Preparation method of large-area perovskite solar cell module

Abstract

The invention discloses a preparation method of a large-area perovskite solar cell module. The perovskite solar cell module structurally comprises a substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, an electron blocking layer and a back electrode in sequence from a light receiving surface to a backlight surface, the perovskite light absorption layer is prepared by adding an additive into a perovskite precursor solution, and the additive is iodoimidazole, bromo-imidazole or chloro-imidazole. According to the method, the compact and uniform perovskite thin film can be prepared in large-area preparation, and due to the special effect of the perovskite thin film and the perovskite precursor, the performance and stability of the prepared device are guaranteed.

Description

Technical Field

[0001] The invention belongs to the technical field of solar cells, and in particular relates to a method for preparing a large-area perovskite solar cell component. Background Art

[0002] Solution-processed halide perovskite semiconductors (hereinafter referred to as perovskites) are mainly used in the photovoltaic field. At present, the photovoltaic efficiency of single-junction perovskites exceeds 25%, and the 228 cm 2 The performance of large-area modules has reached 18% (Zhao et al., Science 385, 433–438 (2024)), showing its importance for sustainable development and application. Perovskite photovoltaic cell modules can embody the advantages of rapid production, high efficiency, and low cost. Usually, the precursor is dissolved in a solvent, and then printed and annealed to form a polycrystalline perovskite film. For large-scale production, the air tolerance of the perovskite film during the preparation process and the quality of the film after annealing need to meet the corresponding requirements.

[0003] The preparation of perovskite thin films needs to be carried out in an inert gas environment (such as nitrogen), which places high demands on the preparation conditions, that is, expensive nitrogen systems and equipment must be installed, and a certain amount of space is occupied. If the nitrogen environment is removed and the perovskite thin film is assembled in the air, the photoelectric conversion efficiency of the device will decrease and the stability will deteriorate due to the easy phase change of its water vapor. Therefore, the key to preparing perovskite solar cell modules in the air is how to reduce the impact of moisture on the perovskite thin film during the preparation process. Summary of the invention

[0004] In view of the problem that air affects the quality of perovskite film during the current solution method for preparing large-area perovskite film, the present invention provides a preparation method for a perovskite solar cell module that can avoid the influence of air and obtain a highly efficient and stable perovskite solar cell module.

[0005] To achieve the above object, the present invention adopts the following technical solutions: A perovskite solar cell module, wherein the structure of the perovskite solar cell module comprises, from the light-receiving side to the backlight side, a substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, an electron blocking layer, and a back electrode; the perovskite light-absorbing layer is prepared by adding an additive to a perovskite precursor solution, wherein the additive is iodine imidazole, bromine imidazole or chlorine imidazole.

[0006] Furthermore, the structural formula of the perovskite precursor is ABX3, where A can be a cesium ion (Cs + ), formamidinyl (FA + ) can be mixed in any proportion, or cesium ion, formamidinium group and methylamine group (MA + ) are mixed in any proportion; B is lead ion (Pb2+ ); X is an iodide ion (I - ), bromide ion (Br - ) can be mixed in any proportion.

[0007] A method for preparing a perovskite solar cell module comprises the following steps: Step 1, laser scribing P1 on the substrate; Step 2, depositing a hole transport layer on the substrate of step 1; Step 3, coating a perovskite precursor solution containing an additive on the surface of the hole transport layer to prepare a perovskite light absorbing layer; Step 4, depositing an electron transport layer on the surface of the perovskite light absorbing layer; Step 5, depositing an electron blocking layer on the surface of the electron transport layer; Step 6, laser scribing P2 on the electron blocking layer; Step 7, preparing a back electrode on the surface of the electron blocking layer; Step 8, laser scribing P3 on the back electrode; The additive is iodine imidazole, bromide imidazole or chloride imidazole.

[0008] Furthermore, in the perovskite precursor solution, the concentration of the perovskite precursor is 0.4-1.6 mmol / mL, the concentration of the additive is 0.01-0.1 mmol / mL, and the concentration of the additive is preferably 0.05 mmol / mL.

[0009] Furthermore, the structural formula of the perovskite precursor is ABX3, where A can be a cesium ion (Cs + ), formamidinyl (FA + ) can be mixed in any proportion, or cesium ion, formamidinium group and methylamine group (MA + ) are mixed in any proportion; B is lead ion (Pb 2+ ); X is an iodide ion (I - ), bromide ion (Br - ) can be mixed in any proportion.

[0010] In the present invention, the solvent for dissolving the perovskite precursor is any one or more of dimethyl sulfoxide (DMSO), 2-methoxyethanol (2-ME), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) and acetonitrile (ACN).

[0011] In the present invention, the perovskite light absorbing layer is prepared by one of the two methods of scraping or slit coating, and the perovskite precursor solution is evenly spread on the surface of the hole transport layer prepared on the substrate by a scraper, the solvent is volatilized, and then annealing is performed to form a perovskite polycrystalline film.

[0012] In the present invention, when the perovskite light absorbing layer is prepared by blade coating or slit coating, a preparation method with nitrogen blowing assistance or vacuum drying should be used to accelerate the volatilization of the solvent and the film formation of the perovskite. The pressure of the nitrogen blowing can be 0.2-0.6 MPa.

[0013] In the present invention, after the perovskite precursor film is prepared on the substrate using the above method, it should be transferred to an environment of 100-150°C for heat treatment for 10-20 minutes to remove the residual solvent and assist the nucleation and growth of perovskite crystals to form a dense and uniform perovskite polycrystalline film. Too high or too low a heat treatment temperature and too long or too short a heat treatment time will have an adverse effect on device performance. Preferably, the heat treatment temperature is 120°C and the time is 15 minutes.

[0014] In the present invention, the substrate may be FTO, ITO or other transparent conductive glass substrates.

[0015] Compared with the existing perovskite preparation technology, the preparation process of the present invention has the following advantages: (1) The present invention avoids the dependence on nitrogen environment in the traditional preparation process, ensuring the feasibility of large-scale preparation and industrial application of perovskite films.

[0016] (2) The preparation process developed by the present invention is a universal process, that is, by adjusting the amount of imidazole halogen added, it is applicable to perovskite precursors with different band gaps, which further highlights the prospect of the application of this preparation process.

[0017] (3) The preparation process of the present invention can produce dense and uniform perovskite films in large-area preparation, and due to its special effect with the perovskite precursor, the performance and stability of the prepared device are guaranteed. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic structural diagram of the inverted perovskite solar cell module of the present invention.

[0019] Figure 2 This is a scanning electron microscope image of the perovskite film prepared in Example 3.

[0020] Figure 3 This is the X-ray diffraction pattern of the perovskite film prepared in Example 3.

[0021] Figure 4 The 30*40 cm 2 Current-voltage curve of a perovskite device. DETAILED DESCRIPTION

[0022] The preferred embodiments of the present invention will be described in detail below in conjunction with examples. It should be understood that the following examples are provided only for the purpose of illustration and are not intended to limit the scope of the present invention. Those skilled in the art may make various modifications and substitutions to the present invention without departing from the purpose and spirit of the present invention.

[0023] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0024] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources. Example

[0025] In this embodiment, an inverse perovskite solar cell module with a band gap of 1.55 eV is prepared, and the specific preparation process is as follows: 1. In 10*10 cm 2 P1 was prepared by laser scribing on an ITO glass substrate. The glass substrate was wiped with a dust-free cloth dipped in pure water, and then the substrate was ultrasonically treated in isopropanol for 30 minutes. The ITO after ultrasonication was blown dry with nitrogen, and then treated with UV ozone for 10 minutes.

[0026] 2. A hole transport layer is deposited on the UV-ozone treated substrate, where nickel oxide is used.

[0027] 3. Weigh the perovskite precursor powder and dissolve it in a mixed solvent of DMF:DMSO=8:2 (v:v) to prepare a precursor component of FA 0.95 Cs 0.05 The perovskite precursor solution of PbI3 has a perovskite concentration of 1.2 mol / L, and iodine imidazole (C3H3IN2) is additionally added as an additive with an additive concentration of 0.05 mmol / mL; the perovskite light-absorbing layer is prepared by a scraping method in air, and nitrogen blowing assists solvent volatilization and perovskite crystallization. The scraping speed is 25 mm / s, and the blowing pressure is 0.5 MPa. The film is then heated at 120°C for 15 minutes. The thickness of the prepared perovskite film is about 800 nm.

[0028] 4. A layer of electron transport layer is deposited by vacuum method, where C60 is used with a thickness of about 26nm.

[0029] 5. Deposit a layer of SnO2 using atomic layer deposition with a thickness of about 12nm.

[0030] 6. Preparation of P2 using laser scribing.

[0031] 7. Use thermal evaporation to deposit a 150nm thick Cu layer as the back electrode.

[0032] 8. Preparation of P3 using laser scribing.

[0033] 9. Finally, package and test in air. Example

[0034] In this embodiment, an inverse perovskite solar cell module with a band gap of 1.55 eV is prepared, and the specific preparation process is as follows: 1. 30*40 cm 2 P1 was prepared by laser scribing on an ITO glass substrate. The glass substrate was wiped with a dust-free cloth dipped in pure water, and then the substrate was ultrasonically treated in isopropanol for 30 minutes. The ITO after ultrasonication was blown dry with nitrogen, and then treated with UV ozone for 10 minutes.

[0035] 2. A hole transport layer is deposited on the UV-ozone treated substrate, where nickel oxide is used.

[0036] 3. Weigh the perovskite precursor powder and dissolve it in a mixed solvent of DMF:2-ME:DMSO=1:1:0.3 (v:v:v) to prepare a precursor component of FA 0.95 Cs 0.05 The perovskite precursor solution of PbI3 has a perovskite concentration of 0.6 mol / L, and chloroimidazole (C3H3ClN2) is added as an additive with an additive concentration of 0.05 mmol / mL; the perovskite light-absorbing layer is prepared by a slit coating method in air, and vacuum drying is used to assist solvent evaporation and perovskite crystallization. The coating speed is 25 mm / s, and then the film is heated at 120°C for 15 minutes. The thickness of the prepared perovskite film is about 350 nm.

[0037] 4. Deposit an electron transport layer using a vacuum method, where C 60 , with a thickness of about 26nm.

[0038] 5. A layer of SnO2 is deposited by atomic layer deposition with a thickness of about 12 nm.

[0039] 6. Prepare P2 using laser scribing.

[0040] 7. Use thermal evaporation to deposit a 150nm thick Cu layer as the back electrode.

[0041] 8. Preparation of P3 using laser scribing.

[0042] 9. Finally, package and test in air. Example

[0043] In this embodiment, an inverse perovskite solar cell module with a band gap of 1.55 eV is prepared, and the specific preparation process is as follows: 1. 30*40 cm 2 P1 was prepared by laser scribing on an ITO glass substrate. The glass substrate was wiped with a dust-free cloth dipped in pure water, and then the substrate was ultrasonically treated in isopropanol for 30 minutes. The ITO after ultrasonication was blown dry with nitrogen, and then treated with UV ozone for 10 minutes.

[0044] 2. A hole transport layer is deposited on the UV-ozone treated substrate, where nickel oxide is used.

[0045] 3. Weigh the perovskite precursor powder and dissolve it in a mixed solvent of DMF:2-ME:DMSO=1:1:0.3 (v:v:v) to prepare a precursor component of FA 0.95 Cs 0.05 The perovskite precursor solution of PbI3 has a perovskite concentration of 0.6 mol / L, and iodine imidazole (C3H3IN2) is added as an additive with an additive concentration of 0.05 mmol / mL; the perovskite light-absorbing layer is prepared by a slit coating method in air, and vacuum drying is used to assist solvent evaporation and perovskite crystallization. The coating speed is 25 mm / s, and then the film is heated at 120°C for 15 minutes. The thickness of the prepared perovskite film is about 350 nm.

[0046] 4. Deposit an electron transport layer using a vacuum method, where C 60 , with a thickness of about 26nm.

[0047] 5. A layer of SnO2 is deposited by atomic layer deposition with a thickness of about 12 nm.

[0048] 6. Prepare P2 using laser scribing.

[0049] 7. Use thermal evaporation to deposit a 150nm thick Cu layer as the back electrode.

[0050] 8. Preparation of P3 using laser scribing.

[0051] 9. Finally, package and test in air.

[0052] According to the above embodiments, the present invention prepares Figure 1 The trans-structured perovskite solar cell module shown in FIG. 3 is taken as an example. Figure 2 It can be seen from the scanning electron microscope image that a uniform and dense perovskite film can be prepared in air using the method of the present invention; Figure 3 It can be seen from the X-ray diffraction pattern that the perovskite prepared by the method of the present invention has excellent crystal orientation; Figure 4It can be seen from the current-voltage curve that the perovskite solar cell module prepared by the method of the present invention can achieve an efficiency of 21%, reflecting excellent performance.

Claims

1. A perovskite solar cell module, characterized in that: The structure of the perovskite solar cell module is a substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, an electron blocking layer, and a back electrode from the light-receiving side to the backlight side; the perovskite light-absorbing layer is prepared by adding an additive to a perovskite precursor solution, and the additive is iodine imidazole, bromine imidazole or chlorine imidazole.

2. The perovskite solar cell assembly according to claim 1, characterized in that: The structural formula of the perovskite precursor is ABX3, where A is a cesium ion Cs + , formamidinyl FA + Any mixture of the two, or cesium ion Cs + , formamidinyl FA + and methylamino MA + Mix the three in any proportion; B is lead ion Pb 2+ ; X is iodide ion I - 、Br - Mix the two in any ratio.

3. The method for preparing a perovskite solar cell module according to claim 1, characterized in that: The following steps are involved: Step 1, laser scribing P1 on the substrate; Step 2, depositing a hole transport layer on the substrate of step 1; Step 3, coating a perovskite precursor solution containing an additive on the surface of the hole transport layer to prepare a perovskite light absorbing layer; Step 4, depositing an electron transport layer on the surface of the perovskite light absorbing layer; Step 5, depositing an electron blocking layer on the surface of the electron transport layer; Step 6, laser scribing P2 on the electron blocking layer; Step 7, preparing a back electrode on the surface of the electron blocking layer; Step 8, laser scribing P3 on the back electrode; The additive is iodine imidazole, bromide imidazole or chloride imidazole.

4. The preparation method according to claim 3, characterized in that In the perovskite precursor solution, the concentration of the perovskite precursor is 0.4-1.6 mmol / mL, and the concentration of the additive is 0.001-0.1 mmol / mL.

5. The preparation method according to claim 3, characterized in that: The solvent of the perovskite precursor solution is any one or more of dimethyl sulfoxide, 2-methoxyethanol, N,N-dimethylformamide, N-methylpyrrolidone and acetonitrile.

6. The preparation method according to claim 3, characterized in that: In step 3, the perovskite light absorbing layer is prepared by blade coating or slit coating.

7. The preparation method according to claim 6, characterized in that: When using blade coating or slit coating to prepare the perovskite light-absorbing layer, a nitrogen gas blowing-assisted or vacuum drying preparation method is used to accelerate the volatilization of the solvent and the film formation of the perovskite.

8. The preparation method according to claim 6, characterized in that: After the perovskite precursor film is prepared by blade coating or slit coating, it is transferred to an environment of 100-150°C for heat treatment for 10-20 minutes.

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