtering power of the target is 6 kW, resulting in a cathode layer with a preferred thickness of 90 nm, forming a perovskite solar cell. S9: MgF2 is vapor-deposited under the glass to form an anti-reflective optical coating layer, ultimately forming a perovskite solar cell with a low-temperature vapor-deposited anti-reflective coating. The pressure of the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite photovoltaic cell in the evaporation chamber is 70 mm / s, the temperature of the MgF2 evaporation source is 1400 degrees, the crystal oscillator monitoring rate is 4 Å / s, and the thickness of the obtained MgF2 film is 100 nm.

[0041] Electromagnetic field simulations were performed on the perovskite photovoltaic module to guide the fabrication process of the anti-reflection optical coating. First, the refractive index and extinction coefficient of each layer in the perovskite photovoltaic module were measured using an ellipsometer. Then, the reflection, transmission, and absorption behaviors between layers in the perovskite photovoltaic module were systematically calculated using the matrix transmission method. The results show that for Comparative Example 2, where the anti-reflection optical coating material is MgF2, the preferred thickness of MgF2 is 100 nm; for the example where the anti-reflection optical coating material is Na3AlF6, the preferred thickness of Na3AlF6 is 90 nm. Specifically: Figures 2 to 4 The electromagnetic field distributions of Comparative Example 1, Comparative Example 2, and Example 1 are shown. For Comparative Example 1 without an anti-reflective optical coating, the electromagnetic field energy of the component in the wavelength range of 300 to 800 nm and the vertical position range of -100 to 170 nm is higher than that of Comparative Example 2 and Example 1, where the anti-reflective optical coating material is MgF2. This indicates that more visible light energy is reflected and dissipated before entering the perovskite light-absorbing layer, and less visible light energy participates in photoelectric conversion. Furthermore, compared with Comparative Example 2, in Example 1, more visible light energy can be absorbed by the perovskite light-absorbing layer in the perovskite photovoltaic cell using cryolite as the anti-reflective optical coating, resulting in higher photocurrent and photoelectric conversion efficiency.

[0042] Figures 5 to 6 The exciton generation rates of the perovskite light-absorbing layers in Comparative Examples 1, 2, and 1 are shown, and the magnitude of the exciton generation rate is positively correlated with the light absorption of the perovskite light-absorbing layer. To more intuitively demonstrate the effectiveness of the anti-reflective optical coating in improving the light absorption of perovskite photovoltaic cells, the exciton generation rates of the perovskite light-absorbing layers in Comparative Examples 1, 2, and 1 are subtracted. The results show that the exciton generation rates of the perovskite layers in Comparative Examples 2 and 1 are significantly higher than those in Comparative Example 1. Furthermore, the exciton generation rate of the perovskite light-absorbing layer in the examples is also higher than that in Comparative Example 2, indicating that perovskite photovoltaic cells using cryolite as an anti-reflective optical coating can utilize more visible light energy for photoelectric conversion, resulting in higher photocurrent and photoelectric conversion efficiency.

[0043] Figure 7 The reflectance spectra of Comparative Example 1, Comparative Example 2, and Example 1 are shown. The average reflectance of Comparative Example 1 is 4.5%. The average reflectance of Comparative Example 2 is 3.5% when the preferred thickness is 100 nm. The average reflectance of Example 1 is 2.5% when the preferred thickness is 90 nm.

[0044] Figures 8 to 9The highest temperatures reached during the deposition of antireflective optical coatings in Comparative Example 2 and Example 1 are shown. The results indicate that the highest temperature reached during deposition in Comparative Example 2 exceeded 116 degrees Celsius. Furthermore, the highest temperature reached during deposition in Example 1 did not exceed 82 degrees Celsius. This result can be attributed to two factors: First, cryolite has a higher refractive index than MgF2, therefore a smaller antireflective optical coating thickness is required to achieve the same antireflective effect in the same optical system, indicating a shorter residence time of the perovskite photovoltaic cell within the deposition chamber; second, cryolite has a lower melting point than MgF2, resulting in a lower average temperature within the deposition chamber, indicating less thermal radiation experienced by the perovskite photovoltaic cell within the deposition chamber.

[0045] Figure 10 The comparison examples 1, 2, and 1 are shown under AM 1.5G light source illumination. JV The curves and related photovoltaic parameters are shown in Table 1. Comparing Comparative Example 1 with Comparative Example 2, the short-circuit current density of Comparative Example 2 is higher than that of Comparative Example 1, while the open-circuit voltage, fill factor, and energy conversion efficiency all decrease. This indicates that the 100 nm thick MgF2 can effectively suppress the reflection loss of incident light at the air-glass interface. However, the high temperature encountered during the long-term MgF2 deposition process negatively impacts the perovskite light absorption layer, leading to a decrease in other photovoltaic properties. Furthermore, comparing Comparative Example 2 with the Example, the Example shows improved short-circuit current density, open-circuit voltage, fill factor, and energy conversion efficiency. This not only demonstrates the effectiveness of the 90 nm thick Na3AlF6 as an anti-reflection optical coating layer but also the effectiveness of the low-temperature deposition method in protecting the performance of the perovskite layer. Table 1 is as follows: Table 1: Photovoltaic performance parameters of Comparative Example 1, Comparative Example 2 and Examples The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope disclosed in the present invention, based on the technical solution and concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A perovskite solar cell with a low-temperature evaporation-deposited antireflective film, characterized in that, It includes a transparent substrate, an anode layer, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a hole blocking layer, a cathode layer, and an anti-reflection optical coating layer; The anode layer is disposed on the transparent substrate, the hole transport layer is disposed on the anode layer, the perovskite light absorption layer is disposed on the hole transport layer, the electron transport layer is disposed on the perovskite light absorption layer, the hole blocking layer is disposed on the electron transport layer, and the cathode layer is disposed on the hole blocking layer. The anti-reflective optical coating layer is disposed below the transparent substrate, and the material of the anti-reflective optical coating layer is cryolite.

2. The perovskite solar cell with a low-temperature evaporation antireflective film according to claim 1, characterized in that, The transparent substrate is glass, the anode layer is fluorine-doped tin oxide, the hole transport layer is nickel oxide, and the electron transport layer is C. 60 The hole blocking layer is made of copper bath, and the cathode layer is made of copper.

3. The perovskite solar cell with a low-temperature evaporation antireflective film according to claim 2, characterized in that, The chemical structural formula of the perovskite material in the perovskite light-absorbing layer is: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 3.

4. The perovskite solar cell with a low-temperature evaporation-deposited antireflective film according to claim 3, characterized in that, The solvent for dissolving the perovskite precursor in the perovskite light-absorbing layer is N,N-dimethylformamide and dimethyl sulfoxide.

5. A method for preparing a perovskite solar cell with a low-temperature evaporation-deposited antireflective film, characterized in that, The specific steps for using the material in the perovskite solar cell with a low-temperature evaporation antireflective film as described in any one of claims 2-4 are as follows: S1: The fluorine-doped tin oxide is magnetron sputtered and deposited on the glass surface to form the anode layer, and the glass and the anode layer constitute a fluorine-doped tin oxide substrate; S2: The fluorine-doped tin oxide substrate is sent into a cleaning machine for cleaning; S3: The nickel oxide is magnetron sputtered onto the cleaned fluorine-doped tin oxide substrate to form the hole transport layer. The hole transport layer and the cleaned fluorine-doped tin oxide substrate constitute a nickel oxide substrate. S4: Prepare the perovskite precursor for the perovskite light-absorbing layer according to the chemical formula to obtain Cs. 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3. Precursor solution; S5: Cs 0.05 (FA 0.90 MA 0.10 ) 0.95 Pb(I 0.70 Br 0.30 )3 The precursor solution is slit coated on the nickel oxide substrate to obtain the perovskite light absorption layer. The perovskite light absorption layer and the nickel oxide substrate constitute the perovskite substrate. The width of the slit is 70 μm and the coating speed is 15 mm / s during the slit coating process. S6: Under vacuum conditions, C is deposited by vapor deposition on the surface of the perovskite substrate. 60 The electron transport layer is obtained, and the electron transport layer and the perovskite substrate constitute a C 60 substrate; S7: In a vacuum environment, at C 60 Copper oxide is deposited on the surface of the substrate by vapor deposition to obtain the hole blocking layer, and the hole blocking layer and C 60 The substrate is composed of a copper bath substrate; S8: Copper is magnetron sputtered onto the copper bath substrate to obtain the cathode layer and form a perovskite cell; S9: Ice crystals are vapor-deposited under the glass to form an anti-reflective optical coating layer, ultimately forming a perovskite solar cell with a low-temperature vapor-deposited anti-reflective coating.

6. The method for preparing a perovskite solar cell with a low-temperature evaporation antireflective film according to claim 5, characterized in that, In S9: the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite photovoltaic cell in the vapor deposition chamber is 80 mm / s.

7. The method for preparing a perovskite solar cell with a low-temperature evaporation antireflective film according to claim 6, characterized in that, In S9: the temperature of the cryolite evaporation source was 1100 degrees, the crystal oscillator monitoring rate was 5 Å / s, and the thickness of the resulting Na3AlF6 film was 90 nm.

8. The method for preparing a perovskite solar cell with a low-temperature evaporation antireflective film according to claim 5, characterized in that, In S3, the target material for nickel oxide magnetron sputtering is a nickel target. During the magnetron sputtering process, a mixture of oxygen and argon is introduced to react, and the temperature of the fluorine-doped tin oxide substrate needs to be raised to 250°C before sputtering.

9. The method for preparing a perovskite solar cell with a low-temperature evaporation antireflective film according to claim 5, characterized in that, In S6: the pressure in the vapor deposition chamber must be less than 5 × 10⁻⁶. -4 Pa, the oscillation speed of the perovskite substrate in the evaporation chamber is 10 mm / s, C 60 The temperature of the evaporation source is 600 degrees Celsius, and the crystal oscillator monitoring rate is 1 Å / s.

10. The method for preparing a perovskite solar cell with a low-temperature evaporation antireflective film according to claim 5, characterized in that, In S7: the pressure in the vapor deposition chamber is less than 5 × 10⁻⁶. -4 Pa, C 60 The substrate oscillates at a speed of 16 mm / s within the vapor deposition chamber, the temperature of the copper bath evaporation source is 150 degrees Celsius, and the crystal oscillator monitoring rate is 3 Å / s.

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