Perovskite solar cell and manufacturing method thereof

Abstract

Provided are a perovskite solar cell and a manufacturing method thereof, the manufacturing method comprising: forming a cathode on a transparent substrate; forming an electron transport layer on the cathode; forming a three-dimensional perovskite light absorption layer on the electron transport layer; forming a two-dimensional perovskite light absorption layer on the three-dimensional perovskite light absorption layer by using a vacuum coating method; wherein the material of the two-dimensional perovskite light absorption layer is (COOH(CH2)3NH3)2PbI4 or (COOH(CH2)7NH3)2PbI4; forming a hole transport layer on the two-dimensional perovskite light absorption layer; forming an anode on the hole transport layer to obtain the perovskite solar cell. The manufacturing method provided by the application uses a vacuum evaporation method instead of a solution method to construct a two-dimensional / three-dimensional perovskite heterostructure, avoids inconvenience and uncertainty caused by adding a solvent, and is also conducive to improving the quality, photoelectric properties, stability and interface characteristics of the three-dimensional perovskite thin film, thereby being conducive to improving the stability and efficiency of the perovskite solar cell.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solar cells, in particular to a perovskite solar cell and a manufacturing method thereof. BACKGROUND

[0002] With the continuous development of human society, the demand for energy is rapidly increasing. The main traditional energy sources that support modern society, such as coal, oil, and natural gas, have become increasingly depleted. Therefore, through research and development of renewable energy to reduce or replace the use of part of the traditional energy has become a global hot topic. Among them, solar energy as a renewable clean energy, has the characteristics of cheap, pollution-free, wide application, inexhaustible, etc., has become the focus of energy development in the 21st century. Through the use of the photovoltaic effect of semiconductor materials to convert light energy into electrical energy is the most widely used form of solar energy in the energy field, and its related industry has successfully moved from the laboratory to the market and achieved vigorous development.

[0003] Since the advent of perovskite solar cells in 2009, perovskite solar cells have received widespread attention, and their photoelectric conversion efficiency has developed from 3.8% to 25.5%. Among them, 3D perovskite thin films have high light absorption efficiency, can adjust the band gap by doping to absorb different wavelengths, have long carrier lifetime and large diffusion length, etc. The rapid improvement of the efficiency of perovskite solar cells cannot be ignored. However, 3D perovskite thin films have high requirements for the preparation process, especially they are sensitive to water, oxygen, light, etc. in the air, resulting in poor repeatability. In addition, the 3D perovskite thin films are mostly prepared by solution spin coating at the present stage, which is prone to produce defects such as pinholes and grain boundaries during film formation, and the 3D perovskite thin film is easily decomposed in the air.

[0004] Nowadays, some researchers have targeted 2D perovskite thin films. There is a van der Waals force between the organic amine layer and the inorganic layer of the 2D perovskite thin film, and between the organic amine layers, which makes the structure not easy to be destroyed, and some organic amines themselves have hydrophobicity, thereby bringing the possibility of improving the stability of perovskite solar cells. Therefore, in recent years, researchers have constructed 2D / 3D perovskite heterostructures, effectively combining the advantages of both, thereby improving the defects and interface properties of 3D perovskite thin films, which is conducive to improving the stability and efficiency of perovskite solar cells.

[0005] However, at present, 2D / 3D perovskite heterojunction thin films are mainly formed by a solution method, i.e. by adding organic cations into a 3D perovskite precursor solution or by surface treating a 3D perovskite thin film, so that a solvent is inevitably added in the preparation process, which leads to the following problems: on the one hand, many factors such as the selection of the solvent, the solubility, the corrosion to the perovskite and the transport layer, etc. need to be considered in the preparation of the solvent, which has many difficulties and uncertainties; on the other hand, the preparation of the solution is not conducive to commercialization and large-scale application. SUMMARY

[0006] In order to solve the problems existing in the prior art, the purpose of the present application is to provide a perovskite solar cell and a manufacturing method thereof.

[0007] According to an aspect of an embodiment of the present application, a manufacturing method of a perovskite solar cell is provided, which comprises: forming a cathode on a transparent substrate; forming an electron transport layer on the cathode; forming a three-dimensional perovskite light absorption layer on the electron transport layer; forming a two-dimensional perovskite light absorption layer on the three-dimensional perovskite light absorption layer by a vacuum coating method; wherein the material of the two-dimensional perovskite light absorption layer is (COOH(CH2)3NH3)2PbI4 or (COOH(CH2)7NH3)2PbI4; forming a hole transport layer on the two-dimensional perovskite light absorption layer; and forming an anode on the hole transport layer to obtain the perovskite solar cell.

[0008] Further, the method of forming the two-dimensional perovskite light absorption layer on the three-dimensional perovskite light absorption layer by the vacuum coating method specifically comprises: blowing and cleaning the three-dimensional perovskite light absorption layer by nitrogen; performing first evaporation at a first current and a first temperature under a first rate to seed two-dimensional perovskite seeds on the surface of the three-dimensional perovskite light absorption layer; and performing second evaporation at a second current and a second temperature under a second rate to form the two-dimensional perovskite light absorption layer on the surface of the three-dimensional perovskite light absorption layer.

[0009] Further, the first current is 10A-11A, the first temperature is 140℃-150℃, and the first rate is 0.1A / s-0.2A / s. The time of the first evaporation is 10s-20s, the second current is 12A-15A, the second temperature is 165℃-210℃, and the second rate is 0.1A / s-0.2A / s. The time of the second evaporation is 10s-100s, and the vacuum degree of the first evaporation and the second evaporation is less than 5x10 -4 Pa.

[0010] Further, the thickness of the two-dimensional perovskite seed crystal is 0.1 nm to 0.2 nm; and the thickness of the two-dimensional perovskite light absorption layer is 1 nm to 10 nm.

[0011] Further, the method for forming the three-dimensional perovskite light absorption layer on the electron transport layer specifically comprises: spin coating the prepared precursor solution of the three-dimensional perovskite light absorption layer on the surface of the electron transport layer away from the cathode by a spin coating method with a rotation speed of 3500 r / min, a rotation acceleration of 3000 r / min, and a rotation time of 15 s to 50 s; and annealing the spin-coated precursor solution at an annealing temperature of 100 ℃ to 450 ℃ and an annealing time of 10 min to 30 min to crystallize and form the three-dimensional perovskite light absorption layer with a thickness of 180 nm to 310 nm.

[0012] The material of the three-dimensional perovskite light absorption layer comprises any one of MAPbI3, MAPbBr3, MAPbCl3, MAPbI 3- x Br x , MAPbI 3-x Cl x , MA y FA 1-y PbI3, MA y FA 1-y PbI 3-x Cl x , MA y FA 1-y PbI 3-x Br x , CsSnxPb1-xI3, CsPbI3, CsSnI3, and CsPbBr3.

[0013] Further, the method for forming the cathode on the transparent substrate specifically comprises: uniformly applying a transparent conductive oxide material on the transparent substrate to form the cathode; and the transparent conductive oxide material is indium tin oxide.

[0014] Further, the method for forming the electron transport layer on the cathode specifically comprises: spin coating a prepared precursor solution of the electron transport layer on the surface of the cathode away from the transparent substrate; and annealing at an annealing temperature of 100 ℃ to 450 ℃ and an annealing time of 10 min to 30 min to crystallize and form the electron transport layer; and the material of the electron transport layer comprises any one of TiO2, SnO2, and PC 61 BM.

[0015] Further, the method for forming the hole transport layer on the two-dimensional perovskite light absorption layer specifically comprises: spin coating a precursor solution of the hole transport layer configured on a surface of the two-dimensional perovskite light absorption layer away from the three-dimensional perovskite light absorption layer to form the hole transport layer; wherein the material of the hole transport layer comprises any one of Spiro-OMeTAD, PEDOT:PSS, NiO x and CuSCN.

[0016] Further, the method for forming the anode on the hole transport layer specifically comprises: forming the anode on a surface of the hole transport layer away from the two-dimensional perovskite light absorption layer by a vacuum evaporation instrument;

[0017] wherein the thickness of the anode is 100 nm, and the electrode material of the anode comprises any one of Ag, Au and Al.

[0018] According to another aspect of the embodiments of the present application, a perovskite solar cell is provided, which is manufactured by the above manufacturing method.

[0019] Beneficial effects: The perovskite solar cell and the manufacturing method thereof, the perovskite solar cell is a perovskite solar cell based on two-dimensional / three-dimensional perovskite heterostructure, and the manufacturing method adopts a vacuum evaporation method instead of a solution method to deposit a two-dimensional perovskite material on a three-dimensional perovskite material to construct a two-dimensional / three-dimensional perovskite heterostructure, thereby solving the inconvenience and uncertainty caused by adding a solvent in the solution method, and being beneficial to improving the quality, photoelectric property, stability and interface characteristics of the three-dimensional perovskite thin film, and further being beneficial to improving the stability and efficiency of the perovskite solar cell. In addition, the manufacturing method is simple and convenient, and is suitable for commercialization and large-scale application. BRIEF DESCRIPTION OF DRAWINGS

[0020] The above and other aspects, features and advantages of the embodiments of the present application will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:

[0021] Figure 1 is a flowchart of the manufacturing method of the perovskite solar cell according to the embodiments of the present application;

[0022] Figure 2 is a structural diagram of the perovskite solar cell according to the embodiments of the present application. DETAILED DESCRIPTION

[0023] Hereinafter, specific embodiments of the present application will be described in detail with reference to the accompanying drawings. The present application may, however, be implemented in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the principles of the application to others skilled in the art. Aspects of the present application and various modifications will be apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments, applications, and objects without departing from the scope of the application.

[0024] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," and the like are open-ended terms that are intended to mean "including but not limited to." The terms "based on" and "according to" and the like are intended to mean "based, at least in part, on" and "according, at least in part, to." The terms "one embodiment," "an embodiment," "some embodiments," and / or "one implementations" are understood to mean one or more embodiments. The terms "another embodiment" are understood to mean at least one embodiment different from the preceding embodiment. The terms "first," "second," and / or the like can refer to different or identical objects. Other definitions can be introduced herein that are not explicitly defined but are apparent from the context in which they are used. Unless otherwise explicitly indicated, the definition of a term is the same throughout this specification.

[0025] As described in the background, since the two-dimensional / three-dimensional perovskite heterostructure of the perovskite solar cell in the prior art is mainly prepared by a solution method, a solvent is inevitably added in the process of preparation, which causes the following problems: on the one hand, many factors need to be considered in the process of preparing the solvent, which has too many inconveniences and uncertainties; on the other hand, the preparation of the solution is not conducive to commercialization and large-scale application. Therefore, in order to solve the many technical problems existing in the perovskite solar cell in the prior art, according to the embodiments of the present application, a perovskite solar cell and a manufacturing method thereof are provided.

[0026] The manufacturing method adopts a vacuum evaporation method instead of a solution method, deposits a two-dimensional perovskite material on a three-dimensional perovskite material to construct a two-dimensional / three-dimensional perovskite heterostructure, so as to obtain a perovskite solar cell based on the two-dimensional / three-dimensional perovskite heterostructure, which solves the inconveniences and uncertainties caused by the addition of the solvent in the solution method, and is also conducive to improving the quality, photoelectric properties, stability and interface characteristics of the three-dimensional perovskite thin film, and further conducive to improving the stability and efficiency of the perovskite solar cell.

[0027] Hereinafter, a perovskite solar cell and a manufacturing method thereof according to the embodiments of the present application will be described in detail with reference to the accompanying drawings, Figure 1 is a flowchart of the manufacturing method of the perovskite solar cell according to the embodiments of the present application.

[0028] Reference Figure 1 In step S110, a cathode 20 is formed on the transparent substrate 10.

[0029] Specifically, a transparent conductive oxide material is uniformly coated on the first surface of the transparent substrate 10 to form the cathode 20; wherein the first surface and the second surface of the transparent substrate 10 are two opposite and identical surfaces of the transparent substrate 10.

[0030] In one example, the material of the transparent substrate 10 is glass or quartz to enable the incident light to enter into the perovskite solar cell.

[0031] In one example, the transparent conductive oxide material is indium tin oxide (ITO), and the cathode 20 is used to collect the electrons excited by the perovskite light absorption layer of the cell.

[0032] In step S120, an electron transport layer 30 is formed on the cathode 20.

[0033] Specifically, a spin coater is used to spin-coat the prepared precursor solution of the electron transport layer 30 on the surface of the cathode 20 away from the transparent substrate 10 at a rotation speed of 3000 r / min to 3500 r / min and a rotation time of 30 s; and then a heating table is used to perform annealing at an annealing temperature of 100℃ to 450℃ and an annealing time of 10 min to 30 min to crystallize the electron transport layer 30 with a thickness of 90 nm to 100 nm.

[0034] In one example, the material of the electron transport layer 30 includes metal oxides TiO2, SnO2, and / or organic electron transport materials PCBM. 61 Any one of the BMs; wherein the electron transport layer 30 can effectively play a role in transporting electrons and blocking holes.

[0035] In the present embodiment, after the cathode 20 is formed on the transparent substrate 10 and before the electron transport layer 30 is formed on the cathode 20, the manufacturing method further includes: pretreating the transparent substrate 10, specifically including:

[0036] First, the transparent substrate 10 is ultrasonically cleaned for 15 min by using an aqueous solution composed of deionized water and a small amount of alkaline cleaning solution (Decon-90);

[0037] Then, the transparent substrate 10 is ultrasonically cleaned for 15 min by using an aqueous solution composed of deionized water and acetone, an aqueous solution composed of deionized water and alcohol, and deionized water, respectively, and is dried by using a nitrogen gun after being cleaned;

[0038] Finally, the transparent substrate 10 is subjected to ultraviolet ozone treatment (UV-Ozone) for 15 min.

[0039] In step S130, a three-dimensional perovskite light absorption layer 40 is formed on the electron transport layer 30, specifically including:

[0040] First, in a glove box filled with nitrogen, a prepared precursor solution of the three-dimensional perovskite light absorption layer 40 is spin-coated on the surface of the electron transport layer 30 away from the cathode 20 by using a spin coater with a rotation speed of 3500 r / min, a rotation acceleration of 3000 r / min, and a rotation time of 15 s to 50 s; when the spin-coating time is 45 s, 350 uL of toluene solution is dropped to improve the film forming process of the precursor solution of the three-dimensional perovskite light absorption layer 40.

[0041] Then, the spin-coated precursor solution is annealed by using a heating stage with an annealing temperature of 100℃ to 450℃ and an annealing time of 10 min to 30 min to crystallize the three-dimensional perovskite light absorption layer 40 with a thickness of 180 nm to 310 nm.

[0042] In one example, the material of the three-dimensional perovskite light absorption layer 40 includes any one of MAPbI3, MAPbBr3, MAPbCl3, MAPbI 3-x Br x , MAPbI 3-x Cl x , MA y FA 1-y PbI3, MA y FA 1-y PbI 3-x Cl x , MA y FA 1-y PbI 3-x Br x , CsSnxPb1-xI3, CsPbI3, CsSnI3, and CsPbBr3.

[0043] In this embodiment, the three-dimensional perovskite light absorption layer 40 can absorb incident light and convert light energy into electrical energy.

[0044] In step S140, a two-dimensional perovskite light absorption layer 50 is formed on the three-dimensional perovskite light absorption layer 40 by using a vacuum coating method; the material of the two-dimensional perovskite light absorption layer is ((COOH(CH2)3NH3)2PbI4) or ((COOH(CH2)7NH3)2PbI4); and the thickness of the two-dimensional perovskite light absorption layer 50 is 1 nm to 10 nm.

[0045] Specifically, the step S140 includes:

[0046] First, nitrogen is blown into the three-dimensional perovskite light absorption layer 40 for cleaning: N2 is used to clean the three-dimensional perovskite absorption layer 40 prepared in step S130 for 1 min;

[0047] Second, under the conditions of the first current and the first temperature, the first rate is used for the first evaporation to seed the two-dimensional perovskite seed crystal on the surface of the three-dimensional perovskite light absorption layer 40, specifically including:

[0048] The three-dimensional perovskite absorption layer 40 after the cleaning process is fixed above the vacuum coating instrument, and the two-dimensional perovskite material to be evaporated is placed in the ceramic crucible. Then, the molecular pump is opened, and the vacuum degree is extracted to 5x10 -4 Pa or below, and then the evaporation is started;

[0049] Then, the first current is controlled to 10A-11A, the temperature controller is used to detect and control the first temperature to 140℃-150℃, the shutter is opened, and the sensor is used to detect the evaporation rate. The first rate is The first evaporation is performed at the first rate for 10s-20s to seed the two-dimensional perovskite seed crystal with a thickness of 0.1nm-0.2nm on the surface of the three-dimensional perovskite light absorption layer 40;

[0050] Third, under the conditions of the second current and the second temperature, the second rate is used for the second evaporation to form the two-dimensional perovskite light absorption layer 50 on the surface of the three-dimensional perovskite light absorption layer 40, specifically including:

[0051] The vacuum degree is maintained, the current is increased to the second current 12A-15A, the temperature controller is used to detect and control the second temperature to 165℃-210℃, and the second rate is The second evaporation is performed at the second rate for 10s-100s to form the two-dimensional perovskite light absorption layer 50 on the surface of the three-dimensional perovskite light absorption layer 40.

[0052] The two-dimensional perovskite light absorption layer 50 and the three-dimensional perovskite light absorption layer 40 form a two-dimensional / three-dimensional perovskite heterostructure, which is beneficial to prolong the carrier lifetime, suppress non-radiative recombination loss, and thus improve the photoelectric efficiency of the battery. In addition, it is also beneficial to improve the film quality of the three-dimensional perovskite light absorption layer 40, enhance the hydrophobicity of the three-dimensional perovskite light absorption layer 40, and thus significantly improve the environmental stability and thermal stability of the battery.

[0053] In the embodiment, the material of the two-dimensional perovskite light absorption layer 50 is ((COOH(CH2)3NH3)2PbI4) or ((COOH(CH2)7NH3)2PbI4), the main difference between the two is that the organic cation is a bifunctional amino acid molecule with different numbers of carbon atoms, and the carboxyl-containing organic cation can improve the stability of the material by forming additional hydrogen bonds between the perovskite layers.

[0054] The compounds ((COOH(CH2)3NH3)2PbI4) and ((COOH(CH2)7NH3)2PbI4) differ mainly in structure due to the organic cation [PbI6] 4- The octahedral distortion and the different ways of intermolecular connection cause the symmetry of the crystal system to decrease continuously as the C chain lengthens. The compound ((COOH(CH2)3NH3)2PbI4) is orthorhombic, and the compound ((COOH(CH2)7NH3)2PbI4) is monoclinic. The light absorption cutoff wavelength of the compound ((COOH(CH2)3NH3)2PbI4) is 580 nm, and the light absorption cutoff wavelength of the compound ((COOH(CH2)7NH3)2PbI4) is 530 nm. It can be seen that both the compounds ((COOH(CH2)3NH3)2PbI4) and ((COOH(CH2)7NH3)2PbI4) have strong absorption in the visible light band, which is conducive to enhancing the absorption capacity of the three-dimensional perovskite light absorption layer 40 for visible light. The longer hydrophobic C chain can improve the environmental stability of the material to a greater extent, so the compounds ((COOH(CH2)3NH3)2PbI4) and ((COOH(CH2)7NH3)2PbI4) both have excellent humidity stability. In addition, the decomposition temperature of the compounds ((COOH(CH2)3NH3)2PbI4) and ((COOH(CH2)7NH3)2PbI4) is above 220°C, and they both have good thermal stability, which is conducive to improving the quality of the three-dimensional perovskite thin film 40 and enhancing the hydrophobicity of the three-dimensional perovskite thin film 40.

[0055] In step S150, a hole transport layer 60 is formed on the two-dimensional perovskite light absorption layer 50.

[0056] Specifically, the prepared precursor solution of the hole transport layer 60 is spin-coated on the surface of the two-dimensional perovskite light absorption layer 50 away from the three-dimensional perovskite light absorption layer 40 by a spin coating method of first rotating at 1000 r / min for 5 s and then rotating at 4000 r / min for 45 s, and / or a spin coating method of rotating at 4000 r / min for 45 s, to form the hole transport layer 60.

[0057] In this embodiment, the material of the hole transport layer 60 includes organic hole transport materials Spiro-OMeTAD and PEDOT:PSS, and / or inorganic hole transport material NiO. x It can be any one of CuSCN. The hole transport layer 60 can extract effective charge and block electrons.

[0058] In step S160, an anode 70 is formed on the hole transport layer 60 to obtain the perovskite solar cell.

[0059] Specifically, the anode 70 is formed on the surface of the hole transport layer 60 facing away from the two-dimensional perovskite light absorption layer 50 using a vacuum evaporation apparatus; wherein the evaporation temperature is room temperature and the vacuum degree of evaporation is 5 × 10⁻⁶. -4 Pa~6×10 - 4 Pa, the current for vapor deposition is 68A~70A.

[0060] In this embodiment, the electrode material of the anode 70 includes Ag, Au, or Al, and the thickness of the anode 70 is 100 nm; the anode 70 is used to collect holes.

[0061] The following describes more specific embodiments. Figure 1 The manufacturing method shown will be explained in detail.

[0062] Example 1

[0063] The method for fabricating a perovskite solar cell according to Embodiment 1 of the present invention includes:

[0064] Step 1: Forming a cathode on a glass substrate, specifically including:

[0065] Step 1: A transparent conductive oxide material (ITO) is uniformly coated on the first surface of a glass substrate to form a cathode;

[0066] The second step involves pre-treating the glass substrate. Specifically, firstly, the glass substrate on which the cathode has been formed is ultrasonically cleaned for 15 minutes using an aqueous solution composed of deionized water and a small amount of alkaline cleaning solution (Decon-90). Next, the glass substrate is ultrasonically cleaned for 15 minutes each using an aqueous solution composed of deionized water and acetone, an aqueous solution composed of deionized water and alcohol, and deionized water. After cleaning, the substrate is dried using a nitrogen gun. Finally, the glass substrate is subjected to ultraviolet ozone treatment (UV-Ozone) for 15 minutes.

[0067] Therefore, step one above has been achieved. Figure 1 The method of step S110.

[0068] Step two, forming a SnO2 electron transport layer on the transparent conductive oxide layer of the glass substrate, specifically comprising:

[0069] First step, preparing a SnO2 precursor solution: 2 mL of deionized water is extracted by a pipette, and then 1 mL of SnO2 solution is extracted by a pipette. After mixing in a fume hood, the mixture is stirred on a magnetic heating stirrer at room temperature until completely mixed to obtain the SnO2 precursor solution;

[0070] Second step, using a spin coater to spin coat the prepared SnO2 precursor solution on the surface of the transparent conductive oxide layer of the glass transparent substrate away from the glass transparent substrate at a rotation speed of 3500 r / min and a rotation time of 30 s;

[0071] Third step, using a heating table to anneal at an annealing temperature of 150°C and an annealing time of 30 min to crystallize to form the SnO2 electron transport layer.

[0072] Therefore, the above step one realizes Figure 1 the method of step S120.

[0073] Step three, forming a MAPbI 3-x Cl x perovskite light absorption layer on the SnO2 electron transport layer, specifically comprising:

[0074] First step, preparing a MAPbI 3-x Cl x precursor solution: first, prepare a mixed solvent according to a volume ratio of DMSO (dimethyl sulfoxide): GBL (γ-butyrolactone) = 3:7. Place the mixed solvent on a magnetic stirrer and add a rotor to stir for 20 min. Then, weigh 214.65 mg of MAI and dissolve it in 1 mL of the mixed solvent to obtain a MAI mixed solution with a concentration of 1.35 mol / L. Finally, weigh 580.86 mg of PbI2 and 38.92 mg of PbCl2 and dissolve them in 1 mL of the MAI mixed solution, and heat stir at 75°C for 1 h to obtain the MAPbI 3-x Cl x precursor solution;

[0075] Second step, in a nitrogen-filled glove box, use a pipette to take 75 uL of the MAPbI 3-x Cl x precursor solution, and then use a spin coater to spin coat the prepared MAPbI 3-x Cl xA precursor solution is spin-coated on a surface of the SnO2 electron transport layer opposite to the transparent conductive oxide layer; wherein when the spin-coating time is 45 s, 350 uL of toluene solution is dropped;

[0076] Third step, annealing at an annealing temperature of 100℃ and an annealing time of 30 min to crystallize the MAPbI 3-x Cl x Perovskite light absorption layer, wherein the MAPbI 3-x Cl x The perovskite light absorption layer is a three-dimensional perovskite light absorption layer.

[0077] Therefore, the above step three realizes Figure 1 The method of step S130.

[0078] Fourth step, forming a two-dimensional perovskite light absorption layer on the MAPbI 3-x Cl x The perovskite light absorption layer, specifically comprising:

[0079] First step, blowing the MAPbI 3-x Cl x Perovskite light absorption layer with N2 for 1 min.

[0080] Second step, placing the MAPbI 3-x Cl x Perovskite light absorption layer after the blowing cleaning treatment above the vacuum coating instrument and placing the two-dimensional perovskite material to be evaporated in the ceramic crucible, then opening the molecular pump, vacuumizing, and vacuumizing to 5×10 -4 Pa or below to start evaporation;

[0081] Then, controlling the current to 10A, using the temperature controller to detect and control the temperature to 140℃, opening the shutter, using the sensor to detect the evaporation rate, and evaporating at a rate of 10A / s for the first time for 10s to seed the surface of the MAPbI 3-x Cl x Perovskite light absorption layer with a two-dimensional perovskite seed crystal with a thickness of 0.1 nm;

[0082] Third step, increasing the current to 12A, using the temperature controller to detect and control the temperature to 165℃, and evaporating at a rate of 10A / s for the second time for 10s to seed the surface of the MAPbI 3-x Cl xThe two-dimensional perovskite light absorption layer is formed on the surface of the perovskite light absorption layer facing away from the SnO2 electron transport layer; wherein the material of the two-dimensional perovskite light absorption layer is ((COOH(CH2)3NH3)2PbI4).

[0083] Therefore, the above step four achieves Figure 1 the method in step S140.

[0084] Step five, forming a Spiro-OMeTAD hole transport layer on the two-dimensional perovskite light absorption layer, specifically comprising:

[0085] Firstly, 90mg of Spiro is weighed and dissolved in 1mL of chlorobenzene in a nitrogen-filled glove box, then placed on a magnetic heating stirrer, stirred at room temperature until completely dissolved to obtain a mixed solution with a concentration of 90mg / mL; then 75uL of cobalt salt solution, 45uL of lithium salt solution and 10uL of TBP are sequentially added to the mixed solution using a pipette, and again placed on a magnetic heating stirrer, stirred at room temperature until completely dissolved to obtain the Spiro-OMeTAD precursor solution;

[0086] Secondly, 75uL of the Spiro-OMeTAD precursor solution is taken out using a pipette, and then the prepared Spiro-OMeTAD precursor solution is spin-coated on the surface of the two-dimensional perovskite light absorption layer facing away from the MAPbI 3-x Cl x The surface of the perovskite light absorption layer to obtain the Spiro-OMeTAD hole transport layer.

[0087] Therefore, the above step five achieves Figure 1 the method in step S150.

[0088] Step six, forming an anode on the Spiro-OMeTAD hole transport layer, specifically comprising: forming an Ag electrode on the surface of the Spiro-OMeTAD hole transport layer facing away from the two-dimensional perovskite light absorption layer by a vacuum evaporation instrument, as an anode, to obtain the perovskite solar cell; wherein the evaporation temperature is room temperature, the vacuum degree of evaporation is 5x10 - 4 Pa, and the evaporation current is 68A.

[0089] Therefore, the above step six achieves Figure 1 the method in step S160.

[0090] Step seven, battery test and characterization: the perovskite solar cell obtained in step six is tested for photoelectric response under AM1.5G solar spectrum.

[0091] The perovskite solar cell obtained by the above manufacturing method has an effective area of 7mm 2 , an energy conversion efficiency of 23.1%, an open circuit voltage of 1.18V, a short circuit current density of 25.5mA / cm 2 , and a fill factor of 76.7%.

[0092] Embodiment 2

[0093] The manufacturing method of the perovskite solar cell according to Embodiment 2 of the present application comprises:

[0094] Step one, forming a cathode on a glass substrate, specifically comprising:

[0095] First step, uniformly applying a transparent conductive oxide material (ITO) on the first surface of the glass substrate to form a cathode;

[0096] Second step, pretreating the glass substrate, specifically, first, ultrasonic cleaning the glass substrate on which the cathode has been formed with an aqueous solution composed of deionized water and a small amount of alkaline cleaning solution (Decon-90) for 15 minutes; then, sequentially using an aqueous solution composed of deionized water and acetone, an aqueous solution composed of deionized water and alcohol, and deionized water to ultrasonic clean the glass substrate for 15 minutes each, and then blowing dry with a nitrogen gun after cleaning; finally, performing ultraviolet ozone treatment (UV-Ozone) on the glass substrate for 15 minutes.

[0097] Therefore, the above step one realizes the method of step S110 in Figure 1 .

[0098] Step two, forming a TiO2 electron transport layer on the transparent conductive oxide layer of the glass transparent substrate, specifically comprising:

[0099] First step, preparing a TiO2 precursor solution: using a pipette to suck 550uL of TiCl4 into a beaker, and then adding deionized water to obtain a total volume of 200mL of the TiO2 precursor solution;

[0100] Second step, the glass substrate prepared in step one is placed in the TiO2 precursor solution, the cup is sealed, and the glass substrate is placed in the baking oven and baked at 70°C for 30 min. Then the glass substrate is taken out, washed with deionized water, and the surface moisture is absorbed. Then the prepared TiO2 precursor solution is spin-coated on the surface of the transparent conductive oxide layer of the glass substrate away from the glass substrate by using a glue throwing machine at a speed of 3000r / min for 30s.

[0101] Third step, annealing is performed by using a heating table at an annealing temperature of 100°C and an annealing time of 30 min to crystallize and form the TiO2 electron transport layer.

[0102] Therefore, the above step one realizes Figure 1 the method of step S120.

[0103] Step three, forming a MAPbI3 perovskite light absorption layer on the TiO2 electron transport layer, specifically including:

[0104] First step, preparing a MAPbI3 precursor solution: first, prepare a mixed solvent according to the volume ratio of DMSO: GBL = 3:7, then weigh 1033mg of MAI and 2996mg of PbI2 and dissolve them in 5mL of the mixed solvent, and finally place it on a magnetic heating table and heat and stir at 75°C until completely dissolved to obtain the MAPbI3 precursor solution;

[0105] Second step, in a nitrogen-filled glove box, use a pipette to take 75uL of the MAPbI3 precursor solution, and then use a glue throwing machine to spin-coat the prepared MAPbI3 precursor solution on the surface of the TiO2 electron transport layer away from the transparent conductive oxide layer at a speed of 3500r / min, a rotation acceleration of 3000r / min, and a rotation time of 45s. When the spin-coating time is 45s, 350uL of toluene solution is added;

[0106] Third step, annealing is performed by using a heating table at an annealing temperature of 120°C and an annealing time of 30 min to crystallize and form the MAPbI3 perovskite light absorption layer, wherein the MAPbI3 perovskite light absorption layer is a three-dimensional perovskite light absorption layer.

[0107] Therefore, the above step three realizes Figure 1 the method of step S130.

[0108] Step four, forming a two-dimensional perovskite light absorption layer on the MAPbI3 perovskite light absorption layer by using a vacuum coating method, specifically including:

[0109] First, the MAPbI 3-x Cl x The perovskite light absorption layer is subjected to air blowing cleaning for 1 min.

[0110] Second, the MAPbI 3-x Cl x The perovskite light absorption layer is fixed above the vacuum coating instrument, and the two-dimensional perovskite material to be evaporated is placed in a ceramic crucible. Then, the molecular pump is opened, and the vacuum degree is extracted to 5x10 -4 Pa or below, and the evaporation is started;

[0111] Then, the current is controlled to 11 A, the temperature controller is used to detect and control the temperature to 150°C, the shutter is opened, the sensor is used to detect the evaporation rate, and the first evaporation is performed at a rate of , and the evaporation time is 20 s, so as to form the two-dimensional perovskite light absorption layer on the surface of the MAPbI 3-x Cl x The surface of the perovskite light absorption layer is first seeded with a two-dimensional perovskite seed crystal with a thickness of 0.2 nm;

[0112] Third, the current is increased to 15 A, the temperature controller detects and controls the temperature to 210°C, and the second evaporation is performed at a rate of , and the evaporation time is 100 s, so as to form the two-dimensional perovskite light absorption layer on the surface of the MAPbI3 perovskite light absorption layer facing away from the TiO2 electron transport layer; wherein the material of the two-dimensional perovskite light absorption layer is ((COOH(CH2)7NH3)2PbI4).

[0113] Therefore, the above step four realizes the method of step S140 in Figure 1 .

[0114] Step five, forming a NiO x hole transport layer on the two-dimensional perovskite light absorption layer, specifically comprising:

[0115] First, preparing a NiO x precursor solution: first, 270.79 mg of Ni(NO3)2·6H2O is dissolved in 10 mL of 2-methoxyethanol solution, then placed on a heating stirring table, stirred at 50°C for 1 h, then 100 uL of acetylacetone solution is added, and stirred at room temperature for 12 h to obtain the NiO x precursor solution;

[0116] Second, 75 uL of the NiO x precursor solution is taken by a pipette.The precursor solution is then spin-coated on the surface of the two-dimensional perovskite light absorption layer away from the MAPbI3 perovskite light absorption layer by using a spin coater at a rotation speed of 4000 r / min and a rotation time of 45 s to obtain the NiO x The precursor solution is spin-coated on the surface of the two-dimensional perovskite light absorption layer away from the MAPbI3 perovskite light absorption layer by using a spin coater at a rotation speed of 4000 r / min and a rotation time of 45 s to obtain the NiO x The hole transport layer.

[0117] Therefore, the above step five achieves Figure 1 The method of step S150.

[0118] Step six, forming an anode on the surface of the NiO x The hole transport layer. x The Ag electrode is formed on the surface of the hole transport layer away from the two-dimensional perovskite light absorption layer to serve as an anode, and the perovskite solar cell is obtained; wherein the temperature for evaporation is room temperature, the vacuum degree for evaporation is 6x10 -4 Pa, and the current for evaporation is 70 A.

[0119] Therefore, the above step six achieves Figure 1 The method of step S160.

[0120] Step seven, battery testing and characterization: the perovskite solar cell obtained in step six is subjected to photoelectric response testing under AM1.5G solar spectrum.

[0121] The perovskite solar cell obtained by the above manufacturing method has an effective area of 7mm 2 , an energy conversion efficiency of 23.4%, an open-circuit voltage of 1.17V, a short-circuit current density of 25.4mA / cm 2 , and a fill factor of 78.7%.

[0122] Example 3

[0123] The manufacturing method of the perovskite solar cell according to Example 3 of the present application comprises:

[0124] Step one, forming a cathode on a glass substrate, specifically comprising:

[0125] First step, uniformly applying a transparent conductive oxide material (ITO) on the first surface of the glass substrate to form a cathode.

[0126] Second step, pre-treatment of the glass substrate, specifically, first, the glass substrate with the cathode has been formed is ultrasonically cleaned for 15 min with an aqueous solution composed of deionized water and a small amount of alkaline cleaning solution (Decon-90); then, the glass substrate is ultrasonically cleaned for 15 min with an aqueous solution composed of deionized water and acetone, an aqueous solution composed of deionized water and alcohol, and deionized water, respectively, and dried with a nitrogen gun after cleaning; finally, the glass substrate is treated with ultraviolet ozone (UV-Ozone) for 15 min.

[0127] Therefore, the above step one achieves Figure 1 the method of step S110 in the

[0128] Step two, forming a SnO2 electron transport layer on the transparent conductive oxide layer of the glass substrate, specifically including:

[0129] First step, preparation of SnO2 precursor solution: 2 mL of deionized water is extracted with a pipette, then 1 mL of SnO2 solution is extracted with a pipette, and the two are mixed in a fume hood and stirred on a magnetic heating stirrer at room temperature until completely mixed to obtain the SnO2 precursor solution;

[0130] Second step, using a spin coater, spin coating the prepared SnO2 precursor solution on the surface of the transparent conductive oxide layer of the glass substrate away from the glass substrate at a rotation speed of 3500 r / min and a rotation time of 30 s;

[0131] Third step, using a heating table, annealing at an annealing temperature of 150°C and an annealing time of 30 min to crystallize and form the SnO2 electron transport layer.

[0132] Therefore, the above step one achieves Figure 1 the method of step S120 in the

[0133] Step three, forming a MA 0.7 FA 0.3 PbI3 perovskite light absorption layer, specifically including:

[0134] First step, preparation of MA 0.7 FA 0.3 PbI3 precursor solution: first, prepare a mixed solvent according to a volume ratio of DMSO: GBL = 3:7, then weigh 451 mg of MAI and 209 mg of FAI and dissolve them in 3 mL of the mixed solvent, finally place it on a magnetic heating table and heat and stir at 75°C until completely dissolved to obtain the MA 0.7 FA 0.3 PbI3 precursor solution;

[0135] The second step, in a glove box filled with nitrogen, 75uL of the MA 0.7 FA 0.3 PbI3 precursor solution, and then using a spin coater, the prepared MA 0.7 FA 0.3 PbI3 precursor solution is spin-coated on the surface of the SnO2 electron transport layer opposite to the transparent conductive oxide layer; wherein when the spin-coating time is 45s, 350uL of toluene solution is dropped;

[0136] The third step, using a heating table, annealing at an annealing temperature of 120℃ and an annealing time of 25min to crystallize the MA 0.7 FA 0.3 PbI3 perovskite light absorption layer, wherein the MA 0.7 FA 0.3 The MA 0.7 FA 0.3 PbI3 perovskite light absorption layer is a three-dimensional perovskite light absorption layer.

[0137] Therefore, the above step three realizes Figure 1 The method of step S130 in the method.

[0138] The fourth step, using a vacuum coating method to form a two-dimensional perovskite light absorption layer on the MA 3-x Cl x PbI3 perovskite light absorption layer, specifically comprising:

[0139] The first step, using N2 to blow and clean the MAPbI 3-x Cl x PbI3 perovskite light absorption layer for 1min.

[0140] The second step, placing the MAPbI 3-x Cl x PbI3 perovskite light absorption layer after the blowing and cleaning treatment above the vacuum coating instrument, and placing the two-dimensional perovskite material to be evaporated in a ceramic crucible, then opening the molecular pump, vacuumizing, and vacuumizing to 5x10 -4 Pa or below to start evaporation;

[0141] Then, controlling the current to 11A, using a temperature controller to detect and control the temperature to 150℃, opening the shutter, using a sensor to detect the evaporation rate, and evaporating at a rate of The first time, the evaporation time is 20s, so as to form a two-dimensional perovskite light absorption layer on the MAPbI 3-x Cl xThe surface of the perovskite light absorption layer is first seeded with two-dimensional perovskite seed crystals with a thickness of 0.2 nm;

[0142] Third step, the current is increased to 15A, the temperature controller detects the control temperature to be 210℃, and the second evaporation is carried out at a rate of 0.5A / s for 100s, so that the MA 0.7 FA 0.3 The two-dimensional perovskite light absorption layer is formed on the surface of the PbI3 perovskite light absorption layer facing away from the SnO2 electron transport layer; wherein the material of the two-dimensional perovskite light absorption layer is ((COOH(CH2)3NH3)2PbI4).

[0143] Therefore, the above step four realizes the method of step S140 in the embodiment. Figure 1

[0144] Step five, forming a Spiro-OMeTAD hole transport layer on the two-dimensional perovskite light absorption layer, specifically comprising:

[0145] First step, preparing a Spiro-OMeTAD precursor solution: first, 90mg of Spiro is weighed and dissolved in 1mL of chlorobenzene in a nitrogen-filled glove box, then placed on a magnetic heating stirrer, stirred at room temperature until completely dissolved to obtain a mixed solution with a concentration of 90mg / mL; then 75uL of cobalt salt solution, 45uL of lithium salt solution and 10uL of TBP are sequentially added to the mixed solution using a pipette, and again placed on a magnetic heating stirrer, stirred at room temperature until completely dissolved to obtain the Spiro-OMeTAD precursor solution;

[0146] Second step, 75uL of the Spiro-OMeTAD precursor solution is taken out using a pipette, and then the prepared Spiro-OMeTAD precursor solution is spin-coated on the surface of the two-dimensional perovskite light absorption layer facing away from the MA 0.7 FA 0.3 PbI 3x The surface of the perovskite light absorption layer is first seeded with two-dimensional perovskite seed crystals with a thickness of 0.2 nm;

[0147] Therefore, the above step five realizes the method of step S150 in the embodiment. Figure 1

[0148] ​​​Step six, forming an anode on the Spiro-OMeTAD hole transport layer, specifically comprising: forming an Ag electrode as an anode on the surface of the Spiro-OMeTAD hole transport layer away from the two-dimensional perovskite light absorption layer by vacuum evaporation instrument, to obtain the perovskite solar cell; wherein the temperature of evaporation is room temperature, the vacuum degree of evaporation is 5x10 -4 Pa, and the current of evaporation is 70A.

[0149] Therefore, the above step six realizes Figure 2 the method of step S160.

[0150] Step seven, battery testing and characterization: the perovskite solar cell obtained in step six is tested for photoelectric response under AM1.5G solar spectrum.

[0151] The effective area of the perovskite solar cell obtained by the above manufacturing method is 7mm 2 , the energy conversion efficiency is 22.9%, the open circuit voltage is 1.17V, the short circuit current density is 25.3mA / cm 2 , and the fill factor is 77.3%.

[0152] According to the embodiments of the present application, a perovskite solar cell formed by the above manufacturing method is also provided.

[0153] Figure 2 is a structural schematic diagram of a perovskite solar cell according to the embodiments of the present application, Figure 1 The perovskite solar cell shown in the figure is a two-dimensional / three-dimensional perovskite heterostructure-based perovskite solar cell, which is prepared by the above manufacturing method (i.e. Figure 2 The manufacturing method shown in the figure). Referring to ​ , the perovskite solar cell comprises a transparent substrate 10, a cathode 20, an electron transport layer 30, a three-dimensional perovskite light absorption layer 40, a two-dimensional perovskite light absorption layer 50, a hole transport layer 60, and an anode 70.

[0154] In summary, according to the perovskite solar cell and the manufacturing method thereof, the manufacturing method adopts a vacuum evaporation method instead of a solution method to deposit a two-dimensional perovskite material on a three-dimensional perovskite material, and construct a two-dimensional / three-dimensional perovskite heterostructure, thereby solving the inconvenience and uncertainty caused by a solvent in the preparation process by using the solution method. The two-dimensional perovskite material has good visible light absorption capacity, hydrophobicity and thermal stability, thereby being beneficial to improving the quality, photoelectric property, stability and interface characteristics of the three-dimensional perovskite thin film, and further being beneficial to improving the environmental stability, thermal stability and cell efficiency of the perovskite solar cell. In addition, the manufacturing method of the perovskite solar cell is simple and convenient, and is suitable for commercialization and large-scale application.

[0155] The specific embodiments of the application have been described. Other embodiments are within the scope of the following claims.

[0156] The terms "exemplary," "example," and the like are used as adjectives to indicate that something is used as an example, instance, or illustration. The terms "exemplary," "example," and the like do not denote "preferred" or "superior" over other embodiments. The detailed description includes specific details for the purpose of providing a thorough understanding of the described techniques. However, it will be apparent to those skilled in the art that these techniques can be practiced without these specific details. In some instances, well-known structures and devices are shown in block diagram form in order to avoid obscuring the concepts of the described embodiments.

[0157] The above describes the optional implementation manners of the embodiments of the application in detail in combination with the drawings, but the embodiments of the application are not limited to the specific details in the above implementation manners, and various simple modifications can be made to the technical solutions of the embodiments of the application within the technical concept scope of the embodiments of the application, and these simple modifications all belong to the protection scope of the embodiments of the application.

[0158] The above description of the content of the present specification is provided so that any ordinary person skilled in the art can implement or use the content of the present specification. Various modifications to the content of the present specification are obvious to those skilled in the art, and the general principles defined herein can also be applied to other variants without departing from the protection scope of the content of the present specification. Therefore, the content of the present specification is not limited to the examples and designs described herein, but is consistent with the broadest scope that meets the principles and novel features disclosed herein.

Claims

1. A method for manufacturing a perovskite solar cell, characterized by, The manufacturing method comprises: forming a cathode on a transparent substrate; forming an electron transport layer on the cathode; forming a three-dimensional perovskite light absorption layer on the electron transport layer; forming a two-dimensional perovskite light absorption layer on the three-dimensional perovskite light absorption layer by using a vacuum coating method; wherein the material of the two-dimensional perovskite light absorption layer is (COOH(CH2)3NH3)2PbI4 or (COOH(CH2)7NH3)2PbI4; forming a hole transport layer on the two-dimensional perovskite light absorption layer; forming an anode on the hole transport layer to obtain the perovskite solar cell; wherein the method of forming the two-dimensional perovskite light absorption layer on the three-dimensional perovskite light absorption layer by using the vacuum coating method specifically comprises: blowing and cleaning the three-dimensional perovskite light absorption layer by introducing nitrogen; carrying out first evaporation at a first rate under a first current and a first temperature condition to seed two-dimensional perovskite seeds on the surface of the three-dimensional perovskite light absorption layer; carrying out second evaporation at a second rate under a second current and a second temperature condition to form the two-dimensional perovskite light absorption layer on the surface of the three-dimensional perovskite light absorption layer.

2. The method of manufacturing according to claim 1, wherein, The first current is 10A-11A, the first temperature is 140-150℃, and the first rate is The time of the first evaporation is 10-20s; the second current is 12A-15A, the second temperature is 165-210℃, and the second rate is The time of the second evaporation is 10-100s; the vacuum degree of the first evaporation and the second evaporation is less than 5x10 -4 Pa.

3. The production method according to claim 1 or 2, characterized by, The thickness of the two-dimensional perovskite seeds is 0.1nm-0.2nm; and the thickness of the two-dimensional perovskite light absorption layer is 1nm-10nm.

4. The method of making of claim 1, wherein, The method of forming the three-dimensional perovskite light absorption layer on the electron transport layer specifically comprises: spinning the prepared precursor solution of the three-dimensional perovskite light absorption layer on the surface of the electron transport layer away from the cathode by using a spin coating method with a rotation speed of 3500r / min, a rotation acceleration of 3000r / min and a rotation time of 15s-50s; annealing the spun precursor solution at an annealing temperature of 100℃-450℃ and an annealing time of 10min-30min to crystallize and form the three-dimensional perovskite light absorption layer with a thickness of 180nm-310nm; The material of the three-dimensional perovskite light absorption layer includes any one of MAPbI3, MAPbBr3, MAPbCl3, MAPbI 3-x Br x , MAPbI 3-x Cl x , MA y FA 1-y PbI3, MA y FA 1-y PbI 3-x Cl x , MA y FA 1-y PbI 3-x Br x , CsSnxPb1-xI3, CsPbI3, CsSnI3 and CsPbBr3.

5. The method of making of claim 1, wherein, The method of forming the cathode on the transparent substrate specifically comprises: uniformly applying a transparent conductive oxide material on the transparent substrate to form the cathode; wherein the transparent conductive oxide material is indium tin oxide.

6. The method of making of claim 1, wherein, The method of forming the electron transport layer on the cathode specifically comprises: spinning the prepared precursor solution of the electron transport layer on the surface of the cathode away from the transparent substrate; annealing at an annealing temperature of 100℃-450℃ and an annealing time of 10min-30min to crystallize and form the electron transport layer; The material of the electron transport layer includes TiO2, SnO2 and PC 61 Any of the BMs.

7. The method of making of claim 1, wherein, The method of forming the hole transport layer on the two-dimensional perovskite light absorption layer specifically comprises: spinning the prepared precursor solution of the hole transport layer on the surface of the two-dimensional perovskite light absorption layer away from the three-dimensional perovskite light absorption layer to form the hole transport layer; The material of the hole transport layer includes any one of Spiro-OMeTAD, PEDOT:PSS, NiO x and CuSCN.

8. The method of making of claim 1, wherein, The method of forming the anode on the hole transport layer specifically comprises: forming the anode on the surface of the hole transport layer away from the two-dimensional perovskite light absorption layer by using a vacuum evaporation instrument; The thickness of the anode is 100 nm, and the electrode material of the anode comprises any one of Ag, Au and Al. 9.A perovskite solar cell prepared by the manufacturing method of any one of claims 1-8.

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