A method and spraying facility for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system

Abstract

The present invention discloses a method and a spraying facility for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system, which belongs to the technical field of perovskite solar cell preparation. The method uses a spraying facility to assist in spin coating a large-area perovskite thin film absorption layer to prepare a large area of ​​not less than 3×3 cm 2 This method solves the existing problem of poor crystallinity at the edges of the large-area perovskite film produced by spin coating in ultra-clean air due to the inability of the antisolvent to react evenly with the wet perovskite film. The antisolvent can be evenly sprayed onto the rotating wet perovskite film in a short period of time, improving the overall crystallinity of the perovskite film. The resulting PSCs exhibit uniform and excellent performance across the subcells, and the long-term stability of the cells is also enhanced.

Description

Technical Field

[0001] The present invention belongs to the technical field of perovskite solar cell preparation, and in particular relates to a method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system and a spraying facility. Background Art

[0002] In the context of vigorously developing new energy sources, perovskite solar cells (PSCs) have been widely studied in the field of scientific research due to their advantages such as low cost and diverse structures, and have even reached the scale of commercial production. After years of research and development, in the laboratory, the energy conversion efficiency (PCE) of small-area nip-structured PSCs has exceeded 26%, but the PCE of large-area PSCs is still relatively low. At present, the main preparation methods for large-area PSCs include spraying, scraping, slit coating and vacuum deposition. However, the cost of these large-area PSC preparation methods is relatively high, and they are more suitable for use in assembly line production factories to prepare ultra-large-area PSCs. For the preparation of larger-area PSCs for general applications, spin coating is still the most cost-effective option.

[0003] In the spin-coating method, the antisolvent, as an extractant for the perovskite precursor solvent, can accelerate the volatilization of the solvent in the spin-coated perovskite liquid film, thereby regulating the nucleation and growth of the perovskite crystals. However, in the process of preparing large-area perovskites by spin-coating, the traditional pipette dripping method cannot make the antisolvent drip evenly and quickly onto the rotating liquid film, resulting in uneven performance of large-area PSCs prepared by spin-coating. In particular, the edge of the large-area perovskite film has almost no effect on the antisolvent. As a result, the perovskite crystal quality at these edge portions is very poor. Moreover, since the preparation is carried out in air, water and oxygen are more likely to enter the crystals in this part, resulting in a large number of defects, which hinders the development of its own performance and application in other fields. Summary of the Invention

[0004] The purpose of the present invention is to provide a method and spraying facility for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system, so as to solve the problem of poor crystallinity at the edge of the spin-coated large-area perovskite film due to the inability to uniformly react between the antisolvent and the perovskite wet film when preparing large-area perovskite solar cells by spin coating in air in the prior art. In particular, in high-humidity air, water and oxygen are more likely to enter low-quality crystals, thereby generating a large number of defects. In this case, the optical performance of the cell is poor and uneven, and its stability also decreases sharply.

[0005] To achieve the above objectives, the present invention provides a method for preparing high-quality, large-area perovskite solar cells by spin coating in an ultra-clean environment system, comprising the following steps:

[0006] (1) Prepare perovskite precursor solution in ultra-clean working environment;

[0007] (2) Clean the conductive substrate and treat it with UV ozone for 3 minutes to 30 minutes;

[0008] (3) In an ultra-clean air environment, spin-coating the first charge transport layer on the conductive substrate and annealing at high temperature for 10 min to 90 min;

[0009] (4) spin-coating a perovskite precursor solution on the first charge transport layer, opening the valve of the spray facility above the film during the spin-coating process to accelerate the volatilization rate of the solvent in the perovskite wet film, and performing an annealing treatment for 10 min to 90 min to form a high-quality large-area perovskite film with a perovskite absorption layer;

[0010] (5) Spin coating a second charge transport layer on a high-quality, large-area perovskite film;

[0011] (6) Mechanically scribing the high-quality, large-area perovskite film prepared by spin coating;

[0012] (7) Depositing electrodes to form high-quality large-area perovskite solar cells.

[0013] Preferably, the perovskite precursor solution in step (1) is RNH3 + 、CH3NH3 + NH2CH=NH2 + 、Cs + ;Pb 2+ 、Sn 2+ Br - , I - 、Cl - 、SCN - 、CH3COOH - It is composed of one or more ionic solutes.

[0014] Preferably, the perovskite precursor solution in step (1) is composed of one or more solvents selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, isopropanol, methylammonium acetate ionic liquid, acetonitrile, 2-mercaptoethanol, 1,3-dimethyl-2-imidazolidinone, methylamine, ethanol, and n-butanol.

[0015] Preferably, the concentration of the perovskite precursor solution in step (1) is 0.4 mol / L-2.0 mol / L in terms of divalent cations.

[0016] Preferably, in step (4), an antisolvent needs to be sprayed when spin-coating the perovskite film, and the antisolvent includes one or more of ethyl acetate, methyl formate, propionate, butyrate, ethyl silicate, toluene, trifluorotoluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene, iodobenzene, ethyl ether, anisole, dipropyl ether, dibutyl ether, sec-butyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, chloroform, and tetraethoxymethane.

[0017] Preferably, the high-quality large-area perovskite solar cells prepared by spin coating include formal perovskite solar cells and inverted perovskite solar cells, with an area of ​​not less than 3×3 cm 2 The functional layers in the high-quality large-area perovskite solar cell are a first charge transport layer, a perovskite absorption layer, and a second charge transport layer. The functional layers are all prepared by spin coating in air at a spin coating rate of 800 rpm to 9000 rpm, and the spin coating time of each functional layer is 10 s to 120 s.

[0018] Preferably, in step (4), the annealing temperature is 60° C.-350° C., and the annealing time is 10 min-90 min.

[0019] Preferably, the conductive substrate includes a conductive layer and a non-conductive layer, the conductive layer includes ITO and FTO, the non-conductive layer includes glass, polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the conductive substrate is any one of an ITO / glass substrate, an FTO / glass substrate, an ITO / PI substrate, an FTO / PI substrate, an ITO / PET substrate, an FTO / PET substrate, an ITO / PEN substrate, and an FTO / PEN substrate;

[0020] The conductive layer and the non-conductive layer, the conductive layer includes ITO and FTO, and the non-conductive layer includes glass, polyimide (PI), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN).

[0021] Preferably, the first charge transport layer and the second charge transport layer contain tin dioxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), fullerene (C 60 、C 70 ), [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM), perylene diimide derivatives (PDI), naphthalene diimide derivatives (NDI), hexaazatrinaphthalene derivatives (HATNA), nickel oxide (NiO x), cuprous thiocyanate (CuSCN), cuprous iodide (CuI), 2,2",7,7"-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), poly[bis(4-phenyl)(2,4,6-trimethylphenyl]amine (PTAA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl]amine (PEDOT:PSS), and poly(3-hexylthiophene-2,5-diyl) (P3HT),

[0022] The annealing temperature of the first charge transport layer and the second charge transport layer is 50-450° C., and the thickness of the first charge transport layer and the second charge transport layer is 10-100 nm;

[0023] The electrode comprises one of a carbon electrode, a gold electrode, a silver electrode, an aluminum electrode and a copper electrode, and the thickness of the electrode is 50-500 nm.

[0024] The present invention also provides a spray facility for spin coating to prepare high-quality large-area perovskite solar cells in an ultra-clean environment system. The spray facility includes an iron frame, a glue spreader arranged on the iron frame, and a solution cylinder fixed on the iron frame for placing an anti-solvent. The glue spreader is provided with a substrate suction cup for placing a conductive substrate, a liquid flow channel is provided below the solution cylinder, and the solution cylinder is also provided with a valve. The liquid flow channel is located directly above the substrate suction cup. The valve is opened for 3s-120s after the start of spin coating, and the valve is open for 3s-120s.

[0025] The perovskite precursor solution is dropped onto the substrate. After rotating for a certain period of time, the valve of the spray facility mounted at a certain height is opened, and the antisolvent passes through the valve and is sprayed out through the liquid flow channel below. At the same time, the sprayed antisolvent collides with the high-speed rotating perovskite liquid film, which in turn causes the dripping antisolvent to sputter. Therefore, this method can make the antisolvent react with the entire perovskite wet film, promoting the high-quality crystallization of the film.

[0026] Therefore, the present invention adopts the above-mentioned method and spraying facility for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system, and its beneficial effects are:

[0027] 1. The substrate area of ​​the spin-coated large-area perovskite film of the present invention is (3*3) cm 2 And above, and the crystallinity at the edge of large-area perovskite film is also good. Spin coating preparation is carried out in an ultra-clean studio, which can provide more stable temperature and humidity while maintaining high cleanliness, providing effective and efficient production conditions for the excellent preparation of large-area perovskite solar cells.

[0028] 2. The large-area perovskite solar cell described in the present invention, including the charge transfer layer and the perovskite absorption layer, are all prepared based on the spin coating method. In particular, the perovskite absorption layer is prepared by the spin coating method. The present invention adopts a self-made solution spraying facility to spray the antisolvent evenly and quickly on the rotating large-area perovskite wet film, thereby solving the problem of uneven crystallization quality of large-area perovskite films prepared by the spin coating method.

[0029] 3. Compared with traditional methods such as scraping, spraying and slit coating, the present invention reduces the cost of preparing large-area perovskite films; and the corresponding large-area perovskite solar cells prepared have excellent performance, especially high opening voltage.

[0030] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 A schematic diagram showing a spraying facility of the present invention spraying an antisolvent onto a rotating perovskite wet film to assist spin coating in preparing high-quality, large-area perovskite solar cells;

[0032] Figure 2 A schematic cross-sectional structure diagram of a series-connected perovskite battery module according to Example 1 of the present invention is shown;

[0033] Figure 3 Schematic diagram of cutting and partitioning for sample uniformity testing in Example 1 of the present invention is shown;

[0034] Figure 4 The front side of the large-area perovskite battery module according to Example 1 of the present invention is shown;

[0035] Figure 5 The back side of the large-area perovskite battery module according to Example 1 of the present invention is shown;

[0036] Figure 6 The photovoltaic characteristic curve of 16 series-connected cells in a large-area perovskite cell module according to Example 1 of the present invention is shown;

[0037] Reference numerals:

[0038] 1. Iron stand; 2. Glue spreader; 3. Substrate suction cup; 4. Substrate; 5. Liquid flow channel; 6. Valve; 7. Solution cylinder;

[0039] a1, glass; a2, ITO; a3, first charge transport layer; a4, perovskite absorption layer; a5, second charge absorption layer; a6, electrode; P1, first gap; P2, second gap; P3, third gap. DETAILED DESCRIPTION

[0040] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.

[0041] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

[0042] Furthermore, it should be understood that although this specification describes the embodiments, not every embodiment includes only one independent technical solution. This description is for clarity only. Those skilled in the art should consider the specification as a whole. The technical solutions in the various embodiments may also be appropriately combined to form other embodiments that are understandable to those skilled in the art. These other embodiments are also encompassed within the scope of protection of the present invention.

[0043] The present invention is further described below with reference to the accompanying drawings and specific embodiments.

[0044] The present invention provides a method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system, comprising the following steps:

[0045] (1) Prepare perovskite precursor solution in a clean room;

[0046] (2) Clean the conductive substrate and treat it with UV ozone for 3 minutes to 30 minutes;

[0047] (3) In an ultra-clean air environment, spin-coating the first charge transport layer on the conductive substrate and annealing at high temperature for 10 min to 90 min;

[0048] (4) spin-coating a perovskite precursor solution on the first charge transport layer, opening the valve of the spray facility above the film during the spin-coating process to accelerate the volatilization rate of the solvent in the perovskite wet film, and performing an annealing treatment for 10 min to 90 min to form a high-quality large-area perovskite film with a perovskite absorption layer;

[0049] (5) Spin coating a second charge transport layer on a high-quality, large-area perovskite film;

[0050] (6) Mechanically scribing the high-quality, large-area perovskite film prepared by spin coating;

[0051] (7) Depositing electrodes to form high-quality large-area perovskite solar cells.

[0052] Step (1) The perovskite precursor solution is made of RNH3 + 、CH3NH3 + NH2CH=NH2 + 、Cs + ;Pb 2+ 、Sn 2+Br - , I - 、Cl - 、SCN - 、CH3COOH - It is composed of one or more ionic solutes.

[0053] The perovskite precursor solution in step (1) is composed of one or more solvents selected from dimethyl sulfoxide, N,N-dimethylformamide, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, isopropyl alcohol, methylammonium acetate ionic liquid, acetonitrile, 2-mercaptoethanol, 1,3-dimethyl-2-imidazolidinone, methylamine, ethanol, and n-butanol.

[0054] The concentration of the perovskite precursor solution in step (1) is 0.4 mol / L-2.0 mol / L in terms of divalent cations.

[0055] In step (4), when the perovskite film is spin-coated, an antisolvent needs to be sprayed. The antisolvent includes one or more of ethyl acetate, methyl formate, propionate, butyrate, ethyl silicate, toluene, trifluorotoluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene, iodobenzene, ethyl ether, anisole, dipropyl ether, dibutyl ether, sec-butyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, chloroform, and tetraethoxymethane.

[0056] High-quality large-area perovskite solar cells prepared by spin coating include formal perovskite solar cells and inverted perovskite solar cells, with an area of ​​not less than 3×3cm 2 The functional layers in high-quality large-area perovskite solar cells are the first charge transport layer, the perovskite absorption layer and the second charge transport layer. The functional layers are all prepared by spin coating in air with a spin coating rate of 800-9000 rpm and a spin coating time of 10-120 s for each functional layer.

[0057] In step (4), the annealing temperature is 60° C.-350° C., and the annealing time is 10 min-90 min.

[0058] The conductive substrate includes a conductive layer and a non-conductive layer, the conductive layer includes ITO and FTO, the non-conductive layer includes glass, polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the conductive substrate is any one of an ITO / glass substrate, an FTO / glass substrate, an ITO / PI substrate, an FTO / PI substrate, an ITO / PET substrate, an FTO / PET substrate, an ITO / PEN substrate, and an FTO / PEN substrate;

[0059] The conductive layer and the non-conductive layer, the conductive layer includes ITO and FTO, and the non-conductive layer includes glass, polyimide (PI), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN).

[0060] The first charge transport layer and the second charge transport layer include tin dioxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), fullerene (C 60 、C 70 ), [6,6]-phenyl-C61-butyric acid methyl ester (PC 61 BM), perylene diimide derivatives (PDI), naphthalene diimide derivatives (NDI), hexaazatrinaphthalene derivatives (HATNA), nickel oxide (NiO x ), cuprous thiocyanate (CuSCN), cuprous iodide (CuI), 2,2",7,7"-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), poly[bis(4-phenyl)(2,4,6-trimethylphenyl]amine (PTAA), poly[bis(4-phenyl)(2,4,6-trimethylphenyl]amine (PEDOT:PSS), and poly(3-hexylthiophene-2,5-diyl) (P3HT),

[0061] The annealing temperature of the first charge transport layer and the second charge transport layer is 50-450° C., and the thickness of the first charge transport layer and the second charge transport layer is 10-100 nm;

[0062] The electrode comprises one of a carbon electrode, a gold electrode, a silver electrode, an aluminum electrode and a copper electrode, and the thickness of the electrode is 50-500 nm.

[0063] The present invention also provides a spray facility for spin coating to prepare high-quality large-area perovskite solar cells in an ultra-clean environment system. The spray facility includes an iron frame 1, a glue spreader 2 arranged on the iron frame 1, and a solution cylinder 7 fixed on the iron frame 1 for placing an anti-solvent. The glue spreader 2 is provided with a substrate suction cup 3 for placing a conductive substrate 4, a liquid flow channel 5 is provided below the solution cylinder 7, and the solution cylinder 7 is also provided with a valve 6. The liquid flow channel 5 is located directly above the substrate suction cup 3. The valve 6 is opened for 3s-120s after the start of spin coating, and the valve 6 is open for 3s-120s.

[0064] Example 1

[0065] The present invention provides a method for preparing high-quality, large-area perovskite solar cells by spin coating in an ultra-clean environment system, comprising the following specific steps:

[0066] (1) Prepare a perovskite precursor solution with a chemical composition of ABX3 type, where A is FA + , B is Pb 2+ , X is I -, the solvents were DMF and DMSO;

[0067] (2) The designed ITO / glass substrate was cleaned with deionized water and organic solvents such as acetone, dried with N2, and then treated with UV-ozone for 3 minutes;

[0068] (3) In this embodiment, the first charge transport layer is SnO2. SnO2 colloid is ultrasonically dispersed with a certain amount of deionized water, and the dispersion is spin-coated on the ITO / glass substrate after ozone treatment, and annealed at high temperature for 10 minutes.

[0069] (4) After UV ozone treatment and annealing, SnO2 / ITO / glass substrate is treated, and the perovskite precursor is dropped on SnO2. The spin coater 2 is turned on to spin the perovskite precursor evenly on the substrate 4. The valve 6 of the spray facility is opened 3 seconds after the start of spin coating, and the anti-solvent in the solution cylinder 7 is evenly and quickly sprayed on the perovskite wet film. Figure 1 As shown, finally, high temperature annealing treatment was performed for 10 minutes.

[0070] Because the antisolvent fully extracts the solvent from the wet perovskite film, promoting perovskite crystallization, the large-area perovskite film obtained by spin coating has excellent crystallinity. On the one hand, this reduces the defect density, resulting in good optoelectronic performance of the corresponding perovskite solar cell device. On the other hand, the excellent crystallinity of the perovskite film prevents the intrusion of water and oxygen in the air atmosphere, improving the long-term stability of the perovskite film and the corresponding device.

[0071] Figure 4 The front side of the large-area perovskite solar cell module prepared by the present invention is shown in this embodiment. Figure 5 The back side of the battery is shown, and its substrate area is (13.2*13.2)cm 2 To test the uniformity of the film and to broaden the application of the present invention, this embodiment divides the entire large-area perovskite solar cell into 16 sub-series cells, as shown in the schematic diagram of the segmentation. Figure 3 As shown, the 16 sub-series batteries are numbered 1 to 16, and each sub-series battery has 6 small batteries connected in series. Figure 4 As shown. And from Figure 4 and Figure 5 It can be observed that with the help of the spray facility, the overall color of the perovskite film prepared by spin coating in air is dark black, which is an indication of good crystallization quality;

[0072] (5) The charge transport layer 2 in this embodiment uses Spiro-OMeTAD, and the prepared Spiro-OMeTAD is spin-coated on the perovskite film without annealing treatment;

[0073] (6) Mechanically scribing to create the second gap P2 in the series cell, and then using a blade to scrape off the layers of film directly deposited on the pure glass substrate;

[0074] (7) The surface of the spin-coated film is covered with a metal mask and the electrode is deposited.

[0075] Its structure is as follows Figure 2 As shown, from bottom to top, it includes: glass a1, ITO a2, a first charge transport layer a3, a perovskite absorption layer a4, a second charge absorption layer a5 and an electrode a6, wherein the first charge transport layer a3 is connected to the ITO a2 through a plurality of first slits P1 opened on the ITO a2, and a second slit P2 is longitudinally passed through the second charge transport layer a5, the perovskite absorption layer a4 and the first charge transport layer a3, the electrode a6 passes through the second slit P2, and a third slit P3 is opened on the electrode a6, and the first slit P1, the second slit P2 and the third slit P3 are not connected.

[0076] Based on the above steps, the large-area perovskite solar cell prepared by spin coating in air in this embodiment has high-quality crystallization due to sufficient reaction between the perovskite wet film and the antisolvent during the spin coating process, thereby obtaining good photoelectric performance, such as Figure 6 As shown in the figure, the open circuit voltages of the 16 small cells divided in the large-area perovskite solar cell are all greater than 5V, which greatly expands the application of perovskite solar cells.

[0077] Example 2

[0078] Perovskite precursor solution based on a mixed solvent of DMSO and DMF, the solute in the perovskite precursor solution includes FA + , Sn 2 + , I - and Br - , other steps are the same as in Example 1, and the entire experimental process is carried out in air.

[0079] Example 3

[0080] Perovskite precursor solution based on a mixed solvent of DMSO and DMF, the solute in the perovskite precursor solution includes Cs + , Pb 2 + , I - and Br - , other steps are the same as in Example 1, and the entire experimental process is carried out in air.

[0081] Example 4

[0082] Perovskite precursor solution based on a mixed solvent of acetonitrile, methylamine and ethanol, the solute in the perovskite precursor solution includes MA+ , Pb 2+ , I - and Br - , other steps are the same as in Example 1, and the entire experimental process is carried out in air.

[0083] Therefore, the present invention provides a method and spraying facility for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system, which solves the problem of poor crystallinity at the edges of the spin-coated large-area perovskite film caused by the inability to uniformly react with the antisolvent and the perovskite wet film when spin coating large-area perovskite solar cells in air in the prior art. The antisolvent can be evenly sprayed on the rotating perovskite wet film in a short time, thereby improving the overall crystallinity of the perovskite film. The corresponding sub-cells in the PSCs have uniform and good performance, and the long-term stability of the battery is also improved.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system, characterized in that: The following steps are involved: (1) Prepare perovskite precursor solution in a clean room; (2) Clean the conductive substrate and treat it with UV ozone for 3 minutes to 30 minutes; (3) In an ultra-clean air environment, spin-coating the first charge transport layer on the conductive substrate and annealing at high temperature for 10 min to 90 min; (4) spin-coating a perovskite precursor solution on the first charge transport layer, opening the valve of the spray facility above the film during the spin-coating process to accelerate the volatilization rate of the solvent in the perovskite wet film, and performing an annealing treatment for 10 min to 90 min to form a high-quality large-area perovskite film with a perovskite absorption layer; (5) Spin coating a second charge transport layer on a high-quality, large-area perovskite film; (6) Mechanically scribing the high-quality, large-area perovskite film prepared by spin coating; (7) Depositing electrodes to form high-quality, large-area perovskite solar cells; The spraying facility includes an iron frame, a glue spreader arranged on the iron frame, and a solution cylinder fixed on the iron frame for placing an anti-solvent. The glue spreader is provided with a substrate suction cup for placing a conductive substrate, a liquid flow channel is provided below the solution cylinder, and the solution cylinder is also provided with a valve. The liquid flow channel is located directly above the substrate suction cup. The valve is opened for 3s-120s after the start of spin coating, and the valve is open for 3s-120s.

2. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 1, characterized in that: The perovskite precursor solution in step (1) is made of RNH3 + 、CH3NH3 + NH2CH=NH2 + 、Cs + ;Pb 2+ 、Sn 2+ Br - , I - 、Cl - 、SCN - 、CH3COOH - It is composed of one or more ionic solutes.

3. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 1, characterized in that: The perovskite precursor solution in step (1) is composed of one or more solvents selected from the group consisting of dimethyl sulfoxide, N,N-dimethylformamide, γ-butyrolactone, γ-valerolactone, N-methylpyrrolidone, isopropyl alcohol, methylammonium acetate ionic liquid, acetonitrile, 2-mercaptoethanol, 1,3-dimethyl-2-imidazolidinone, methylamine, ethanol, and n-butanol.

4. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 2, characterized in that: The concentration of the perovskite precursor solution in step (1) is 0.4 mol / L-2.0 mol / L in terms of divalent cations.

5. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 1, characterized in that: In step (4), when the perovskite film is spin-coated, an antisolvent needs to be sprayed. The antisolvent includes one or more of ethyl acetate, methyl formate, propionate, butyrate, ethyl silicate, toluene, trifluorotoluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene, iodobenzene, ethyl ether, anisole, dipropyl ether, dibutyl ether, sec-butyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, chloroform, and tetraethoxymethane.

6. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 1, characterized in that: High-quality large-area perovskite solar cells prepared by spin coating include formal perovskite solar cells and inverted perovskite solar cells, with an area of ​​not less than 3×3cm 2 The functional layers in the high-quality large-area perovskite solar cell are a first charge transport layer, a perovskite absorption layer, and a second charge transport layer. The functional layers are all prepared by spin coating in air at a spin coating rate of 800 rpm to 9000 rpm, and the spin coating time of each functional layer is 10 s to 120 s.

7. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 1, characterized in that: In step (4), the annealing temperature is 60° C.-350° C., and the annealing time is 10 min-90 min.

8. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 7, characterized in that: The conductive substrate includes a conductive layer and a non-conductive layer, the conductive layer includes ITO and FTO, the non-conductive layer includes glass, polyimide, polyethylene terephthalate, polyethylene naphthalate, and the conductive substrate is any one of ITO / glass substrate, FTO / glass substrate, ITO / PI substrate, FTO / PI substrate, ITO / PET substrate, FTO / PET substrate, ITO / PEN substrate, and FTO / PEN substrate; The conductive layer and the non-conductive layer, the conductive layer includes ITO and FTO, and the non-conductive layer includes glass, polyimide, polyethylene terephthalate, and polyethylene naphthalate.

9. The method for preparing high-quality large-area perovskite solar cells by spin coating in an ultra-clean environment system according to claim 1, characterized in that: The first charge transport layer and the second charge transport layer comprise one or more of tin dioxide, titanium dioxide, zinc oxide, fullerene, [6,6]-phenyl-C61-butyric acid methyl ester, perylene diimide derivatives, naphthalene diimide derivatives, hexaazatrinaphthyl derivatives, nickel oxide, cuprous thiocyanate, cuprous iodide, 2,2",7,7"-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene, copper phthalocyanine (CuPc), zinc phthalocyanine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl]amine, poly[bis(4-phenyl)(2,4,6-trimethylphenyl]amine, and poly(3-hexylthiophene-2,5-diyl); The annealing temperature of the first charge transport layer and the second charge transport layer is 50-450° C., and the thickness of the first charge transport layer and the second charge transport layer is 10-100 nm; The electrode comprises one of a carbon electrode, a gold electrode, a silver electrode, an aluminum electrode and a copper electrode, and the thickness of the electrode is 50-500 nm.

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