Perovskite light absorption layer and preparation method thereof, and perovskite solar cell

Abstract

The invention discloses a perovskite light absorption layer and a preparation method thereof, and a perovskite solar cell, and belongs to the technical field of perovskite solar cells. At least one surface of the perovskite light absorption layer is of a suede structure, and the perovskite light absorption layer is of a single-crystal structure. According to the preparation method, a hydrophobic complex solution is dropped on the surface of a suede substrate, the substrate is peeled off after curing, a hydrophobic complex layer with a suede structure on the surface is obtained, a perovskite precursor solution is dropped on the surface of a substrate where the perovskite light absorption layer needs to be prepared, the suede of the hydrophobic complex layer covers the perovskite precursor solution, and the perovskite light absorption layer is prepared. And after crystallization, stripping from the hydrophobic complex layer to obtain the perovskite light absorption layer. The problems that an existing perovskite light absorption layer is high in defect density and poor in crystal stability, and transmission of carriers is hindered, so that the photoelectric conversion efficiency is low, and the stability is poor are solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cells, and in particular relates to a perovskite light-absorbing layer and a preparation method thereof, and a perovskite solar cell. Background Art

[0002] Perovskite solar cells are a new third-generation photovoltaic material with the characteristics of simple preparation process, wide spectral absorption range, and low cost. The perovskite light-absorbing layer is one of the key film layers in perovskite solar cells.

[0003] In the prior art, spin coating, blade coating, spray coating or slit coating are usually used to prepare perovskite thin films as perovskite light absorbing layers.

[0004] However, the perovskite films produced by the above method all form a polycrystalline structure after annealing and crystallization, with small grains and more grain boundaries, making it difficult to ensure uniform coverage on the suede bottom battery. The defect density is high and the crystal stability is poor, which hinders the transfer of carriers, thereby affecting the photoelectric conversion efficiency and stability of the perovskite solar cell. Summary of the Invention

[0005] In view of the above analysis, the present invention aims to provide a perovskite light-absorbing layer and a preparation method, as well as a perovskite solar cell, to solve the problems in the prior art that the perovskite light-absorbing layer has a polycrystalline structure, a high defect density, poor crystal stability, and hinders the transfer of carriers, resulting in low photoelectric conversion efficiency and poor stability of the perovskite solar cell.

[0006] The purpose of the present invention is mainly achieved through the following technical solutions.

[0007] According to a first aspect of the present invention, a perovskite light absorbing layer is provided. At least one surface of the perovskite light absorbing layer has a suede structure, and the perovskite light absorbing layer has a single crystal structure.

[0008] Furthermore, the light-receiving surface of the perovskite light-absorbing layer is a suede structure;

[0009] Alternatively, both the light-receiving side and the backlight side of the perovskite light-absorbing layer have a suede structure.

[0010] Furthermore, the suede structure of the perovskite light-absorbing layer is a concave-convex structure formed by a plurality of protrusions on the surface of the perovskite light-absorbing layer, and the bottom side length of each protrusion is 2 to 3 μm.

[0011] A second aspect of the present invention provides a method for preparing a perovskite light absorbing layer, comprising the following steps:

[0012] Step a: providing a substrate with a suede surface;

[0013] Step b: dropping a hydrophobic complex solution onto the suede structure surface of the substrate, and peeling the hydrophobic complex solution from the substrate after solidification to obtain a hydrophobic complex layer with a suede structure on the surface;

[0014] Step c: providing a substrate on which a perovskite light absorbing layer is to be prepared, and dripping a perovskite precursor solution onto the surface of the substrate on which the perovskite light absorbing layer is to be prepared;

[0015] Step d: Covering the hydrophobic composite layer on the perovskite precursor solution, with the suede structure facing the perovskite precursor solution;

[0016] Step e: After the perovskite precursor solution crystallizes to form a film layer, the hydrophobic complex layer is peeled off, thereby forming at least one single crystal perovskite light-absorbing layer with a suede structure on the surface of the substrate;

[0017] The hydrophobic complex solution comprises a hydrophobic material and a curing agent.

[0018] Furthermore, in the hydrophobic complex solution, the hydrophobic material includes polydimethylsiloxane, epoxy resin, polymethyl methacrylate, polyurethane, polypropylene or polyvinyl alcohol, and the curing agent includes dimethyldichlorosilane, aminosilane, tetraethoxy or diethylenetriamine.

[0019] Furthermore, the volume ratio of the hydrophobic material to the curing agent is 8 to 12:1.

[0020] Furthermore, in step b, the thickness of the hydrophobic complex layer is 4 to 8 μm;

[0021] And / or, in step d, the distance between the substrate surface and the tip of the suede structure of the hydrophobic complex layer is 500-1000 nm.

[0022] Furthermore, in step c, the concentration of perovskite in the perovskite precursor solution is 1.6 to 1.9 mol / ml;

[0023] And / or, in step e, the perovskite precursor solution is crystallized at a temperature of 60-80° C. and a humidity of 45%-55%.

[0024] The third aspect of the present invention further provides a perovskite solar cell comprising the above-mentioned perovskite light-absorbing layer.

[0025] Furthermore, the perovskite solar cell is a perovskite / crystalline silicon tandem cell, the perovskite / crystalline silicon tandem cell further comprising a conductive silicon substrate, and the perovskite light-absorbing layer is provided on the light-receiving surface of the conductive silicon substrate;

[0026] The light-receiving surface of the conductive silicon substrate is a planar structure; or, the light-receiving surface of the conductive silicon substrate is a velvet structure; or, the light-receiving surface of the conductive silicon substrate is a velvet structure, and the velvet structure of the conductive silicon substrate has the same shape as the velvet structure of the perovskite light-absorbing layer.

[0027] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0028] A) At least one surface of the perovskite light-absorbing layer provided by the present invention has a micron-scale suede structure, which can effectively reduce the recombination loss and reflection loss of photogenerated carriers, increase the optical path length of light inside the perovskite solar cell, and thus improve the photoelectric conversion efficiency of the perovskite solar cell.

[0029] B) The perovskite in the perovskite light-absorbing layer provided by the present invention has a single crystal structure, larger grains, a stable crystal structure, and better crystallinity, thereby ensuring uniform contact between the perovskite crystals and the substrate of the perovskite solar cell, reducing grain boundaries and specific surface area, and thus minimizing surface defects and defect density. The perovskite light-absorbing layer is evenly covered, thereby improving the performance stability of the perovskite solar cell during use.

[0030] C) The preparation method of the perovskite light-absorbing layer provided by the present invention comprises: curing a hydrophobic replica solution to replicate the velvet structure of the substrate onto the surface of the hydrophobic replica layer; then, utilizing the velvet structure on the surface of the hydrophobic replica layer to restrict the crystallization of the perovskite precursor solution, so that a velvet structure is formed on the surface of the obtained perovskite single crystal.

[0031] D) In ​​the preparation method of the perovskite light-absorbing layer provided by the present invention, the hydrophobicity of the surface of the laminated structure is lower than that of the hydrophobic complex layer. Due to the difference in hydrophobicity, a concentration gradient is generated in the perovskite precursor solution. The concentration of the perovskite precursor solution gradually decreases from the laminated structure to the hydrophobic complex layer. During the crystallization process, attachment sites are first generated in the perovskite precursor solution near the laminated structure, and crystal nuclei are formed at the attachment sites, gradually growing into a single crystal structure in the direction close to the perovskite.

[0032] In the present invention, the above-mentioned technical solutions can be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description, and some advantages will become apparent from the description or be understood through practice of the present invention. The objectives and other advantages of the present invention can be achieved and obtained through the embodiments of the description and the contents particularly pointed out in the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The accompanying drawings are only for the purpose of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference symbols denote like parts throughout the drawings.

[0034] Figure 1a A schematic structural diagram of a perovskite single-junction battery provided by the present invention;

[0035] Figure 1bA schematic structural diagram of the perovskite silicon tandem battery provided by the present invention;

[0036] Figure 2 XRD test patterns of the perovskite solar cells prepared in Examples 1 to 3 and Comparative Example 1;

[0037] Figure 3 EQE test comparison chart of the perovskite solar cells prepared in Examples 1 to 3 and Comparative Example 1;

[0038] Figure 4 This is a scanning electron microscope image of the pyramid-shaped complex layer protrusions in the suede structure of the hydrophobic complex layer prepared in Example 1;

[0039] Figure 5 This is a scanning electron microscope image of the pyramid-shaped light-absorbing layer protrusions in the textured structure of the perovskite light-absorbing layer prepared in Example 1.

[0040] Reference numerals:

[0041] 1-conductive silicon substrate; 2-hole transport layer; 3-perovskite light absorption layer; 4-electron transport layer; 5-buffer layer; 6-front composite layer; 7-positive electrode; 8-back electrode; 9-antireflection layer. DETAILED DESCRIPTION

[0042] The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein the accompanying drawings constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0043] According to a first aspect of the present invention, a perovskite light absorbing layer is provided. At least one surface of the perovskite light absorbing layer has a suede structure, and the perovskite light absorbing layer has a single crystal structure.

[0044] It should be noted that the light-receiving surface of the perovskite light-absorbing layer has a suede structure, or both the light-receiving surface and the backlight surface of the perovskite light-absorbing layer have a suede structure.

[0045] Compared with the prior art, on the one hand, at least one surface of the perovskite light-absorbing layer provided by the present invention is a micron-scale velvet surface, which can effectively reduce the recombination loss and reflection loss of photogenerated carriers, increase the optical path length of light inside the perovskite solar cell, and thus improve the photoelectric conversion efficiency of the perovskite solar cell; on the other hand, the perovskite in the perovskite light-absorbing layer is a single crystal structure with larger grains, a stable crystal structure, and better crystallinity, thereby ensuring uniform contact between the perovskite crystals and the substrate of the perovskite solar cell, reducing grain boundaries and specific surface area, and thus minimizing surface defects and defect density. The perovskite light-absorbing layer is evenly covered, thereby improving the performance stability of the perovskite solar cell during use. In actual applications, the photoelectric conversion efficiency of the perovskite solar cell prepared using the perovskite light-absorbing layer of the present invention can reach 27-30%.

[0046] Illustratively, the textured structure of the perovskite light absorbing layer is a concave-convex structure formed by a plurality of light absorbing layer protrusions on the surface of the perovskite light absorbing layer, and the bottom side length of each light absorbing layer protrusion (eg, a pyramid-shaped protrusion) is 2 to 3 μm.

[0047] In a second aspect, the present invention provides a method for preparing a perovskite light-absorbing layer, comprising the following steps:

[0048] Step a: providing a substrate with a suede surface;

[0049] Step b: dropping a hydrophobic complex solution onto the surface of the suede structure of the substrate, and peeling the hydrophobic complex solution from the substrate after solidification to obtain a hydrophobic complex layer with a suede structure on the surface;

[0050] Step c: providing a substrate (e.g., a laminated structure consisting of a substrate and a hole transport layer) on a surface of which a perovskite light absorbing layer is to be prepared, and dripping a perovskite precursor solution onto the surface of the substrate on which the perovskite light absorbing layer is to be prepared, wherein the concentration of perovskite in the perovskite precursor is preferably 1.6 to 1.9 mol / ml;

[0051] Step d: Covering the perovskite precursor solution with a hydrophobic composite layer, with the suede structure facing the perovskite precursor solution, wherein the hydrophobicity of the hydrophobic composite layer is greater than the hydrophobicity of the substrate surface on which the perovskite light absorbing layer is to be prepared (e.g., the surface of the hole transport layer in the stacked structure);

[0052] Step e: After the perovskite precursor solution crystallizes to form a film layer, the hydrophobic complex layer is peeled off, thereby forming at least one single crystal perovskite light-absorbing layer with a suede structure on the surface of the substrate.

[0053] Compared with the prior art, the preparation method of the perovskite light-absorbing layer provided by the present invention, on the one hand, adopts the hydrophobic replica solution to solidify and then replicate the velvet structure of the substrate to the surface of the hydrophobic replica layer, and then utilizes the velvet structure on the surface of the hydrophobic replica layer to restrict the crystallization of the perovskite precursor solution, so that the surface of the obtained perovskite single crystal forms a velvet structure; on the other hand, the hydrophobicity of the surface of the substrate to be prepared for the perovskite light-absorbing layer is lower than that of the hydrophobic replica layer. Due to the difference in hydrophobicity, a concentration gradient is generated in the perovskite precursor solution. From the substrate to the hydrophobic replica layer, the concentration of the perovskite precursor solution gradually decreases. During the crystallization process, an attachment site is first generated in the perovskite precursor solution close to the substrate, and a crystal nucleus is formed at the attachment site, which gradually grows into a single crystal structure in the direction close to the perovskite.

[0054] For example, for the preparation of the hydrophobic composite layer, the above step b includes the following steps:

[0055] The hydrophobic material and the curing agent are mixed and stirred evenly, and then allowed to stand to remove bubbles until no bubbles are visible in the mixture, thereby obtaining a hydrophobic complex solution, wherein the volume ratio of the hydrophobic material to the curing agent is 8 to 12:1 (for example, 10:1);

[0056] The hydrophobic composite solution is dropped onto the surface of the textured silicon battery, cured (eg, UV-cured) at a temperature of 20-30° C., and then peeled off to obtain a hydrophobic composite layer with a textured structure on the surface.

[0057] In order to ensure that the hydrophobic complex layer has sufficient mechanical strength, the thickness of the hydrophobic complex layer is 4 to 8 μm (for example, 5 μm).

[0058] To better penetrate the velvet structure of the velvet substrate, the hydrophobic material illustratively includes polydimethylsiloxane (PDMS), epoxy resin (EP), polymethyl methacrylate (PMMA), polyurethane (PU), polypropylene (PP), or polyvinyl alcohol (PVA). The hydrophobic restoration solution prepared using the above materials can better penetrate the velvet structure of the velvet substrate, thereby restoring the velvet structure of the velvet substrate to the surface of the hydrophobic restoration layer, achieving micron-scale restoration.

[0059] In order to better cure the hydrophobic material, illustratively, the curing agent is a mixture of one or more of dimethyldichlorosilane, aminosilane, tetraethoxysilane, and diethylenetriamine in any proportion.

[0060] Based on the texture structure size of the perovskite light absorbing layer, correspondingly, in the texture structure of the hydrophobic complex layer, the bottom side length of a single complex layer protrusion (for example, a pyramid-shaped protrusion) is 2 to 3 μm.

[0061] In order to confine and induce the perovskite precursor solution to form a single crystal structure between the substrate and the hydrophobic complex layer, illustratively, in step d, the distance between the substrate surface and the tip of the velvet structure of the hydrophobic complex layer is 500-1000 nm.

[0062] In order to better form a single crystal structure, illustratively, in the above step e, the perovskite precursor solution is crystallized at 60-80° C. and a humidity of 45%-55%.

[0063] The preparation of the perovskite precursor solution includes the following steps:

[0064] The perovskite precursor raw materials are stirred and mixed to obtain a perovskite precursor solution, wherein the perovskite precursor raw materials include an A-site cationic compound, a lead halide, and an organic solvent, wherein the molar ratio of the A-site cationic compound to the lead halide is 1:1 to 1:1.5, the stirring temperature is 20 to 30° C. (for example, 25° C.), and the stirring time is 5 to 12 h (for example, 8 h).

[0065] Exemplarily, the A-site cationic compound is a mixture of one or more of methyl ether iodide (FAI), methyl ether bromide (FABr), methyl ether chloride (FACl), methylammonium iodide (MAI), methylammonium bromide (MABr2), methylammonium chloride (MACl), butylammonium iodide (BAI), butylammonium bromide (BABr) and butylammonium chloride (BACl) in any proportion.

[0066] The lead halide is lead iodide (PbI2) or lead bromide (PbBr2).

[0067] The organic solvent is a mixture of one or more of N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethanol and propanol in any proportion.

[0068] In a third aspect, the present invention provides a perovskite solar cell comprising the perovskite light-absorbing layer provided in the first aspect.

[0069] Compared with the prior art, the beneficial effects of the perovskite solar cell provided by the present invention are substantially the same as the beneficial effects of the perovskite light-absorbing layer provided by the first aspect, and are not described in detail here.

[0070] It should be noted that based on the different types of substrates of perovskite solar cells, the specific structure of the above perovskite solar cells is as follows:

[0071] When the substrate 1 is a glass substrate, the perovskite solar cell is a perovskite single junction cell. Figure 1a , including a glass substrate and a hole transport layer 2, a perovskite light absorption layer 3, an electron transport layer 4 and a positive electrode 7 stacked in sequence on the light-receiving surface of the glass substrate.

[0072] When the substrate 1 is a conductive silicon substrate, the perovskite solar cell is a perovskite / crystalline silicon tandem cell. For the structure of the perovskite silicon tandem cell, see Figure 1b It includes a conductive silicon substrate, a hole transport layer 2, a perovskite light absorption layer 3, an electron transport layer 4, a buffer layer 5, a front composite layer 6 and a positive electrode 7 stacked in sequence on the light-receiving surface of the conductive silicon substrate, an anti-reflection layer 9 arranged on the surface of the front composite layer 6 and located between the two positive electrodes 7, and a back electrode 8 formed on the backlight surface of the conductive silicon substrate.

[0073] In order to further increase the optical path length of light inside the perovskite solar cell, thereby improving the photoelectric conversion efficiency of the perovskite solar cell, the light-receiving surface of the above-mentioned substrate 1 is a planar structure; or, the light-receiving surface of the above-mentioned substrate 1 is a velvet structure, or the light-receiving surface of the substrate 1 is a velvet structure, and the velvet structure of the substrate 1 has the same shape as the velvet structure of the perovskite light-absorbing layer 3.

[0074] It should be noted that the above-mentioned method for preparing a perovskite solar cell includes the following steps:

[0075] Step 1: providing a laminated structure formed by laminating a substrate 1 and a hole transport layer 2;

[0076] Step 2: forming a perovskite light absorption layer 3 on the surface of the hole transport layer 2. The perovskite light absorption layer 3 is formed by the method for preparing the perovskite light absorption layer provided in the second aspect.

[0077] It should be noted that, in the process of preparing the perovskite light-absorbing layer 3 , the size of the textured substrate used is the same as that of the conductive silicon substrate 1 .

[0078] For a perovskite single-junction cell, the preparation method includes the following steps:

[0079] Step A: providing a glass substrate;

[0080] Step B: forming a hole transport layer 2, a perovskite light absorption layer 3, an electron transport layer 4 and a positive electrode 7 (eg, an Au electrode or an Ag electrode) in sequence on the surface of a glass substrate to obtain a perovskite solar cell.

[0081] For perovskite silicon tandem cells, the preparation method includes the following steps:

[0082] Step A': providing a conductive silicon substrate;

[0083] Step B': forming a hole transport layer 2, a perovskite light absorption layer 3, an electron transport layer 4, a buffer layer 5, a front recombination layer 6 and a positive electrode 7 (for example, an Ag electrode) in sequence on the surface of a conductive silicon substrate;

[0084] Step C': forming an anti-reflection layer 9 between the two positive electrodes 7 and on the surface of the front composite layer 6, and forming a back electrode 8 on the backlight side of the conductive silicon substrate to obtain a perovskite solar cell.

[0085] Specifically, the formation methods of the above layers are as follows:

[0086] The method for forming the hole transport layer 2 includes the following steps:

[0087] Placing the conductive silicon substrate 1 in the mask of the hole transport layer 2;

[0088] A nickel oxide layer is sputtered on the surface of the conductive silicon substrate 1 using a radio frequency magnetron sputtering mode, wherein the vacuum degree is 9.5 to 10.5×10 -4 Pa, sputtering power is 85-90W, argon flow rate is 18-25sccm, and sputtering time is 8-15min;

[0089] A (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz) layer is spin-coated on the surface of the nickel oxide layer, wherein the amount of 2PACz is 50-110 μL, the spin-coating speed is 2800-3000 rpm, the spin-coating acceleration is 2800-3000 rpm / s, and the spin-coating time is 25-30 s;

[0090] The conductive silicon substrate 1 with the 2PACz layer spin-coated thereon is placed on a hot stage and annealed at 95-100° C. for 8-10 minutes to form a hole transport layer 2.

[0091] The method for forming the electron transport layer 4 includes the following steps:

[0092] The stacked structure consisting of a conductive silicon substrate 1, a hole transport layer 2 and a perovskite light absorbing layer 3 is placed in the mask of the electron transport layer 4, and a lithium fluoride layer (LiF layer) and a graphene layer (C60 layer) are sequentially deposited on the surface of the perovskite light absorbing layer 3 at a deposition rate of The vacuum degree is 9.5~10.5×10 -4 Pa, the thickness of the lithium fluoride layer is 0.8 to 1.2 nm, and the thickness of the graphene layer is 8 to 12 nm.

[0093] The method for forming the buffer layer 5 includes the following steps:

[0094] A stacked structure consisting of a conductive silicon substrate 1, a hole transport layer 2, a perovskite light absorbing layer 3 and an electron transport layer 4 is placed in an atomic layer deposition chamber, and a buffer layer 5 is deposited on the surface of the electron transport layer 4, wherein the vacuum degree is 18-25 Pa, the deposition temperature is 145-155°C, the pressure of the water source is 45-55 Pa, the pressure of the tin source is 20-30 Pa, and the number of cycles is 180-220 times.

[0095] The method for forming the front composite layer 6 includes the following steps:

[0096] A stacked structure consisting of a conductive silicon substrate 1, a hole transport layer 2, a perovskite light absorbing layer 3, an electron transport layer 4, and a buffer layer 5 is placed in a mask of a composite layer, and a front composite layer 6 is sputtered (for example, by DC magnetron sputtering) on ​​the surface of the buffer layer 5. The substrate temperature during sputtering is 58-63°C (for example, 60°C), and the pressure in the sputtering chamber is 9.8-10.0×10 -4 Pa (e.g., 9.9×10 -4 Pa), the argon flow rate is 18-20 sccm, the oxygen flow rate is 0.25-0.5 sccm (for example, 0.3 sccm), the sputtering is divided into two times (including a primary sputtering and a secondary sputtering performed in sequence), the primary sputtering intensity is 35-40 W, the sputtering time is 5-7 min (for example, 6.5 min), the secondary sputtering intensity is 140-155 W (for example, 150 W), and the sputtering time is 3.5-5 min (for example, 4 min).

[0097] The method for forming the positive electrode 7 and the back electrode 8 includes the following steps:

[0098] The stacked structure consisting of a conductive silicon substrate 1, a hole transport layer 2, a perovskite light absorption layer 3, an electron transport layer 4, a buffer layer 5 and a front composite layer 6 is placed in a mask placed on a positive electrode 7 and a back electrode 8 respectively, and then the mask is placed in a vacuum deposition device to prepare the positive electrode 7 and the back electrode 8, wherein the vacuum degree is 6 to 7×10 -4 Pa, the thickness of the positive electrode 7 is 385-400 nm, and the thickness of the back electrode 8 is 185-200 nm.

[0099] The method for forming the anti-reflection layer 9 includes the following steps:

[0100] The stacked structure consisting of the back electrode 8, the conductive silicon substrate 1, the hole transport layer 2, the perovskite light absorbing layer 3, the electron transport layer 4, the buffer layer 5, the front composite layer 6 and the positive electrode 7 is placed on the mask, and then the mask is placed in a vacuum deposition device to prepare the anti-reflection layer 9. The vacuum degree is 9.9-10.3×10 -4 Pa, thickness is 100~105nm.

[0101] Example 1

[0102] The perovskite solar cell of this embodiment is prepared by the following steps:

[0103] Step a: Place 15×15cm 2 The silicon wafer is cut into 2×2cm 2 The center of the silicon wafer has a 1.2×1.2cm 2The substrate composite layer is cut with a cutting accuracy error within 1 mm, and the cut silicon wafer is annealed at 200° C. for 15 min to obtain a conductive silicon substrate, wherein the thickness of the conductive silicon substrate is 3 μm and the thickness of the substrate composite layer is 10 nm;

[0104] Step b: Place the conductive silicon substrate obtained in step a on the mask of sputtering nickel oxide hole transport layer, place the mask with the conductive silicon substrate in the magnetron sputtering equipment, and evacuate to 9.9×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 90 W, the argon flow rate was set to 20 sccm, and the sputtering time was 10 min;

[0105] Step c: After the sputtering, the conductive silicon substrate was transferred to a spin coater in a nitrogen glove box and a 2PACz layer was spin-coated at a speed of 3000 rpm, an acceleration of 3000 rpm / s, and a time of 30 s. The substrate was then annealed on a hot plate at 100°C for 8 min to obtain a conductive silicon substrate / hole transport layer stacked structure.

[0106] Step d: Provide a suede silicon battery; take 10ml of polydimethylsiloxane (PDMS) and 1ml of dimethyldichlorosilane curing agent and mix them in a glass bottle. Stir well and let it stand to remove bubbles until there are no visible bubbles in the mixture. Then, extract 300ul of the mixed solution of polydimethylsiloxane and dimethyldichlorosilane and drop it on a suede silicon battery of the same specifications as the conductive silicon substrate. Use a UV light curing lamp to cure it at 25°C and then peel it off to form a hydrophobic composite layer. The thickness of the hydrophobic composite layer is 5μm. The contact surface between the hydrophobic composite layer and the suede silicon battery is called "suede". In the suede structure of the hydrophobic composite layer, the protrusion of a single rejuvenation layer is pyramidal with a bottom side length of 2μm. Figure 4 ;

[0107] Step e: Methylammonium bromide (MABr2) and lead bromide (PbBr2) were mixed in N,N-dimethylformamide (DMF) at a molar ratio of 1:1 and stirred at 25°C for 8 hours to obtain a perovskite precursor solution. The concentration of perovskite in the perovskite precursor solution was 1.6 mol / ml;

[0108] Step f: placing the laminated structure obtained in step c horizontally, and dripping the perovskite precursor solution onto the laminated structure obtained in step c;

[0109] Step g: The velvet surface of the hydrophobic composite layer is placed close to the surface of the laminated structure, and a preset gap (500 nm) is formed between the hydrophobic composite layer and the hole transport layer. After crystallization at a temperature of 60°C and a humidity of 45% until a film is formed, the hydrophobic composite layer is peeled off, and the perovskite is epitaxially grown and crystallized in the horizontal direction to form a single crystal perovskite light-absorbing layer, thereby obtaining a laminated structure of a conductive silicon substrate / hole transport layer / perovskite light-absorbing layer. In the velvet structure of the perovskite light-absorbing layer, the protrusion of a single light-absorbing layer is pyramidal, with a bottom side length of 2 μm. Figure 5 ;

[0110] Step h: Place the stacked structure obtained in step g on the mask of the electron transport layer, and place the mask in a vacuum deposition device with a vacuum degree of 9.9×10 -4 LiF and C60 were evaporated at a deposition rate of The thicknesses are 1 nm and 10 nm, respectively, to obtain a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer;

[0111] Step i: placing the laminated structure obtained in step h in an atomic layer deposition chamber to prepare a buffer layer, with a vacuum degree of 20 Pa, a chamber temperature of 150° C., water source and tin source pressures of 50 Pa and 25 Pa, respectively, and 200 cycles to obtain a laminated structure of a conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer;

[0112] Step j: Place the laminated structure obtained in step i on the mask of the ITO front composite layer, and then place the mask in a magnetron sputtering apparatus to prepare the ITO front composite layer. The substrate temperature is 60°C and the pressure in the chamber is 9.9×10 -4 Pa, argon flow rate was 20 sccm, oxygen flow rate was 0.3 sccm, sputtering mode was DC magnetron sputtering, 40 W sputtering for 6.5 min, 150 W sputtering for 4 min, and a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer was obtained;

[0113] Step k: Place the laminated structure obtained in step j in the masks of the positive electrode and the back electrode respectively, and then place the masks in a vacuum deposition device to prepare the electrodes. The vacuum degree is 7×10 -4 Pa, the thickness of the positive electrode and the back electrode are 400nm and 200nm respectively, and a stacked structure of back electrode / conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer / positive electrode is obtained;

[0114] Step 1: Place the laminated structure obtained in step k on a 1.1×1.1 cm 2The mask is then placed in a vacuum deposition device to prepare an anti-reflection layer with a vacuum degree of 9.9×10 -4 Pa with a thickness of 100 nm to obtain a perovskite solar cell.

[0115] Example 2

[0116] The perovskite solar cell of this embodiment is prepared by the following steps:

[0117] Step a: Place 15×15cm 2 The silicon wafer is cut into 2×2cm 2 The center of the silicon wafer has a 1.2×1.2cm 2 The substrate composite layer is cut with a cutting accuracy error within 1 mm, and the cut silicon wafer is annealed at 200° C. for 15 min to obtain a conductive silicon substrate, wherein the thickness of the conductive silicon substrate is 3 μm and the thickness of the substrate composite layer is 10 nm;

[0118] Step b: Place the conductive silicon substrate obtained in step a on the mask of sputtering nickel oxide hole transport layer, place the mask with the conductive silicon substrate in the magnetron sputtering equipment, and evacuate to 10.3×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 88 W, the argon flow rate was set to 18 sccm, and the sputtering time was 14 min;

[0119] Step c: After the sputtering, the conductive silicon substrate was transferred to a spin coater in a nitrogen glove box and a 2PACz layer was spin-coated. The amount of 2PACz was 60 μL, the rotation speed was 2850 rpm, the acceleration was 2850 rpm / s, and the time was 26 s. Then, the substrate was annealed on a hot plate at 95°C for 10 min to obtain a conductive silicon substrate / hole transport layer stacked structure.

[0120] Step d: Providing a textured silicon battery; taking 8ml of epoxy resin (EP) and 1ml of diethylenetriamine curing agent, mixing them in a glass bottle, stirring them evenly, and then letting them stand to remove bubbles until no bubbles are visible in the mixture. Then, taking 350ul of the epoxy resin and diethylenetriamine mixed solution and dropping it onto a textured silicon battery of the same specifications as the conductive silicon substrate, curing it under a UV light curing lamp at 30°C, and then peeling it off to form a hydrophobic composite layer. The hydrophobic composite layer has a thickness of 6μm. The contact surface between the hydrophobic composite layer and the textured silicon battery is called "texture". In the texture structure of the hydrophobic composite layer, the protrusion of a single rejuvenation layer is pyramidal, with a bottom side length of 3μm.

[0121] Step e: Mixing methyl ether iodine (FAI) and lead iodide (PbI2) in a molar ratio of 1:1.5 in dimethyl sulfoxide (DMSO) and stirring at 30°C for 5 hours to obtain a perovskite precursor solution, wherein the concentration of perovskite in the perovskite precursor solution is 1.9 mol / ml;

[0122] Step f: placing the laminated structure obtained in step c horizontally, and dripping the perovskite precursor solution onto the laminated structure obtained in step c;

[0123] Step g: placing the suede surface of the hydrophobic composite layer close to the surface of the laminated structure, forming a preset gap (750 nm) between the hydrophobic composite layer and the hole transport layer, and peeling off the hydrophobic composite layer after crystallization at a temperature of 70°C and a humidity of 55% until a film is formed. The perovskite epitaxially grows and crystallizes in the horizontal direction to form a single crystal perovskite light-absorbing layer, thereby obtaining a laminated structure of a conductive silicon substrate / hole transport layer / perovskite light-absorbing layer. In the suede structure of the perovskite light-absorbing layer, the protrusion of a single light-absorbing layer is pyramidal, with a bottom side length of 2 μm;

[0124] Step h: Place the stacked structure obtained in step g into the mask of the electron transport layer, and place the mask in a vacuum deposition device with a vacuum degree of 10.3×10 -4 LiF and C60 were evaporated at a deposition rate of The thicknesses are 0.9 nm and 11 nm, respectively, to obtain a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer;

[0125] Step i: placing the stacked structure obtained in step h in an atomic layer deposition chamber to prepare a buffer layer, with a vacuum degree of 18 Pa, a chamber temperature of 155° C., water source and tin source pressures of 45 Pa and 20 Pa, respectively, and a cycle number of 220 to obtain a stacked structure of a conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer;

[0126] Step j: Place the laminated structure obtained in step i on the mask of the ITO front composite layer, and then place the mask in a magnetron sputtering apparatus to prepare the ITO front composite layer. The substrate temperature is 62°C and the pressure in the chamber is 10.0×10 -4 Pa, argon flow rate was 18 sccm, oxygen flow rate was 0.45 sccm, sputtering mode was DC magnetron sputtering, 35 W sputtering for 6 min, 140 W sputtering for 5 min, and a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer was obtained;

[0127] Step k: Place the laminated structure obtained in step j in the masks of the positive electrode and the back electrode respectively, and then place the masks in a vacuum deposition device to prepare the electrodes. The vacuum degree is 6×10 -4Pa, the thickness of the positive electrode and the back electrode are 385nm and 185nm respectively, and a stacked structure of back electrode / conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer / positive electrode is obtained;

[0128] Step 1: Place the laminated structure obtained in step k on a 1.1×1.1 cm 2 The mask is then placed in a vacuum deposition device to prepare an anti-reflection layer with a vacuum degree of 10.3×10 -4 Pa with a thickness of 105 nm to obtain a perovskite solar cell.

[0129] Example 3

[0130] The perovskite solar cell of this embodiment is prepared by the following steps:

[0131] Step a: Place 15×15cm 2 The silicon wafer is cut into 2×2cm 2 The center of the silicon wafer has a 1.2×1.2cm 2 The substrate composite layer is cut with a cutting accuracy error within 1 mm, and the cut silicon wafer is annealed at 180° C. for 18 minutes to obtain a conductive silicon substrate, wherein the thickness of the conductive silicon substrate is 5 μm and the thickness of the substrate composite layer is 8 nm;

[0132] Step b: Place the conductive silicon substrate obtained in step a on the mask of the sputtered nickel oxide hole transport layer, place the mask with the conductive silicon substrate in a magnetron sputtering device, and evacuate to 10.5×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 85 W, the argon flow rate was set to 24 sccm, and the sputtering time was 8 min;

[0133] Step c: After the sputtering, the conductive silicon substrate was transferred to a spin coater in a nitrogen glove box and a 2PACz layer was spin-coated at 80 μL of 2PACz, a rotation speed of 2800 rpm, an acceleration of 2800 rpm / s, and a time of 25 s. The substrate was then annealed on a hot plate at 100°C for 10 min to obtain a conductive silicon substrate / hole transport layer stacked structure.

[0134] Step d: Providing a suede silicon battery; taking 12 ml of polyurethane (PU) and 1 ml of aminosilane curing agent, mixing them in a glass bottle, stirring them evenly, and then standing them to remove bubbles until no bubbles are visible in the mixture. Then, 400 ul of the mixed solution of polyurethane and aminosilane is dripped onto a suede silicon battery of the same specifications as the conductive silicon substrate. After curing it under a UV light curing lamp at 25°C, it is peeled off to form a hydrophobic composite layer. The thickness of the hydrophobic composite layer is 8 μm. The contact surface between the hydrophobic composite layer and the suede silicon battery is called "suede". In the suede structure of the hydrophobic composite layer, the protrusion of a single rejuvenation layer is pyramidal, and the bottom side length is 3 μm.

[0135] Step e: mixing butylammonium chloride (BACl) and lead bromide (PbBr2) in ethanol at a molar ratio of 1:1 and stirring at 20°C for 12 hours to obtain a perovskite precursor solution, wherein the concentration of perovskite in the perovskite precursor solution is 1.6 mol / ml;

[0136] Step f: placing the laminated structure obtained in step c horizontally, and dripping the perovskite precursor solution onto the laminated structure obtained in step c;

[0137] Step g: placing the suede surface of the hydrophobic composite layer close to the surface of the laminated structure, forming a preset gap (1000 nm) between the hydrophobic composite layer and the hole transport layer, and peeling off the hydrophobic composite layer after crystallization at a temperature of 80°C and a humidity of 50% until a film is formed. The perovskite epitaxially grows and crystallizes in the horizontal direction to form a single crystal perovskite light-absorbing layer, thereby obtaining a laminated structure of a conductive silicon substrate / hole transport layer / perovskite light-absorbing layer. In the suede structure of the perovskite light-absorbing layer, the protrusion of a single light-absorbing layer is pyramidal, with a bottom side length of 3 μm.

[0138] Step h: Place the stacked structure obtained in step g on the mask of the electron transport layer, and place the mask in a vacuum deposition device with a vacuum degree of 9.5×10 -4 LiF and C60 were evaporated at a deposition rate of The thicknesses are 1.2nm and 12nm, respectively, to obtain a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer;

[0139] Step i: placing the stacked structure obtained in step h in an atomic layer deposition chamber to prepare a buffer layer, with a vacuum degree of 25 Pa, a chamber temperature of 145° C., water source and tin source pressures of 55 Pa and 30 Pa, respectively, and 180 cycles to obtain a stacked structure of a conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer;

[0140] Step j: Place the laminated structure obtained in step i on the mask of the ITO front composite layer, and then place the mask in a magnetron sputtering apparatus to prepare the ITO front composite layer. The substrate temperature is 58°C and the pressure in the chamber is 9.8×10 -4 Pa, argon flow rate was 19 sccm, oxygen flow rate was 0.5 sccm, sputtering mode was DC magnetron sputtering, 38 W sputtering for 7 min, 155 W sputtering for 3.5 min, and a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer was obtained;

[0141] Step k: Place the laminated structure obtained in step j in the masks of the positive electrode and the back electrode respectively, and then place the masks in a vacuum deposition device to prepare the electrodes. The vacuum degree is 6.5×10 -4 Pa, the thicknesses of the positive electrode and the back electrode are 390nm and 190nm, respectively, to obtain a stacked structure of back electrode / conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer / positive electrode;

[0142] Step 1: Place the laminated structure obtained in step k on a 1.1×1.1 cm 2 The mask is then placed in a vacuum deposition device to prepare an anti-reflection layer with a vacuum degree of 10.0×10 -4 Pa, with a thickness of 102 nm, to obtain a perovskite solar cell.

[0143] Example 4

[0144] The perovskite solar cell of this embodiment is prepared by the following steps:

[0145] Step a: Place 15×15cm 2 The silicon wafer is cut into 2×2cm 2 The center of the silicon wafer has a 1.2×1.2cm 2 The substrate composite layer is cut with a cutting accuracy error within 1 mm, and the cut silicon wafer is annealed at 180° C. for 18 minutes to obtain a conductive silicon substrate, wherein the thickness of the conductive silicon substrate is 5 μm and the thickness of the substrate composite layer is 8 nm;

[0146] Step b: Place the conductive silicon substrate obtained in step a on the mask of the sputtered nickel oxide hole transport layer, place the mask with the conductive silicon substrate in a magnetron sputtering device, and evacuate to 10.5×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 85 W, the argon flow rate was set to 24 sccm, and the sputtering time was 8 min;

[0147] Step c: After the sputtering, the conductive silicon substrate was transferred to a spin coater in a nitrogen glove box and a 2PACz layer was spin-coated at 80 μL of 2PACz, a rotation speed of 2800 rpm, an acceleration of 2800 rpm / s, and a time of 25 s. The substrate was then annealed on a hot plate at 100°C for 10 min to obtain a conductive silicon substrate / hole transport layer stacked structure.

[0148] Step d: providing a textured silicon cell; taking 12 ml of polyvinyl alcohol (PVA) and 1 ml of tetraethoxysilane curing agent, mixing them in a glass bottle, stirring them evenly, and then letting them stand to remove bubbles until no bubbles are visible in the mixture. Then, taking 400 ul of the mixed solution of polyvinyl alcohol and tetraethoxysilane and dropping it onto a textured silicon cell of the same specifications as the conductive silicon substrate, curing it under a UV light curing lamp at 25°C, and then peeling it off to form a hydrophobic composite layer. The thickness of the hydrophobic composite layer is 8 μm. The contact surface between the hydrophobic composite layer and the textured silicon cell is called "texture". In the texture structure of the hydrophobic composite layer, the protrusion of a single rejuvenation layer is pyramidal, and the bottom side length is 3 μm.

[0149] Step e: mixing butylammonium chloride (FACl) and lead bromide (PbI2) in propanol at a molar ratio of 1:1.2 and stirring at 20°C for 12 hours to obtain a perovskite precursor solution, wherein the concentration of perovskite in the perovskite precursor solution is 1.7 mol / ml;

[0150] Step f: placing the laminated structure obtained in step c horizontally, and dripping the perovskite precursor solution onto the laminated structure obtained in step c;

[0151] Step g: placing the suede surface of the hydrophobic composite layer close to the surface of the laminated structure, forming a preset gap (600 nm) between the hydrophobic composite layer and the hole transport layer, and peeling off the hydrophobic composite layer after crystallization at a temperature of 65°C and a humidity of 50% until a film is formed. The perovskite epitaxially grows and crystallizes in the horizontal direction to form a single crystal perovskite light-absorbing layer, thereby obtaining a laminated structure of a conductive silicon substrate / hole transport layer / perovskite light-absorbing layer. In the suede structure of the perovskite light-absorbing layer, the protrusion of a single light-absorbing layer is pyramidal, with a bottom side length of 3 μm.

[0152] Step h: Place the stacked structure obtained in step g on the mask of the electron transport layer, and place the mask in a vacuum deposition device with a vacuum degree of 9.8×10 -4 LiF and C60 were evaporated at a deposition rate of The thicknesses are 1.0 nm and 10 nm, respectively, to obtain a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer;

[0153] Step i: placing the stacked structure obtained in step h in an atomic layer deposition chamber to prepare a buffer layer, with a vacuum degree of 25 Pa, a chamber temperature of 145° C., water source and tin source pressures of 55 Pa and 30 Pa, respectively, and 180 cycles to obtain a stacked structure of a conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer;

[0154] Step j: Place the laminated structure obtained in step i on the mask of the ITO front composite layer, and then place the mask in a magnetron sputtering apparatus to prepare the ITO front composite layer. The substrate temperature is 58°C and the pressure in the chamber is 9.8×10 -4 Pa, argon flow rate was 19 sccm, oxygen flow rate was 0.5 sccm, sputtering mode was DC magnetron sputtering, 38 W sputtering for 7 min, 155 W sputtering for 3.5 min, and a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer was obtained;

[0155] Step k: Place the laminated structure obtained in step j in the masks of the positive electrode and the back electrode respectively, and then place the masks in a vacuum deposition device to prepare the electrodes. The vacuum degree is 6.5×10 -4 Pa, the thicknesses of the positive electrode and the back electrode are 390nm and 190nm, respectively, to obtain a stacked structure of back electrode / conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer / positive electrode;

[0156] Step 1: Place the laminated structure obtained in step k on a 1.1×1.1 cm 2 The mask is then placed in a vacuum deposition device to prepare an anti-reflection layer with a vacuum degree of 10.0×10 -4 Pa, with a thickness of 102 nm, to obtain a perovskite solar cell.

[0157] Example 5

[0158] The perovskite solar cell of this embodiment is prepared by the following steps:

[0159] Step a: Place 15×15cm 2 The silicon wafer is cut into 2×2cm 2 The center of the silicon wafer has a 1.2×1.2cm 2 The substrate composite layer is cut with a cutting accuracy error within 1 mm, and the cut silicon wafer is annealed at 190° C. for 16 min to obtain a conductive silicon substrate, wherein the thickness of the conductive silicon substrate is 6 μm and the thickness of the substrate composite layer is 10 nm;

[0160] Step b: Place the conductive silicon substrate obtained in step a on the mask of the sputtered nickel oxide hole transport layer, place the mask with the conductive silicon substrate in a magnetron sputtering device, and evacuate to 10.5×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 85 W, the argon flow rate was set to 24 sccm, and the sputtering time was 8 min;

[0161] Step c: After the sputtering, the conductive silicon substrate was transferred to a spin coater in a nitrogen glove box and a 2PACz layer was spin-coated at 95 μL of 2PACz, a rotation speed of 2900 rpm, an acceleration of 2900 rpm / s, and a time of 28 s. The substrate was then annealed on a hot plate at 100°C for 10 min to obtain a conductive silicon substrate / hole transport layer stacked structure.

[0162] Step d: Providing a textured silicon cell; taking 12 ml of polymethyl methacrylate (PMMA) and 1 ml of tetraethoxysilane curing agent, mixing them in a glass bottle, stirring them evenly, and then letting them stand to remove bubbles until no bubbles are visible in the mixture. Then, taking 400 ul of the mixed solution of polymethyl methacrylate and tetraethoxysilane, dripping it onto a textured silicon cell of the same specifications as the conductive silicon substrate, curing it under a UV light curing lamp at 25°C, and then peeling it off to form a hydrophobic composite layer. The thickness of the hydrophobic composite layer is 8 μm. The contact surface between the hydrophobic composite layer and the textured silicon cell is called "texture". In the textured structure of the hydrophobic composite layer, the protrusion of a single rejuvenation layer is pyramidal, with a bottom side length of 2.5 μm.

[0163] Step e: mixing butylammonium chloride (FACl) and lead bromide (PbI2) in propanol at a molar ratio of 1:1.3 and stirring at 25°C for 10 hours to obtain a perovskite precursor solution, wherein the concentration of perovskite in the perovskite precursor solution is 1.8 mol / ml;

[0164] Step f: placing the laminated structure obtained in step c horizontally, and dripping the perovskite precursor solution onto the laminated structure obtained in step c;

[0165] Step g: placing the suede surface of the hydrophobic composite layer close to the surface of the laminated structure, forming a preset gap (800 nm) between the hydrophobic composite layer and the hole transport layer, and peeling off the hydrophobic composite layer after crystallization at a temperature of 70°C and a humidity of 55% until a film is formed. The perovskite is epitaxially grown and crystallized in the horizontal direction to form a single crystal perovskite light-absorbing layer, thereby obtaining a laminated structure of a conductive silicon substrate / hole transport layer / perovskite light-absorbing layer. In the suede structure of the perovskite light-absorbing layer, the protrusion of a single light-absorbing layer is pyramidal, with a bottom side length of 2.5 μm.

[0166] Step h: Place the stacked structure obtained in step g on the mask of the electron transport layer, and place the mask in a vacuum deposition device with a vacuum degree of 9.9×10-4 LiF and C60 were evaporated at a deposition rate of The thicknesses are 1.0 nm and 10 nm, respectively, to obtain a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer;

[0167] Step i: placing the stacked structure obtained in step h in an atomic layer deposition chamber to prepare a buffer layer, with a vacuum degree of 25 Pa, a chamber temperature of 150° C., water source and tin source pressures of 55 Pa and 30 Pa, respectively, and a cycle number of 196 to obtain a stacked structure of a conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer;

[0168] Step j: Place the laminated structure obtained in step i on the mask of the ITO front composite layer, and then place the mask in a magnetron sputtering apparatus to prepare the ITO front composite layer. The substrate temperature is 60°C and the pressure in the chamber is 9.9×10 -4 Pa, argon flow rate was 19 sccm, oxygen flow rate was 0.5 sccm, sputtering mode was DC magnetron sputtering, 38 W sputtering for 7 min, 155 W sputtering for 3.5 min, and a stacked structure of conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer was obtained;

[0169] Step k: Place the laminated structure obtained in step j in the masks of the positive electrode and the back electrode respectively, and then place the masks in a vacuum deposition device to prepare the electrodes. The vacuum degree is 6.8×10 -4 Pa, the thickness of the positive electrode and the back electrode are 395nm and 195nm respectively, and a stacked structure of back electrode / conductive silicon substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer / positive electrode is obtained;

[0170] Step 1: Place the laminated structure obtained in step k on a 1.1×1.1 cm 2 The mask is then placed in a vacuum deposition device to prepare an anti-reflection layer with a vacuum degree of 10.1×10 -4 Pa, with a thickness of 103 nm, to obtain a perovskite solar cell.

[0171] Example 6

[0172] The perovskite solar cell of this embodiment is prepared by the following steps:

[0173] Step a: 1.5 x 1.5 cm 2 The substrate (ITO glass substrate) was ultrasonically cleaned in acetone and anhydrous ethanol for 20 minutes, then dried with nitrogen and treated in ozone for 30 minutes.

[0174] Step b: Place the glass substrate in the mask of sputtered nickel oxide hole transport layer, place the mask with glass substrate in magnetron sputtering equipment, and evacuate to 9.9×10 -4 When Pa, the RF magnetron sputtering mode was selected, the power was adjusted to 90 W, the argon flow rate was set to 20 sccm, and the sputtering time was 10 min;

[0175] Step c: After sputtering, the glass substrate was transferred to a spin coater in a nitrogen glove box and a 2PACz layer was spin-coated at a speed of 3000 rpm, an acceleration of 3000 rpm / s, and a time of 30 s. The substrate was then annealed on a hot plate at 100°C for 8 min to obtain a glass substrate / hole transport layer structure.

[0176] Step d: Provide a suede silicon battery; take 10ml of polydimethylsiloxane (PDMS) and 1ml of dimethyldichlorosilane curing agent and mix them in a glass bottle. After stirring evenly, let it stand to remove bubbles until there are no visible bubbles in the mixture. Then, extract 300ul of the mixed solution of polydimethylsiloxane and dimethyldichlorosilane and drop it on a suede silicon battery of the same specifications as the glass substrate. After curing it under a UV light curing lamp at 25°C, peel it off to form a hydrophobic composite layer. The thickness of the hydrophobic composite layer is 5μm. The contact surface between the hydrophobic composite layer and the suede silicon battery is called "suede". In the suede structure of the hydrophobic composite layer, the protrusion of a single rejuvenation layer is pyramidal with a bottom side length of 2μm. Figure 4 ;

[0177] Step e: Methylammonium bromide (MABr2) and lead bromide (PbBr2) were mixed in N,N-dimethylformamide (DMF) at a molar ratio of 1:1 and stirred at 25°C for 8 hours to obtain a perovskite precursor solution. The concentration of perovskite in the perovskite precursor solution was 1.6 mol / ml;

[0178] Step f: placing the laminated structure obtained in step c horizontally, and dripping the perovskite precursor solution onto the laminated structure obtained in step c;

[0179] Step g: placing the suede surface of the hydrophobic composite layer close to the surface of the laminated structure, forming a preset gap (500 nm) between the hydrophobic composite layer and the hole transport layer, and peeling off the hydrophobic composite layer after crystallization at a temperature of 60°C and a humidity of 45% until a film is formed. The perovskite epitaxially grows and crystallizes in the horizontal direction to form a single crystal perovskite light-absorbing layer, thereby obtaining a laminated structure of a glass substrate / hole transport layer / perovskite light-absorbing layer. In the suede structure of the perovskite light-absorbing layer, the protrusion of a single light-absorbing layer is pyramidal, with a bottom side length of 2 μm.

[0180] Step h: Place the stacked structure obtained in step g on the mask of the electron transport layer, and place the mask in a vacuum deposition device with a vacuum degree of 9.9×10 -4 LiF and C60 were evaporated at a deposition rate of The thicknesses were 1 nm and 10 nm, respectively, to obtain a stacked structure of glass substrate / hole transport layer / perovskite light absorbing layer / electron transport layer;

[0181] Step i: placing the laminated structure obtained in step h in an atomic layer deposition chamber to prepare a buffer layer, with a vacuum degree of 20 Pa, a chamber temperature of 150° C., water source and tin source pressures of 50 Pa and 25 Pa, respectively, and 200 cycles to obtain a laminated structure of glass substrate / hole transport layer / perovskite light absorbing layer / electron transport layer / buffer layer;

[0182] Step j: Place the laminated structure obtained in step i on the mask of the ITO front composite layer, and then place the mask in a magnetron sputtering apparatus to prepare the ITO front composite layer. The substrate temperature is 60°C and the pressure in the chamber is 9.9×10 -4 Pa, argon flow rate was 20 sccm, oxygen flow rate was 0.3 sccm, sputtering mode was DC magnetron sputtering, 40 W sputtering for 6.5 min, 150 W sputtering for 4 min, and a stacked structure of glass substrate / hole transport layer / perovskite light absorption layer / electron transport layer / buffer layer / front composite layer was obtained;

[0183] Step k: Place the laminated structure obtained in step j in the mask of the positive electrode, and then place the mask in a vacuum deposition device to prepare the electrode. The vacuum degree is 7×10 -4 Pa, and the positive electrode thicknesses are 400 nm and 200 nm, respectively, to obtain perovskite solar cells.

[0184] Comparative Example 1

[0185] The raw materials, steps, and process conditions used in Comparative Example 1 are substantially the same as those in Example 1, except that Comparative Example 1 adopts a one-step spin coating method (corresponding to steps d to g of Example 1):

[0186] Step d: Mixing methylammonium bromide (MABr2) and lead bromide (PbBr2) in a molar ratio of 1:1 in N,N-dimethylformamide (DMF);

[0187] Step e: stirring at 25° C. for 8 h to obtain a perovskite precursor solution;

[0188] Step f: placing the laminated structure obtained in step c on a spin coater, adding 115 μL of the perovskite precursor solution dropwise and performing spin coating at a rotation speed of 4000 rpm, an acceleration of 4000 rpm / s, and a time of 30 s;

[0189] Step g: placing the spin-coated perovskite precursor solution stacked structure on a hot plate at an ambient humidity of 70% and a temperature of 150° C. for annealing for 30 minutes to obtain a stacked structure of a conductive silicon substrate / hole transport layer / perovskite light absorbing layer.

[0190] The solar cells prepared in Examples 1 to 5 and Comparative Example 1 were subjected to relevant performance tests, as shown in Table 1. The short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF), and power conversion efficiency (PCE) were measured under standard test conditions (AM1.5, 25°C, 1000 W / m 2 ) was measured.

[0191] Table 1 Battery electrical properties of Examples 1 to 5 and Comparative Example 1

[0192]

[0193] As can be seen from Table 1, the electrical performance parameters of Examples 1 to 5 are significantly better than those of Comparative Example 1, as follows:

[0194] For stacked perovskite solar cells, the short-circuit current density is 20-21 mA / cm 2 , the open circuit voltage is 1.79~1.87V, the fill factor is 72~81%, and the conversion efficiency is 27~30%.

[0195] For a single-cell perovskite solar cell, the short-circuit current density is 20.5-20.7 mA / cm 2 , the open circuit voltage is 1.10~1.12V, the fill factor is 81~82%, and the conversion efficiency is 18.5~18.7%.

[0196] Figure 2 The XRD test diagrams of the perovskite solar cells prepared in Examples 1 to 3 and Comparative Example 1 are shown in FIG. Figure 2 It can be seen that the peak intensity of the characteristic peak of perovskite in Example 1 is the strongest, and there are no other impurity peaks, indicating that the reaction conversion is relatively complete and the crystal quality is good. Secondly, the crystal quality of Example 1 is significantly lower than that of Examples 1 to 3, the peak intensity of the characteristic peak of perovskite is weak, and relatively obvious impurity peaks appear in Comparative Example 1, indicating that the perovskite conversion is incomplete.

[0197] In addition, it can be seen from the XRD test diagram that the grain size of the perovskite crystal decreases in Example 1, Example 2, Example 3 and Comparative Example 1 in this order.

[0198] Figure 3 The EQE test comparison chart of the perovskite solar cells prepared in Examples 1 to 3 and Comparative Example 1 is shown in FIG. Figure 3It can be seen that the integrated short-circuit current density of Examples 1 to 3 and the comparative example is consistent with the short-circuit current density of the perovskite solar cell test.

[0199] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered by the scope of protection of the present invention.

Claims

1. A perovskite light-absorbing layer, characterized in that: At least one surface of the perovskite light absorption layer is a suede structure, and the perovskite light absorption layer is a single crystal structure.

2. The perovskite light absorbing layer according to claim 1, characterized in that The light-receiving surface of the perovskite light-absorbing layer has a suede structure; or, The light-receiving surface and the backlight surface of the perovskite light-absorbing layer both have a suede structure.

3. The perovskite light absorbing layer according to claim 1, characterized in that The velvet structure of the perovskite light-absorbing layer is a concave-convex structure formed by a plurality of protrusions on the surface of the perovskite light-absorbing layer, and the bottom side length of each protrusion is 2 to 3 μm.

4. A method for preparing a perovskite light-absorbing layer, characterized in that: The steps include: Step a: providing a substrate with a suede surface; Step b: dropping a hydrophobic complex solution onto the suede structure surface of the substrate, and peeling the hydrophobic complex solution from the substrate after solidification to obtain a hydrophobic complex layer with a suede structure on the surface; Step c: providing a substrate on which a perovskite light absorbing layer is to be prepared, and dripping a perovskite precursor solution onto the surface of the substrate on which the perovskite light absorbing layer is to be prepared; Step d: Covering the hydrophobic composite layer on the perovskite precursor solution, with the suede structure facing the perovskite precursor solution; Step e: After the perovskite precursor solution crystallizes to form a film layer, the hydrophobic complex layer is peeled off, thereby forming at least one single crystal perovskite light-absorbing layer with a suede structure on the surface of the substrate; Wherein, the hydrophobic complex solution comprises a hydrophobic material and a curing agent.

5. The method for preparing a perovskite light absorbing layer according to claim 4, wherein: In the hydrophobic complex solution, the hydrophobic material includes polydimethylsiloxane, epoxy resin, polymethyl methacrylate, polyurethane, polypropylene or polyvinyl alcohol, and the curing agent includes at least one or more of dimethyldichlorosilane, aminosilane, tetraethoxy and diethylenetriamine mixed in any proportion.

6. The method for preparing a perovskite light absorbing layer according to claim 5, wherein: The volume ratio of the hydrophobic material to the curing agent is 8 to 12:

1.

7. The method for preparing a perovskite light absorbing layer according to any one of claims 4 to 6, characterized in that: In the step b, the thickness of the hydrophobic complex layer is 4 to 8 μm; And / or, in the step d, the distance between the substrate surface and the tip of the suede structure of the hydrophobic complex layer is 500-1000 nm.

8. The method for preparing a perovskite light absorbing layer according to claim 4, wherein: In the step c, the concentration of perovskite in the perovskite precursor solution is 1.6 to 1.9 mol / ml; and / or, In the step e, the perovskite precursor solution is crystallized at a temperature of 60 to 80° C. and a humidity of 45% to 55%.

9. A perovskite solar cell, characterized in that: Comprising the perovskite light-absorbing layer according to any one of claims 1 to 3.

10. The perovskite solar cell according to claim 9, characterized in that The perovskite solar cell is a perovskite / crystalline silicon tandem cell, which further includes a conductive silicon substrate, and the perovskite light-absorbing layer is provided on the light-receiving surface of the conductive silicon substrate; The light-receiving surface of the conductive silicon substrate is a planar structure; or, the light-receiving surface of the conductive silicon substrate is a velvet structure; or, the light-receiving surface of the conductive silicon substrate is a velvet structure, and the velvet structure of the conductive silicon substrate has the same shape as the velvet structure of the perovskite light-absorbing layer.

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