A perovskite solar cell and a preparation method thereof

Abstract

This application relates to the technical field of perovskite solar cells, and particularly to a perovskite solar cell and a preparation method thereof. A perovskite solar cell includes a conductive thin film substrate, a perovskite photoactive layer, a hole transport layer, and an electrode layer; a doped conductive enrichment layer is formed on the surface of the conductive thin film substrate; the doped conductive enrichment layer contains conductive particles A and conductive particles B that can form a conductive network; conductive particle A is composed of an inorganic metal-based carrier and a doped metal atom; conductive particle B is at least one of ZnO, SnO2, and In2O3. This application uses a special conductive thin film as a substrate, which serves as a light-transmitting conductive material and simultaneously functions as an electron transport material to collect electrons, replacing the structure of ITO or FTO transparent conductive material + electron transport material TiO2 or SnO2, reducing the number of layers of the battery and simplifying the structure of the perovskite solar cell, eliminating the cumbersome preparation process, and improving the overall production efficiency.

Description

Technical Field

[0001] This application relates to the technical field of perovskite solar cells, and in particular to a perovskite solar cell and a preparation method thereof. Background Art

[0002] A solar cell is a device that can convert light into electrical energy by means of the photovoltaic effect, realizing the utilization of clean energy - solar energy. In the international situation of resource and energy shortage, the development and utilization of solar energy is the focus of research by R & D personnel in various countries. The basis for a solar cell to convert solar energy (light) into electrical energy: When light reaches the solar cell, a part of the incident light is reflected by the surface, and the remaining incident light is transmitted into the solar cell. The transmitted photons are absorbed by the absorber material of the solar cell, and the absorbed light energy excites the electrons of the absorber material to generate electron-hole pairs, and these electron-hole pairs are then separated and collected by the conductive electrodes on the surface of the solar cell.

[0003] Currently, the typical structure of a perovskite solar cell in the related art is fluorine-doped tin oxide (FTO) / low-valent titanium oxide (TiOx) / perovskite / hole transport layer / conductive electrode. For the perovskite solar cell in the related art, the applicant found that the technical solution has the following defects: The preparation steps of the perovskite solar cell in the related art are relatively cumbersome, and the production efficiency is relatively low. Summary of the Invention

[0004] In order to solve the problems that the preparation steps of the perovskite solar cell in the related art are relatively cumbersome and the production efficiency is relatively low, this application provides a perovskite solar cell and a preparation method thereof.

[0005] In a first aspect, a perovskite solar cell provided by this application is achieved through the following technical solution: A perovskite solar cell includes a conductive thin film substrate, and a perovskite photoactive layer, a hole transport layer, and an electrode layer are sequentially compounded on the conductive thin film substrate; a doped conductive enrichment layer is formed on the surface of the conductive thin film substrate facing the perovskite photoactive layer; the doped conductive enrichment layer contains conductive particles A and conductive particles B that can form a conductive network; the mass ratio of the conductive particles A and the conductive particles B is 1:(3 - 7); the particle sizes of the conductive particles A and the conductive particles B are controlled within 10 - 50 nm; the conductive particle A is composed of an inorganic metal-based carrier and a doped metal atom, and the doped metal atom is fixedly connected to the surface of the inorganic metal-based carrier; the mass ratio of the doped metal atom to the inorganic metal-based carrier in the conductive particle is 1:(5 - 8); the doped metal atom is at least one of Zn and Al; the inorganic metal-based carrier is at least one of ZnO and SnO2; the conductive particle B is at least one of ZnO, SnO2, and In2O3.

[0006] This application uses a special conductive thin film as the substrate, which serves as a transparent conductive material and simultaneously functions as an electron transport material to collect electrons, replacing the structure of ITO or FTO transparent conductive material + electron transport material TiO2 or SnO2, reducing the number of battery layers and simplifying the structure of the perovskite solar cell, eliminating the cumbersome preparation process, improving the overall production efficiency, and facilitating the popularization and application of perovskite solar cells.

[0007] Preferably, the conductive particle B is In2O3; the mass ratio of the conductive particle A to the conductive particle B is 1:4; the conductive particle A is composed of zinc oxide and a doped metal atom Zn; the mass ratio of the zinc oxide to the doped metal atom Zn is 1:4.

[0008] The doped conductive enrichment layer formed by adopting the above preferred technical solution has better conductivity, that is, the sheet resistance of the doped conductive enrichment layer can be comparable to that of the ITO transparent conductive thin film. In addition, the doped conductive enrichment layer serves as a transparent conductive material and simultaneously functions as an electron transport material to collect electrons, thereby replacing the structure of ITO or FTO transparent conductive material + electron transport material TiO2 or SnO2, reducing the number of battery layers and simplifying the structure of the perovskite solar cell, eliminating the cumbersome preparation process, and improving the overall production efficiency.

[0009] Preferably, the conductive thin film substrate is mainly prepared from a polymer resin, conductive particle A, and conductive particle B: the total mass of the conductive particle A and the conductive particle B accounts for 10-15% of the mass of the polymer resin.

[0010] By adopting the above technical solution, while ensuring that the doped conductive enrichment layer can serve as a transparent conductive material and simultaneously function as an electron transport material to collect electrons, the production cost is further reduced, thereby facilitating the popularization and application of perovskite solar cells.

[0011] Preferably, the polymer resin includes one of polyether sulfone PES, polyacrylate PAR, polyether-imide PEI, polyethylene naphthalate PEN, polyethylene terephthalate PET, polyphenylene sulfide PPS, polyallylate, polyimide, polycarbonate PC, cellulose triacetate TAC, cellulose acetate propionate CAP, and thermoplastic polyurethane elastomer rubber TPU.

[0012] By adopting the above technical solution, it is ensured that the conductive particle A and the conductive particle B can migrate to the surface under the traction of the electric field force to form a doped conductive enrichment layer, and at the same time, it is ensured that this application has good transparency, mechanical strength, and flexibility, and a flexible perovskite solar cell can be prepared, facilitating the popularization and application of perovskite solar cells.

[0013] Preferably, the preparation method of the conductive particle A includes the following steps:

[0014] S1. The inorganic metal-based support is calcined at 400 - 600 °C and 0.8 - 1.0 Mpa for 10 - 15 min, and after cooling, it is planetary ball milled to a particle size of 10 - 50 nm for standby;

[0015] S2. Preparation of the precursor: 20 - 40 mL of 3 - 5% ammonia water solution is dropped into the metal salt solution at a rate of 80 - 120 μL / s and stirred. The metal salt is at least one of zinc acetylacetonate, zinc nitrate, and aluminum nitrate. The concentration of the metal salt solution is 80 - 120 g / L, and the solvent of the metal salt solution is deionized water. After stirring for 3 - 5 h, the temperature is raised to 60 ± 2 °C within 30 min and stirring continues for 3 h to obtain a mixed solution;

[0016] S3. In-situ coprecipitation synthesis of the conductive particle precursor: The mass ratio of the doped metal atoms to the inorganic metal-based support is 1:(5 - 8). According to the ratio, the inorganic metal-based support precursor in S1 is added to the mixed solution in S2, and the reaction is carried out at 120 - 150 °C for 20 - 28 h. After the reaction is completed, it is cooled to room temperature, and the solid product is obtained by centrifugal separation. The obtained solid product is washed with ethanol and water at least 3 times respectively, and then vacuum dried at 100 °C for 3 - 5 h, and planetary ball milled to obtain a conductive particle powder with a particle size of 10 - 150 nm;

[0017] S4. One-step in-situ generation of the finished conductive particles: The conductive particle powder obtained in S3 is placed in an atmosphere of 5% hydrogen-argon mixed gas and heat-treated at 200 - 400 °C for 2 - 3 h, cooled to room temperature, and ground to obtain the finished conductive particles A.

[0018] By adopting the above technical solutions, the conductive particles A can be prepared in batches, the production cost of the conductive particles A is reduced, and the preparation process difficulty of the conductive particles A is relatively low and the production cost is relatively low. Furthermore, the overall production cost can be reduced, which is convenient for the popularization and application of perovskite solar cells.

[0019] Preferably, the perovskite light-absorbing layer is one of CH3NH3SnI3, CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbCl3, CH(NH2)2PbI3, CH(NH2)2PbBr3, CsSnI3, CsSnBr3, CsSnCl3.

[0020] By adopting the above technical solutions, the obtained perovskite light-absorbing layer with a flat surface and uniform particle size can play a better photoelectric conversion role and ensure the quality of the perovskite solar cell prepared in this application.

[0021] Preferably, the hole transport layer is one of an inorganic hole transport layer and an organic hole transport layer; the inorganic hole transport layer is one of nickel oxide, molybdenum oxide, and tungsten oxide; the organic hole transport layer is one of spiro-OMeTAD, P3HT, PCPDTBT, HTM-TPSI, and Li-TFSI; the electrode layer is one of magnesium (Mg), aluminum (Al), platinum (Pt), silver (Ag), copper (Cu), molybdenum (Mo), titanium (Ti), graphite, and carbon nanotubes.

[0022] By adopting the above technical solution, the hole transport layer is better used to receive the holes generated in the perovskite light absorption layer and transmit them to the electrode layer, which can ensure the quality of the perovskite solar cell prepared in this application.

[0023] Second, a preparation method of a perovskite solar cell provided in this application is realized through the following technical solution:

[0024] A preparation method of a perovskite solar cell includes the following steps:

[0025] Step 1, preparation of a conductive thin film substrate; Step 2, cleaning the doped conductive enrichment layer of the conductive thin film substrate, drying it with dry nitrogen, and performing low-temperature plasma pretreatment;

[0026] Step 2, forming a perovskite light absorption layer on the doped conductive enrichment layer of the conductive thin film substrate;

[0027] Step 3, on the perovskite light absorption layer, preparing a hole transport layer by spin coating;

[0028] Step 4, preparing an electrode layer on the hole transport layer;

[0029] Step 5, encapsulating in a glove box filled with inert gas to obtain a finished perovskite solar cell

[0030] By adopting the above technical solution.

[0031] Preferably, the preparation method of the conductive thin film substrate includes the following steps:

[0032] S1.1, drying treatment of the polymer resin, and at the same time performing surface modification treatment on conductive particle A and conductive particle B;

[0033] S1.2, mixing the dried organic polymer resin with accurately metered conductive particle A and conductive particle B that have completed surface modification treatment evenly, extruding, and granulating to obtain a film-forming masterbatch;

[0034] S1.3, using the film-forming masterbatch for extrusion, casting, and cooling to obtain a semi-finished film;

[0035] S1.4 Heat the semi-finished film to 3 - 8 °C above Tg to make the molecular chain segments in the semi-finished film move freely, and perform particle migration treatment in a uniform electric field. The electric field strength is controlled at 10 4 -10 6 N / C. Perform particle migration treatment for 4 - 6 h to form a doped conductive enrichment layer on the surface layer of the semi-finished film, and cool it to room temperature to obtain a semi-finished conductive thin film substrate;

[0036] S1.5 The semi-finished conductive thin film substrate in Step 4 is treated by an irradiation cross-linking process for 6 - 10 s, and the irradiation dose is controlled at 10 - 15 Mrad to obtain a finished conductive thin film substrate.

[0037] By adopting the above technical solution,

[0038] Preferably, in Step 2, a perovskite light-absorbing layer is formed on the hetero-conductive enrichment layer of the conductive thin film substrate:

[0039] S2.1 Preparation of perovskite precursor solution: Dissolve 1 - 1.2 mol of methylammonium iodide and 1 - 1.2 mol of lead iodide in 1 L of N,N-dimethylformamide. The concentrations of methylammonium iodide and lead iodide are the same, and then add 80 - 120 g of BHT, heat and stir evenly, let it stand for a period of time, and filter. The obtained filtrate is the perovskite precursor solution;

[0040] S2.2 Preparation of perovskite light-absorbing layer: Drop the perovskite precursor solution prepared in S2.1 onto the surface of the hetero-conductive enrichment layer and spin-coat it. Spin-coat at 3000 - 3500 rpm with a rotational acceleration of 180 - 200 rpm / s for 30 ± 2 s, rotate to remove the excess solution. After the spin-coating is completed, place the prepared sample on a heating table and heat it at 90 - 100 °C for 20 - 25 min, and then dry it in air at 120 - 130 °C for 150 - 180 s to obtain a CH3NH3PbI3 perovskite light-absorbing layer.

[0041] By adopting the above technical solution,

[0042] In summary, the present application has the following advantages:

[0043] 1. The present application uses a special conductive thin film as the substrate, which can reduce the number of layers of the battery and simplify the structure of the perovskite solar cell, eliminating the cumbersome preparation process and improving the overall production efficiency.

[0044] 2. The perovskite solar cell produced by the present application has a good conversion efficiency and can be applied industrially. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 is a schematic diagram of the overall structure of the perovskite solar cell in the present application.

[0046] In the figure, 1 is a conductive thin film substrate; 10 is a doped conductive enrichment layer; 2 is a perovskite photoactive layer; 3 is a hole transport layer; 4 is an electrode layer. Specific Embodiments

[0047] The present application will be further described in detail below with reference to the accompanying drawings, comparative examples, and examples.

[0048] Preparation Examples

[0049] Preparation Example 1

[0050] The particle size of conductive particle A is controlled within 10 - 50 nm, and it is composed of an inorganic metal-based carrier and doped metal atoms. The inorganic metal-based carrier is rutile-structured tin dioxide, and the doped metal atoms are Zn.

[0051] The preparation method of conductive particle A includes the following steps:

[0052] S1. Rutile-structured tin dioxide is calcined at 400 °C and 1.0 Mpa for 15 min, cooled, and then planetary ball milled to a particle size of 10 - 50 nm to obtain activated rutile-structured tin dioxide, which is reserved for later use;

[0053] S2. Preparation of the precursor: 40 ml of 5% ammonia water solution is dropped into a 100 g / L zinc acetylacetonate aqueous solution at a rate of 100 μL / s and stirred. After stirring for 4 h, the temperature is raised to 60 °C within 30 min and stirring is continued for 3 h to obtain a mixed solution;

[0054] S3. In-situ coprecipitation synthesis of the conductive particle precursor: The mass ratio of doped metal atoms Zn to tin dioxide is 1:5. According to the ratio, the activated rutile-structured tin dioxide precursor in S1 is added to the mixed solution in S2, and the reaction is carried out at 140 °C for 26 h. After the reaction ends, it is cooled to room temperature, and the solid product is obtained by centrifugal separation. The obtained solid product is washed 3 times with ethanol and water respectively, and then vacuum dried at 100 °C for 4 h, and planetary ball milled to obtain a conductive particle powder with a particle size of 10 - 50 nm;

[0055] S4. One-step in-situ generation of the finished conductive particles: The conductive particle powder obtained in S3 is placed in an atmosphere of 5% hydrogen-argon mixed gas and heat-treated at 400 °C for 4 h, cooled to room temperature, and ball milled to obtain finished conductive particle A with a particle size in the range of 10 - 50 nm.

[0056] Preparation Example 2

[0057] The difference between Preparation Example 2 and Preparation Example 1 is that:

[0058] The particle size of conductive particle A is controlled within 10 - 50 nm, and it is composed of an inorganic metal-based carrier and doped metal atoms. The inorganic metal-based carrier is rutile-structured tin dioxide, and the doped metal atoms are Zn and Al, with the mass percentage of Zn in the doped metal atoms being 80% and that of Al being 20%.

[0059] The preparation method of conductive particle A includes the following steps:

[0060] S1, The rutile-structured tin dioxide is calcined at 400 °C and 1.0 Mpa for 15 min, and after cooling, it is planetary ball-milled to a particle size of 10 - 50 nm to obtain activated rutile-structured tin dioxide for standby;

[0061] S2, Preparation of the precursor: 40 ml of 5% ammonia water solution is added dropwise at a rate of 100 μL / s to an aqueous solution of zinc nitrate / aluminum nitrate with a concentration of 100 g / L and stirred. The mass ratio of zinc nitrate to aluminum nitrate is 0.8:0.2. After stirring for 4 h, the temperature is raised to 60 °C within 30 min and stirring is continued for 3 h to obtain a mixed solution;

[0062] S3, In-situ coprecipitation synthesis of the conductive particle precursor: The mass ratio of the doped metal atoms Zn and Al to tin dioxide is 0.8:0.2:5. According to the ratio, the activated rutile-structured tin dioxide precursor in S1 is added to the mixed solution in S2, and the reaction is carried out at 140 °C for 26 h. After the reaction is completed, it is cooled to room temperature, and the solid product is obtained by centrifugal separation. The obtained solid product is washed 3 times with ethanol and water respectively, and then vacuum-dried at 100 °C for 4 h and planetary ball-milled to obtain a conductive particle powder with a particle size of 10 - 50 nm;

[0063] S4, One-step in-situ generation of the finished conductive particles: The conductive particle powder obtained in S3 is placed in an atmosphere of 5% hydrogen-argon mixed gas and heat-treated at a temperature of 400 °C for 4 h, cooled to room temperature, and ball-milled to obtain finished conductive particle A with a particle size in the range of 10 - 50 nm.

[0064] Preparation Example 3

[0065] The difference between Preparation Example 3 and Preparation Example 1 lies in:

[0066] The particle size of conductive particle A is controlled within 10 - 50 nm, and it is composed of an inorganic metal-based carrier and doped metal atoms. The inorganic metal-based carrier is wurtzite-phase zinc oxide, and the doped metal atoms are Al.

[0067] The preparation method of conductive particle A includes the following steps:

[0068] S1, The rutile-structured tin dioxide is calcined at 400 °C and 1.0 Mpa for 15 min, and after cooling, it is planetary ball-milled to a particle size of 10 - 50 nm to obtain activated rutile-structured tin dioxide for standby;

[0069] S2, Preparation of precursor: 40 ml of 5% ammonia water solution was added dropwise into 100 g / L aluminum nitrate aqueous solution at a rate of 100 μL / s and stirred. After stirring for 4 h, the temperature was raised to 60 °C within 30 min and stirring continued for 3 h to obtain a mixed solution;

[0070] S3, In-situ coprecipitation synthesis of conductive particle precursor: The mass ratio of doped metal atom Al to tin dioxide is 1:5. The tin dioxide precursor with activated rutile structure in S1 was added to the mixed solution in S2 according to the ratio, and the reaction was carried out at 140 °C for 26 h. After the reaction, it was cooled to room temperature, and the solid product was obtained by centrifugal separation. The obtained solid product was washed 3 times with ethanol and water respectively, and then dried in vacuum at 100 °C for 4 h, and planetary ball milling was carried out to obtain conductive particle powder with a particle size of 10 - 50 nm;

[0071] S4, One-step in-situ generation of finished conductive particles: The conductive particle powder obtained in S3 was placed in an atmosphere of 5% hydrogen-argon mixed gas and heat-treated at 400 °C for 4 h, cooled to room temperature, and ball milled to obtain finished conductive particles A with a particle size of 10 - 50 nm.

[0072] Preparation Example 4

[0073] The difference between Preparation Example 4 and Preparation Example 1 is that:

[0074] The particle size of conductive particles A is controlled within 10 - 50 nm and is composed of an inorganic metal-based carrier and doped metal atoms. The inorganic metal-based carrier is zinc oxide with a wurtzite phase, and the doped metal atoms are Al and Zn, among which the mass percentage of Al is 80%.

[0075] The preparation method of conductive particles A includes the following steps:

[0076] S1, Rutile-structured tin dioxide was calcined at 400 °C and 1.0 Mpa for 15 min, cooled and then planetary ball milled to a particle size of 10 - 50 nm to obtain activated rutile-structured tin dioxide for standby;

[0077] S2, Preparation of precursor: 40 ml of 5% ammonia water solution was added dropwise into 100 g / L aluminum nitrate / zinc nitrate aqueous solution and stirred. The mass ratio of zinc nitrate / aluminum nitrate is 0.2:0.8. After stirring for 4 h, the temperature was raised to 60 °C within 30 min and stirring continued for 3 h to obtain a mixed solution;

[0078] S3. In-situ coprecipitation synthesis of conductive particle precursors: The mass ratio of doped metal atoms Zn, Al to tin dioxide is 0.2:0.8:5. Add the activated rutile-structured tin dioxide precursor in S1 to the mixed solution in S2 according to the ratio, react at 140 °C for 26 h. After the reaction, cool to room temperature, centrifuge to obtain a solid product. Wash the obtained solid product with ethanol and water three times respectively, then vacuum dry at 100 °C for 4 h, and perform planetary ball milling to obtain conductive particle powder with a particle size of 10 - 50 nm;

[0079] S4. One-step in-situ generation of finished conductive particles: Place the conductive particle powder obtained in S3 in an atmosphere of 5% hydrogen-argon mixed gas, heat-treat at 400 °C for 4 h, cool to room temperature, and perform ball milling to obtain finished conductive particles A with a particle size of 10 - 50 nm.

[0080] Preparation Example 5

[0081] The difference between Preparation Example 5 and Preparation Example 4 lies in:

[0082] S3. In-situ coprecipitation synthesis of conductive particle precursors: The mass ratio of doped metal atoms Zn, Al to tin dioxide is 0.2:0.8:6. Add the activated rutile-structured tin dioxide precursor in S1 to the mixed solution in S2 according to the ratio, react at 140 °C for 26 h. After the reaction, cool to room temperature, centrifuge to obtain a solid product. Wash the obtained solid product with ethanol and water three times respectively, then vacuum dry at 100 °C for 4 h, and perform planetary ball milling to obtain conductive particle powder with a particle size of 10 - 50 nm.

[0083] Preparation Example 6

[0084] The difference between Preparation Example 6 and Preparation Example 4 lies in:

[0085] S3. In-situ coprecipitation synthesis of conductive particle precursors: The mass ratio of doped metal atoms Zn, Al to tin dioxide is 0.2:0.8:8. Add the activated rutile-structured tin dioxide precursor in S1 to the mixed solution in S2 according to the ratio, react at 140 °C for 26 h. After the reaction, cool to room temperature, centrifuge to obtain a solid product. Wash the obtained solid product with ethanol and water three times respectively, then vacuum dry at 100 °C for 4 h, and perform planetary ball milling to obtain conductive particle powder with a particle size of 10 - 50 nm.

[0086] Preparation Example 7

[0087] The difference between Preparation Example 7 and Preparation Example 4 lies in:

[0088] S3. In-situ coprecipitation synthesis of conductive particle precursors: The mass ratio of doped metal atoms Zn and Al to tin dioxide is 0.2:0.8:4. Add the activated rutile-structured tin dioxide precursor in S1 to the mixed solution in S2 according to the ratio, react at 140 °C for 26 h. After the reaction, cool to room temperature, and centrifuge to obtain a solid product. Wash the obtained solid product with ethanol and water three times respectively, then vacuum dry at 100 °C for 4 h, and perform planetary ball milling to obtain conductive particle powder with a particle size of 10 - 50 nm.

[0089] Preparation Example 8

[0090] The difference between Preparation Example 8 and Preparation Example 4 lies in:

[0091] S3. In-situ coprecipitation synthesis of conductive particle precursors: The mass ratio of doped metal atoms Zn and Al to tin dioxide is 0.2:0.8:10. Add the activated rutile-structured tin dioxide precursor in S1 to the mixed solution in S2 according to the ratio, react at 140 °C for 26 h. After the reaction, cool to room temperature, and centrifuge to obtain a solid product. Wash the obtained solid product with ethanol and water three times respectively, then vacuum dry at 100 °C for 4 h, and perform planetary ball milling to obtain conductive particle powder with a particle size of 10 - 50 nm.

[0092] Example

[0093] Example 1

[0094] Reference Figure 1 , a perovskite solar cell disclosed in the present application, includes a conductive thin film substrate 1, and a doped conductive enrichment layer 10 is formed on the surface of the conductive thin film substrate 1. A perovskite photoactive layer 2, a hole transport layer 3, and an electrode layer 4 are sequentially formed on the surface of the doped conductive enrichment layer 10. The doped conductive enrichment layer 10 contains conductive particles A and conductive particles B that can form a conductive network. The particle sizes of the conductive particles A and conductive particles B are controlled within 10 - 50 nm. The perovskite light-absorbing layer 2 is CH3NH3PbI3. The hole transport layer 3 is spiro-OMeTAD. The electrode layer 4 is silver Ag.

[0095] The mass ratio of the conductive particles A and the conductive particles B is 1:3 - 7.

[0096] In this example, the mass ratio of the conductive particles A and the conductive particles B is 1:3.

[0097] The conductive particle A is composed of an inorganic metal-based carrier and doped metal atoms. The doped metal atoms are fixedly connected to the surface of the inorganic metal-based carrier through M-O covalent bonds. The mass ratio of the doped metal atoms to the inorganic metal-based carrier in the conductive particles is 1:5 - 8. The doped metal atoms are at least one of Zn and Al. The inorganic metal-based carrier is at least one of ZnO and SnO2. In this example, the conductive particle A used is the one in Preparation Example 1.

[0098] The conductive particle B is at least one of ZnO, SnO2, and In2O3.

[0099] In this embodiment, the conductive particle B is In2O3, and the particle size is controlled within 10 - 50 nm.

[0100] The conductive film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 2.5 parts of the conductive particle A in Preparation Example 1, 7.5 parts of the conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0101] A method for preparing a perovskite solar cell includes the following steps:

[0102] Step 1, preparation of the conductive film substrate 1;

[0103] S1.1, Place the PET resin in an oven at 100 °C and dry for 6 h for later use;

[0104] At the same time, perform surface modification on the conductive particle A and the conductive particle B: Place the conductive particle A in Preparation Example 1 and the In2O3 conductive particle B in an aqueous solution of propyl dioleate (dioctyl phosphate) titanate at 5 g / L, and perform ultrasonic treatment for 30 min. Take out and dry for later use;

[0105] S1.2, Mix 1800 g of the dried PET resin evenly with 50 g of the conductive particle A in Preparation Example 1, 150 g of the In2O3 conductive particle B, 10 g of antioxidant 1010, and 10 g of antioxidant BHT that have been accurately metered and surface - modified. Place the mixture in a twin - screw extruder. The first heating zone is at 240 - 250 °C, the second heating zone is at 255 - 260 °C, the third heating zone is at 265 - 270 °C, the fourth heating zone is at 275 - 280 °C, the first heating zone is at 280 - 282 °C, and the die head is at 282 - 283 °C. Extrude, cool with water, and pelletize to obtain the film - making masterbatch;

[0106] S1.3, The film-forming masterbatch is dried at 100 °C for 6.0 h. The dried film-forming masterbatch is placed in a twin-screw extruder. The first heating zone is at 240 - 250 °C, the second heating zone is at 255 - 260 °C, the third heating zone is at 265 - 270 °C, the fourth heating zone is at 275 - 280 °C, the first heating zone is at 280 - 282 °C, and the die head is at 282 - 283 °C for extrusion. The extruded hot-melt material is cast into a prefabricated film. The prefabricated film is first longitudinally stretched by a longitudinal stretching machine at 115 °C with a longitudinal stretching ratio of 2.8 times, and then transversely stretched by a transverse stretching machine at 115 °C with a transverse stretching ratio of 3.0 times. After that, it is shaped at 230 °C for 15 s, annealed in an electric heating blast drying oven at 95 °C for 10 min, and naturally cooled to obtain a semi-finished BOPET film with a thickness of 100 ± 5 microns;

[0107] S1.4, Load the semi-finished film into a quartz mold. One end of the quartz mold is open and the other end is closed. The quartz mold loaded with the semi-finished film is placed in an environment of 168 °C. A positive electrode plate is placed parallel on the open end face of the quartz mold. The linear distance between the open end face of the quartz mold and the lower surface of the positive electrode plate is 0.5 mm. A negative electrode plate is placed parallel on the closed end face of the quartz mold. The linear distance between the closed end face of the quartz mold and the lower surface of the negative electrode plate is 18 mm. The electric field strength formed between the positive electrode plate and the negative electrode plate is controlled at 8*10 5 N / C, and particle migration treatment is carried out for 5 h. A doped conductive enrichment layer 10 is formed on the surface of the semi-finished film. Then, cooling gas is introduced, and the temperature is reduced to 45 °C at a rate of 10 - 12 °C / min, and then naturally cooled to room temperature to obtain a semi-finished conductive thin film substrate;

[0108] S1.5, The semi-finished conductive thin film substrate in S1.4 is treated by an irradiation cross-linking process: The semi-finished conductive thin film substrate in S1.4 is placed in an electron irradiation cross-linking device. Cobalt is used as the radiation source. The electron gun emits low-energy electron beams, which are accelerated to 10 MeV by an accelerator and then output, and directly irradiated on the surface of the finished conductive thin film under the accelerator. The irradiation dose is controlled at 10 Mrad, and the cross-linking treatment time is controlled at 6 s to obtain a finished conductive thin film substrate 1;

[0109] Step two, ultrasonically clean the surface of the doped conductive enrichment layer 10 of the conductive thin film substrate 1 with isopropyl alcohol and deionized water for 20 min, then dry it with dry nitrogen, and then perform low-temperature plasma pretreatment for 10 min. The treatment temperature is 0 - 4 °C, and the treatment gas is air;

[0110] Step two, a perovskite light-absorbing layer 2 is formed on the doped conductive enrichment layer 10 of the conductive thin film substrate 1:

[0111] S2.1, Preparation of perovskite precursor solution: Dissolve 1.2 mol of methylammonium iodide and 1.2 mol of lead iodide in 1 L of N,N-dimethylformamide. The concentrations of methylammonium iodide and lead iodide are the same. Then add 100 g of BHT, heat and stir evenly. Let it stand for a period of time, and then filter. The obtained filtrate is the perovskite precursor solution;

[0112] S2.2, Preparation of perovskite light-absorbing layer 2: Drop the perovskite precursor solution prepared in S2.1 onto the surface of the heteroconductive enrichment layer 10 and spin-coat it. Spin-coat at 3200 rpm with a rotational acceleration of 200 rpm / s for 30 s, and rotate to remove the excess solution. After the spin-coating is completed, place the prepared sample on a heating table and heat it at 98 °C for 25 min, and then dry it in air at 130 °C for 150 s to obtain the CH3NH3PbI3 perovskite light-absorbing layer 2;

[0113] Step 3, Prepare the hole transport layer 3 on the perovskite light-absorbing layer 2 by spin-coating method:

[0114] S3.1, Preparation of solution A: Dissolve 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene in chlorobenzene to obtain solution A;

[0115] S3.2, Preparation of solution B: Dissolve lithium bis(trifluoromethanesulfonyl)imide in acetonitrile to obtain solution B;

[0116] S3.3, Add solution B and tetrabutylpyridine to solution A to prepare a mixed solution C. Among them, the concentration of 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene is 0.06 mol / L, the concentration of lithium bis(trifluoromethanesulfonyl)imide is 0.03 mol / L, and the concentration of tetrabutylpyridine is 0.2 mol / L;

[0117] S3.4, Drop the mixed solution C prepared in S3.3 onto the surface of the CH3NH3PbI3 perovskite light-absorbing layer 2 and spin-coat it at 3200 rpm with a rotational acceleration of 200 rpm / s. After spin-coating on the surface of the perovskite light-absorbing layer 2, place it in dry and light-proof air for 4 h to obtain the hole transport layer 3;

[0118] Step 4, Evaporate a 60 - 70 nm thick silver layer on the hole transport layer 3 by vacuum thermal evaporation method as the electrode to prepare the electrode layer 4:

[0119] Step 5, Package in a glove box filled with inert gas to obtain the finished perovskite solar cell.

[0120] Example 2

[0121] The difference between Example 2 and Example 1 lies in:

[0122] In this embodiment, the conductive particle A in Preparation Example 2 is adopted.

[0123] Example 3

[0124] The difference between Example 3 and Example 1 lies in:

[0125] In this embodiment, the conductive particle A in Preparation Example 3 is adopted.

[0126] Example 4

[0127] The difference between Example 4 and Example 1 lies in:

[0128] In this embodiment, the conductive particle A in Preparation Example 4 is adopted.

[0129] Example 5

[0130] The difference between Example 5 and Example 1 lies in:

[0131] In this embodiment, the conductive particle A in Preparation Example 5 is adopted.

[0132] Example 6

[0133] The difference between Example 6 and Example 1 lies in:

[0134] In this embodiment, the conductive particle A in Preparation Example 6 is adopted.

[0135] Example 7

[0136] The difference between Example 7 and Example 1 lies in:

[0137] In this embodiment, the mass ratio of the conductive particle A to the conductive particle B is 1:4.

[0138] The conductive film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 2 parts of the conductive particle A in Preparation Example 1, 8 parts of the conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0139] Example 8

[0140] The difference between Example 8 and Example 1 lies in:

[0141] In this embodiment, the mass ratio of the conductive particle A to the conductive particle B is 1:5.

[0142] Example 9

[0143] The difference between Example 9 and Example 1 lies in:

[0144] In this embodiment, the mass ratio of the conductive particle A to the conductive particle B is 1:7.

[0145] Example 10

[0146] The difference between Example 10 and Example 7 lies in:

[0147] The conductive thin film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 2.4 parts of conductive particle A in Preparation Example 1, 9.6 parts of conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0148] Example 11

[0149] The difference between Example 11 and Example 7 lies in:

[0150] The conductive thin film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 3 parts of conductive particle A in Preparation Example 1, 12 parts of conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0151] Example 12

[0152] The difference between Example 12 and Example 1 lies in:

[0153] The conductive thin film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 1 part of conductive particle A in Preparation Example 1, 2 parts of conductive particle A in Preparation Example 4, 9 parts of conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0154] Comparative Example

[0155] Comparative Example 1

[0156] The difference between Comparative Example 1 and Example 1 lies in:

[0157] In this example, conductive particle A in Preparation Example 7 is used.

[0158] Comparative Example 2

[0159] The difference between Comparative Example 2 and Example 1 lies in:

[0160] In this example, conductive particle A in Preparation Example 8 is used.

[0161] Comparative Example 3

[0162] The difference between Comparative Example 3 and Example 1 lies in:

[0163] In this example, the mass ratio of conductive particle A to conductive particle B is 1:2.

[0164] Comparative Example 4

[0165] The difference between Comparative Example 4 and Example 1 lies in:

[0166] In this embodiment, the mass ratio of conductive particle A to conductive particle B is 1:10.

[0167] Comparative Example 5

[0168] The difference between Comparative Example 5 and Example 1 lies in:

[0169] The conductive thin film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 1.5 parts of conductive particle A in Preparation Example 1, 6 parts of conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0170] Comparative Example 6

[0171] The difference between Comparative Example 6 and Example 1 lies in:

[0172] The conductive thin film substrate 1 is prepared from the following raw materials in parts by weight: 100 parts of PET resin, 4 parts of conductive particle A in Preparation Example 1, 16 parts of conductive particle B, 0.5 part of antioxidant 1010, and 0.5 part of antioxidant BHT.

[0173] Comparative Example 7

[0174] The difference between Comparative Example 7 and Example 1 lies in:

[0175] The finished conductive thin film substrate was not subjected to the S1.5 irradiation cross-linking process.

[0176] Comparative Example 8

[0177] The difference between Comparative Example 8 and Example 1 lies in:

[0178] The conductive thin film substrate 1 is replaced with an ITO transparent glass substrate, with a sheet resistance of 25 Ω*sq -1 , and a light transmittance of 85.2%.

[0179] Preparation method of perovskite solar cell

[0180] Step 1, the ITO transparent glass substrate is ultrasonically cleaned with acetone, isopropanol, and deionized water for 20 min, then dried with dry nitrogen, and subjected to ultraviolet ozone pretreatment;

[0181] Step 2, after cleaning, a TiO2 dense thin film layer with a thickness of 60 nm is deposited on the ITO transparent glass substrate by a vacuum coating process, which is the electron transport layer;

[0182] Step 3, a perovskite light-absorbing layer is formed on the electron transport layer:

[0183] S2.1, Preparation of perovskite precursor solution: Dissolve 1.2 mol of methylammonium iodide and 1.2 mol of lead iodide in 1 L of N,N-dimethylformamide. The concentrations of methylammonium iodide and lead iodide are the same. Then add 100 g of BHT, heat, stir evenly, let stand for a period of time, filter, and the obtained filtrate is the perovskite precursor solution;

[0184] S2.2, Preparation of perovskite light-absorbing layer 2: Drop the perovskite precursor solution prepared in S2.1 onto the surface of the electron transport layer and spin-coat it. Spin-coat at 3200 rpm with a rotational acceleration of 200 rpm / s for 30 s, spin to remove the excess solution. After the spin-coating is completed, place the prepared sample on a heating table and heat at 98 °C for 25 min, then dry in air at 130 °C for 150 s to obtain the CH3NH3PbI3 perovskite light-absorbing layer;

[0185] Step Four, Prepare the hole transport layer on the perovskite light-absorbing layer by spin-coating method:

[0186] S4.1, Preparation of solution A: Dissolve 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene in chlorobenzene to obtain solution A;

[0187] S4.2, Preparation of solution B: Dissolve lithium bis(trifluoromethanesulfonyl)imide in acetonitrile to obtain solution B;

[0188] S4.3, Add solution B and tetrabutylpyridine to solution A to prepare a mixed solution C. Among them, the concentration of 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene is 0.06 mol / L, the concentration of lithium bis(trifluoromethanesulfonyl)imide is 0.03 mol / L, and the concentration of tetrabutylpyridine is 0.2 mol / L;

[0189] S4.4, Drop the mixed solution C prepared in S4.3 onto the surface of the CH3NH3PbI3 perovskite light-absorbing layer and spin-coat it at 3200 rpm with a rotational acceleration of 200 rpm / s. After spin-coating on the surface of the perovskite light-absorbing layer, place it in dry and light-proof air for 4 h to obtain the hole transport layer;

[0190] Step Five, Evaporate a 60 - 70 nm thick silver layer on the hole transport layer as the electrode by vacuum thermal evaporation method, prepare the electrode layer, and encapsulate it in a glove box filled with inert gas to obtain the finished perovskite solar cell.

[0191] Performance detection test

[0192] Detection method / Test method

[0193] 1. At room temperature, the test was carried out according to the indoor light energy simulator. Using a solar simulator with 100 mW*cm -2 , AM 1.5G as the light source, the current-voltage curve of the fabricated battery was obtained through a Keithley 2611 source meter. According to the European standard EN 60904-3, the photoelectric conversion efficiency PCE, current density J SC , open-circuit voltage V oc of the perovskite solar cell were calculated.

[0194] 2. Fill factor FF: FF = (V mpp * J mpp ) / (V oc * J SC ) Vmpp is the voltage, and Jmpp is the current density (mmp) at the "maximum energy point" on the battery characteristic line during illumination.

[0195] 3. Sheet resistance of the conductive film substrate: The sheet resistance of the conductive film substrates prepared in Examples 1-12 and Comparative Examples 1-7 and the sheet resistance of the conductive substrate in Comparative Example 8 were measured by a four-probe resistance test system (RTS-9, China).

[0196] Data Analysis

[0197] Table 1 shows the test parameters of the perovskite solar cells in Examples 1-12 and Comparative Examples 1-8.

[0198]

[0199] Combining Examples 1-12 and Comparative Examples 1-8 and referring to Table 1, it can be seen that comparing Examples 1 and Examples 7-9 with Comparative Examples 3-4, the photoelectric conversion efficiency of Examples 1 and Examples 7-9 is better than that of Comparative Examples 3-4. Therefore, the mass ratio of conductive particle A to conductive particle B is preferably 1:3 - 7.

[0200] Combining Examples 1-12 and Comparative Examples 1-8 and referring to Table 1, it can be seen that comparing Examples 4-6 with Comparative Examples 1-2, the photoelectric conversion efficiency of Examples 4-6 is slightly lower than that of Comparative Example 1 but better than that of Comparative Example 2. Therefore, considering the production cost comprehensively, the mass ratio of the doped metal atoms to zinc oxide in conductive particle A is preferably 1:5 - 8.

[0201] Combining Examples 1-12 and Comparative Examples 1-8 and referring to Table 1, it can be seen that when comparing Example 1, Examples 10-11 with Comparative Examples 5-6, the photoelectric conversion efficiency of Example 1, Examples 10-11 is slightly lower than that of Comparative Example 6, but better than that of Comparative Example 5. Therefore, based on comprehensive consideration of production costs, it is appropriate that the total mass of conductive particle A and conductive particle B accounts for 10-15% of the mass of the polymer resin.

[0202] Combining Examples 1-12 and Comparative Examples 1-8 and referring to Table 1, it can be seen that when comparing Example 1 with Comparative Example 7, the sheet resistance of the conductive thin film substrate in Example 1 is less than that of the conductive thin film substrate in Comparative Example 7, and the current density and fill factor of the conductive thin film substrate in Example 1 are greater than those of the conductive thin film substrate in Comparative Example 7; moreover, the photoelectric conversion efficiency of the conductive thin film substrate in Example 1 is better than that of Comparative Example 7. In summary, the S1.5 irradiation cross-linking process can improve the performance of perovskite solar cells.

[0203] Combining Examples 1-12 and Comparative Examples 1-8 and referring to Table 1, it can be seen that when comparing Example 1 with Comparative Example 8: the resistance of the perovskite solar cell prepared in Example 1 is similar to that of the ITO perovskite solar cell in Comparative Example 8, the current density of the perovskite solar cell prepared in Example 1 is slightly lower than that of the ITO perovskite solar cell in Comparative Example 8, but the fill factor of the perovskite solar cell prepared in Example 1 is greater than that of the ITO perovskite solar cell in Comparative Example 8; in terms of photoelectric conversion efficiency, the photoelectric conversion efficiency of the perovskite solar cell prepared in this application is similar to that of the ITO perovskite solar cell, and even the photoelectric conversion efficiency of some perovskite solar cells in this application has been better than that of the ITO perovskite solar cell. Therefore, the conductive thin film substrate prepared in this application can be used as a transparent conductive material and at the same time play the role of collecting electrons as an electron transport material.

[0204] In summary, the conductive thin film substrate prepared in this application can be used as a transparent conductive material and at the same time play the role of collecting electrons as an electron transport material, replacing the ITO or FTO transparent conductive material + electron transport material TiO2 or SnO2 structure, reducing the number of battery layers and simplifying the structure of perovskite solar cells, eliminating the cumbersome preparation process, improving the overall production efficiency, and facilitating the popularization and application of perovskite solar cells.

[0205] This specific embodiment is only an explanation of this application, and it is not a limitation of this application. Those skilled in the art can make modifications to this embodiment without creative contributions according to needs after reading this specification, but as long as they are within the scope of the claims of this application, they are protected by the patent law.

Claims

1. A perovskite solar cell, characterized in that: It includes a conductive thin film substrate (1), on which a perovskite photoactive layer (2), a hole transport layer (3), and an electrode layer (4) are sequentially laminated; a doped conductive enrichment layer (10) is formed on the surface of the conductive thin film substrate (1) facing the perovskite photoactive layer (2); the doped conductive enrichment layer (10) contains conductive particles A and conductive particles B that can form a conductive network; the mass ratio of the conductive particles A to the conductive particles B is 1:(3 - 7); the particle sizes of the conductive particles A and the conductive particles B are controlled to be 10 - 50 nm; the conductive particle A is composed of an inorganic metal-based carrier and a doped metal atom, and the doped metal atom is fixedly connected to the surface of the inorganic metal-based carrier; the mass ratio of the doped metal atom to the inorganic metal-based carrier in the conductive particle A is 1:(5 - 8); the doped metal atom is at least one of Zn and Al; the inorganic metal-based carrier is at least one of ZnO and SnO2; the conductive particle B is at least one of ZnO, SnO2, and In2O3.

2. A perovskite solar cell according to claim 1, characterized in that: The conductive particle B is In2O3; the mass ratio of the conductive particle A to the conductive particle B is 1:4; the conductive particle A is composed of zinc oxide and the doped metal atom Zn; the mass ratio of the zinc oxide to the doped metal atom Zn is 1:

4.

3. A perovskite solar cell according to claim 1, characterized in that: The conductive thin film substrate (1) is mainly prepared from a polymer resin, conductive particles A, and conductive particles B: the total mass of the conductive particles A and the conductive particles B accounts for 10 - 15% of the mass of the polymer resin.

4. A perovskite solar cell according to claim 3, characterized in that: The polymer resin includes one of polyethersulfone PES, polyacrylate PAR, polyether-imide PEI, polyethylene naphthalate PEN, polyethylene terephthalate PET, polyphenylene sulfide PPS, polyallylate, polyimide, polycarbonate PC, cellulose triacetate TAC, cellulose acetate propionate CAP, and thermoplastic polyurethane elastomer rubber TPU.

5. A perovskite solar cell according to claim 1, characterized in that: The preparation method of the conductive particle A includes the following steps: S1, the inorganic metal-based carrier is calcined at 400 - 600 °C and 0.8 - 1.0 Mpa for 10 - 15 min, cooled, and then planetary ball milled to a particle size of 10 - 50 nm for standby; S2, preparation of the precursor: 20 - 40 mL of 3 - 5% ammonia water solution is dropped into the metal salt solution at a speed of 80 - 120 μL / s and stirred. The metal salt is at least one of zinc acetylacetonate, zinc nitrate, and aluminum nitrate. The concentration of the metal salt solution is 80 - 120 g / L, and the solvent of the metal salt solution is deionized water. After stirring for 3 - 5 h, the temperature is raised to 60 ± 2 °C within 30 min and stirred for another 3 h to obtain a mixed solution; S3. In-situ coprecipitation synthesis of conductive particle precursors: The mass ratio of the doped metal atoms to the inorganic metal-based carrier is 1:(5 - 8). Add the inorganic metal-based carrier precursor in S1 to the mixed solution in S2 according to the ratio, react at 120 - 150 °C for 20 - 28 h. After the reaction, cool to room temperature, centrifuge to separate the solid product. Wash the obtained solid product with ethanol and water at least 3 times respectively, then dry in vacuum at 100 °C for 3 - 5 h, and perform planetary ball milling to obtain conductive particle powder with a particle size of 10 - 50 nm; S4. One-step in-situ generation of finished conductive particles: Place the conductive particle powder obtained in S3 in an atmosphere of 5% hydrogen-argon mixed gas, heat-treat at a temperature of 200 - 400 °C for 2 - 3 h, cool to room temperature, and grind to obtain finished conductive particles A.

6. A perovskite solar cell according to claim 1, characterized in that: The perovskite photoactive layer (2) is one of CH3NH3SnI3, CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbCl3, CH(NH2)2PbI3, CH(NH2)2PbBr3, CsSnI3, CsSnBr3, CsSnCl3.

7. A perovskite solar cell according to claim 1, characterized in that: The hole transport layer (3) is one of an inorganic hole transport layer and an organic hole transport layer; the inorganic hole transport layer is one of nickel oxide, molybdenum oxide, tungsten oxide; the organic hole transport layer is one of spiro-OMeTAD, P3HT, PCPDTBT, HTM-TPSI, Li-TFSI; the electrode layer (4) is one of magnesium Mg, aluminum Al, platinum Pt, silver Ag, copper Cu, molybdenum Mo, titanium Ti, graphite, carbon nanotubes.

8. A method for preparing a perovskite solar cell according to any one of claims 1-7, characterized in that: It includes the following steps: Step 1. Preparation of the conductive thin film substrate (1); Step 2. Clean the doped conductive enrichment layer (10) of the conductive thin film substrate (1), blow dry with dry nitrogen, and perform low-temperature plasma pretreatment; Step 2. Fabricate the perovskite photoactive layer (2) on the doped conductive enrichment layer (10) of the conductive thin film substrate (1); Step 3. On the perovskite photoactive layer (2), prepare the hole transport layer (3) by spin coating; Step 4. Prepare the electrode layer (4) on the hole transport layer (3); Step 5. Package in a glove box filled with inert gas to obtain the finished perovskite solar cell.

9. A method for preparing a perovskite solar cell according to claim 8, characterized in that: The preparation method of the conductive thin film substrate (1) includes the following steps: S1.

1. Drying treatment of the polymer resin, and simultaneously performing surface modification treatment on conductive particles A and conductive particles B; S1.

2. Mix the dried organic polymer resin with accurately metered and surface-modified conductive particles A and conductive particles B evenly, extrude and granulate to obtain the film-making masterbatch; S1.

3. Use the film-making masterbatch for extrusion, casting, and cooling to obtain a semi-finished film; S1.4 Heat the semi-finished film to 3 - 8 °C above Tg to make the molecular chain segments in the semi-finished film in free movement, and perform particle migration treatment in a uniform electric field. The electric field strength is controlled at 10 4 - 10 6 N / C. After 4 - 6 h of particle migration treatment, a doped conductive enrichment layer (10) is formed on the surface layer of the semi-finished film, and it is cooled to room temperature to obtain a semi-finished conductive film substrate; In step S1.5, the semi-finished conductive thin film substrate in step 4 is treated by an irradiation cross-linking process for 6 - 10 s, and the irradiation dose is controlled at 10 - 15 Mrad to obtain the finished conductive thin film substrate.

10. The preparation method of a perovskite solar cell according to claim 8, characterized in that: In step 2, fabricate the perovskite photoactive layer (2) on the doped conductive enrichment layer (10) of the conductive thin film substrate (1): S2.1, Preparation of perovskite precursor solution: 1 - 1.2 mol of methylammonium iodide and 1 - 1.2 mol of lead iodide are dissolved in 1 L of N,N - dimethylformamide. The concentrations of methylammonium iodide and lead iodide are the same. Then 80 - 120 g of BHT is added, heated, stirred evenly, allowed to stand for a period of time, filtered, and the obtained filtrate is the perovskite precursor solution; S2.2, Preparation of perovskite photoactive layer (2): The perovskite precursor solution prepared in S2.1 is drop - coated on the surface of the heteroconductive enrichment layer (10) and spin - coated at 3000 - 3500 rpm with a rotational acceleration of 180 - 200 rpm / s for 30 ± 2 s. The excess solution is removed by rotation. After the spin - coating is completed, the prepared sample is placed on a heating table and heated at 90 - 100 °C for 20 - 25 min, and then dried in air at 120 - 130 °C for 150 - 180 s to obtain the CH3NH3PbI3 perovskite photoactive layer (2).

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