Application of a multi-active site hydrazine molecule in inverted perovskite solar cells

Abstract

The application relates to application of a multi-active-site hydrazine molecule in an inverted perovskite solar cell and belongs to the technical field of perovskite solar cells. The multi-active-site hydrazine molecule is introduced into a perovskite precursor solution, chemical forces such as coordination bonds and hydrogen bonds are utilized to interact with the perovskite, the crystallization of the perovskite is regulated, multiple types of defects in the perovskite grain boundary are effectively passivated, residual stress in the grain boundary is released, ion migration in the perovskite film is inhibited, the defect density of the perovskite film is reduced, the stability of the perovskite film is improved, the efficiency and stability of the inverted perovskite solar cell are simultaneously improved, the inverted perovskite solar cell prepared by the application and modified by the multi-active-site hydrazine molecule can realize a power conversion efficiency of 26.96%, and 90.0% of the initial efficiency is still retained after the inverted perovskite solar cell continuously works at a maximum power point for 1000 hours. The application has simple process, good reproducibility and good universality, and lays a solid foundation for industrialized production of the inverted perovskite solar cell.

Description

Technical Field

[0001] This invention relates to the application of a multi-active-site hydrazide molecule in an inverted perovskite solar cell, belonging to the field of perovskite solar cell technology. Background Technology

[0002] In recent years, inverted perovskite solar cells (PSCs) have attracted widespread attention in the photovoltaic field due to their advantages such as low-temperature fabrication, simple process, low hysteresis, high stability, and good compatibility with tandem cells. However, the perovskite light-absorbing layer suffers from key problems such as high defect density, poor crystallinity, and easy ion migration, making it difficult to simultaneously improve the efficiency and stability of inverted perovskite solar cells.

[0003] To address these challenges, researchers have developed various strategies, primarily including solvent engineering, dimensional engineering, and additive engineering. Among these, additive engineering is an effective means of controlling the crystallization behavior of perovskite thin films, improving film morphology, reducing defect density, and enhancing device performance. Traditional additives, such as organic ammonium salts, ionic liquids, and Lewis acids / bases, can reduce defect density or inhibit ion migration to some extent, but their functions are often relatively singular. They are difficult to simultaneously passivate different types of defects at the perovskite surface and grain boundaries, resulting in limited control effects. Furthermore, while improving efficiency, they often come at the cost of sacrificing the long-term stability of the device.

[0004] Therefore, developing a multifunctional control strategy that can simultaneously passivate multiple types of defects, suppress ion migration, and improve humidity stability in order to achieve a simultaneous improvement in the efficiency and stability of inverted perovskite solar cells has become a pressing technical challenge in this field. Summary of the Invention

[0005] To address the problem that it is difficult to simultaneously improve the efficiency and stability of inverted perovskite solar cells in existing technologies, the present invention aims to provide an application of multi-active-site acylhydrazine molecules in inverted perovskite solar cells, using multi-active-site acylhydrazine molecules as additives in inverted perovskite precursor solutions.

[0006] Preferably, the multi-active-site acylhydrazide molecule of the present invention is one of P1 to P8; wherein the specific structural formulas of P1 to P8 are as follows: .

[0007] Preferably, the amount of the multi-active-site hydrazide molecule of the present invention added to the inverted perovskite precursor solution is 0.1 mg / mL to 0.5 mg / mL.

[0008] Preferably, the inverted perovskite solar cell of the present invention is composed of, from bottom to top, a conductive substrate layer, a hole transport layer, a perovskite light-absorbing layer modified with multi-active-site hydrazide molecules, an electron transport layer, a hole blocking layer, and a metal back electrode layer.

[0009] Preferably, the method for preparing the perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecules of the present invention is as follows: an inverted perovskite precursor solution containing multi-active-site acylhydrazine molecules is spin-coated onto the hole transport layer using an antisolvent method or a vacuum flash evaporation method, followed by annealing.

[0010] Preferably, the steps of the antisolvent method of the present invention are as follows: first spin coating at a speed of 1000 rpm to 3000 rpm for 5 s to 60 s, then spin coating at a speed of 2000 rpm to 5000 rpm for 10 s to 60 s, and then adding antisolvent dropwise at the 5th to 20th s.

[0011] Preferably, the antisolvent of the present invention is any one or more of diethyl ether, chlorobenzene, toluene, dichloromethane or chloroform.

[0012] Preferably, the steps of the vacuum flash evaporation method of the present invention are as follows: first spin coating at a speed of 1000 rpm to 3000 rpm for 5 s to 10 s, then spin coating at a speed of 3000 rpm to 6000 rpm for 30 s to 60 s, and then placing it in a vacuum chamber with a vacuum degree of 10 Pa to 20 Pa for 5 s to 30 s.

[0013] Preferably, the annealing conditions of the present invention are: annealing temperature of 100 ℃~150 ℃ and annealing time of 10 min~60 min.

[0014] The inverted perovskite solar cell of the present invention has a conventional structure, wherein the conductive substrate layer is ITO or FTO.

[0015] The hole transport layer of this invention is composed of poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and nickel oxide (NiO). xThe material of the self-assembled molecular layer is any one or more of the following: [4-3,6-(dimethyl-9H-carbazole-9-yl)butyl]phosphoric acid (Me-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (4PADCB), 4-(diphenylamino)phenyl)phosphonic acid (PATPA), [4-(5,9-dimethoxy-7H-dibenzocarbazole-7-yl)butyl]phosphoric acid (MeO-4PADBC), [4-(3,6-diphenyl-9H-carbazole-9-yl)butyl]phosphoric acid (Ph-4PACz), and [4-(diphenylamino)phenyl]phosphonic acid (4PABCz).

[0016] The perovskite light-absorbing layer of this invention is made of ABX3 type perovskite crystal material, wherein A is CH3NH3. + CH(NH2)2 + Cs + or Rb + Any one or more of the following, where B is Pb 2+ or Sn 2+ Any one or more of them, X is Cl - ,Br - Or I - Any one or more of the following.

[0017] The electron transport layer of this invention is made of methyl [6,6]-phenyl-C61-butyrate (PC). 61 BM), fullerene (C 60 ), SnO2, BaSnO3, TiO2 or ZnO.

[0018] The hole blocking layer of the present invention is made of any one or more of dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), zirconium acetylacetonate, or lithium fluoride.

[0019] The metal back electrode layer of the present invention is any one or more of Cu, Ag, or low-temperature carbon electrode.

[0020] The fabrication process of the inverted perovskite solar cell described in this invention is a conventional process, specifically including the following steps: (1) The conductive substrate is pretreated to obtain a conductive substrate layer; (2) The hole transport layer is prepared by spin-coating a solution containing the hole transport layer material onto the conductive substrate layer described in step (1) and then annealing. The hole transport layer material is poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], or nickel oxide (NiO). x ), self-assembled molecules; When the hole transport layer is NiO x When layering, the preparation process is as follows: NiO x NiO was obtained by dispersing nanoparticles in deionized water. x Nanoparticle dispersion, containing NiO x The nanoparticle dispersion was spin-coated onto the conductive substrate layer described in step (1) and then annealed to obtain a hole transport layer; When the hole transport layer is one or more of poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], or a self-assembled molecule, the solution of the hole transport layer material is spin-coated onto the NiO. x On the thin film, a hole transport layer is obtained after annealing. When the hole transport layer is NiO x When NiO is combined with one or more of the following: poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], or self-assembled molecules, the preparation process is as follows: first, NiO... x NiO was obtained by dispersing nanoparticles in deionized water. x Nanoparticle dispersion, containing NiO x The nanoparticle dispersion was spin-coated onto the conductive substrate layer described in step (1) and then annealed to obtain NiO. x Layer; subsequently, a solution of other hole transport layer materials is spin-coated onto the NiO. x On the top layer, after annealing, a hole transport layer is obtained; (3) Spin-coat the inverted perovskite precursor solution containing multi-active-site acylhydrazine molecules onto the hole transport layer described in step (2). During the spin-coating process, use the anti-solvent method or the vacuum flash evaporation method. After annealing, the perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecules can be prepared. (4) Spin-coat the solution containing the electron transport layer material onto the perovskite light-absorbing layer modified with the multi-active-site acylhydrazine molecule described in step (3) to prepare the electron transport layer; (5) Spin-coat the solution containing the hole blocking layer material onto the electron transport layer described in step (4) to obtain the hole blocking layer; (6) Deposit metal on the hole blocking layer described in step (5) to form a metal back electrode layer. After the deposition is completed, an inverted perovskite solar cell device is obtained.

[0021] Preferably, the pretreatment step in step (1) of the present invention is as follows: the conductive substrate is ultrasonically cleaned sequentially with detergent, deionized water and anhydrous ethanol, then dried with nitrogen, and treated with ultraviolet ozone for 10 min to 30 min.

[0022] Preferably, in step (2) of the present invention, when the hole transport layer is NiO x When layering, the preparation process is as follows: NiO x Nanoparticles were dispersed in deionized water to obtain NiO with concentrations ranging from 5 mg / mL to 35 mg / mL. x The nanoparticle dispersion was filtered using a polyvinylidene fluoride (PVDF) filter, and then the dispersion was dropped onto the conductive substrate layer in step (1). The substrate was spin-coated at a speed of 2000 rpm to 6000 rpm for 10 s to 60 s, and then annealed at 100 ℃ to 200 ℃ for 5 min to 30 min to obtain the hole transport layer.

[0023] Preferably, in step (2) of the present invention, when the hole transport layer is one or more of poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], or a self-assembled molecule, the preparation process is as follows: 0.1 mg / mL to 10 mg / mL of other hole transport layer materials are dissolved in an organic solvent, and the mixture is stirred at a rotation speed of 2000 rpm to 6000 rpm in the NiO x Spin-coating the layer for 10 to 60 seconds, followed by annealing at 60 to 120 °C for 5 to 20 minutes, yields the hole transport layer.

[0024] Preferably, in step (2) of the present invention, when the hole transport layer is NiO x When NiO is combined with one or more of the following: poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], or self-assembled molecules, the preparation process is as follows: first, NiO... x Nanoparticles were dispersed in deionized water to obtain NiO with concentrations ranging from 5 mg / mL to 35 mg / mL. x The nanoparticle dispersion was filtered using a polyvinylidene fluoride (PVDF) filter, and then the dispersion was dropwise added to the conductive substrate layer in step (1). The substrate was spin-coated at 2000 rpm to 6000 rpm for 10 to 60 seconds, and then annealed at 100 °C to 200 °C for 5 to 30 minutes. Subsequently, 0.1 mg / mL to 10 mg / mL of other hole transport layer materials were dissolved in an organic solvent and coated onto the NiO substrate at 2000 rpm to 6000 rpm.x Spin-coating the layer for 10 to 60 seconds, followed by annealing at 60 to 120 °C for 5 to 20 minutes, yields the hole transport layer.

[0025] As a further preferred embodiment of the present invention, the organic solvent is any one or more of ethanol, isopropanol or methanol.

[0026] As a preferred embodiment, the electron transport layer in step (4) of the present invention is prepared by: adding a solution containing electron transport layer material with a concentration of 1 mg / mL to 30 mg / mL to the perovskite light-absorbing layer modified with multi-active site acylhydrazine molecules in step (3) and spin-coating at a speed of 2000 rpm to 6000 rpm for 20 s to 60 s.

[0027] As a preferred embodiment, the hole blocking layer in step (5) of the present invention is prepared by: adding a solution containing hole blocking layer material with a concentration of 0.5 mg / mL to 10 mg / mL to the electron transport layer described in step (4) and spin-coating it at a speed of 2000 rpm to 6000 rpm for 20 s to 60 s.

[0028] Preferably, the metal back electrode layer in step (6) of the present invention is prepared by evaporating the metal back electrode layer material onto the hole blocking layer described in step (5) at an evaporation rate of 0.1~1 Å / s to prepare an inverted perovskite solar cell device.

[0029] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention provides a perovskite light-absorbing layer based on multi-active-site acylhydrazine molecule modification. By adding multi-active-site acylhydrazine molecules to the inverted perovskite precursor solution, the functional groups of the multi-active-site acylhydrazine molecules interact with the defect sites in the perovskite film, thereby reducing the surface defect density of the perovskite film, suppressing non-radiative recombination, and thus increasing the open-circuit voltage of the inverted perovskite solar cell device. V OC The effects of ) and fill factor (FF).

[0030] (2) This invention improves the power conversion efficiency of inverted perovskite solar cells with different band gaps modified by multi-active-site acylhydrazine molecules by using vacuum flash evaporation or anti-solvent method. Among them, the inverted perovskite solar cell with a band gap of 1.53 eV modified by multi-active-site acylhydrazine molecules prepared by vacuum flash evaporation achieves a power conversion efficiency (PCE) of 26.96%; the inverted perovskite solar cell with a band gap of 1.68 eV prepared by anti-solvent method achieves a PCE of 24.02%; and the inverted perovskite solar cell with a band gap of 1.78 eV prepared by anti-solvent method achieves a PCE of 20.27%.

[0031] (3) The inverted perovskite solar cell based on the multi-active-site acylhydrazine molecule modification of the present invention also has the effect of high long-term operation stability; the 1.53 eV bandgap inverted perovskite solar cell based on the multi-active-site acylhydrazine molecule modification still retains 90.1% of the initial efficiency after working continuously at the maximum power point for 1000 h, compared with the control device which decayed to 78.2% of the initial efficiency after only 700 h, the operating stability of the device is significantly improved.

[0032] (4) The process of this invention is simple, reproducible and universal, and it is of great significance in promoting the commercial application of inverted perovskite solar cells. Attached Figure Description

[0033] Figure 1 In Example 1, a is the differential charge density diagram of the interaction between P1 and the perovskite containing lead-iodine antisite defects; b is the differential charge density diagram of the interaction between P1 and the perovskite containing formamidinium vacancy defects; c is the differential charge density diagram of the interaction between P1 and the perovskite containing iodine vacancy defects; d is the differential charge density diagram of the interaction between P1 and the perovskite containing lead interstitial defects; e is the differential charge density diagram of the interaction between P1 and the perovskite containing iodine interstitial defects; and f is the differential charge density diagram of the interaction between P1 and the perovskite containing lead-formamidinium antisite defects. Figure 2 In Example 1, a represents the Fourier transform infrared (FTIR) spectra of P1 and P1 + FAI; b represents the FTIR spectra of P1 and P1 + PbI2. Figure 3 The diagram shows the energy level arrangement of the devices in Comparative Example 1 (Control) and Example 1 (P1); Figure 4 In Figure a, the space charge-limited current diagram (SCLC) of the purely electronic device in Comparative Example 1 is shown; in Figure b, the space charge-limited current diagram (SCLC) of the purely electronic device in Example 1 is shown. Figure 5In Figure a, dynamic light scattering (DLS) diagram of the perovskite precursor solution in Comparative Example 1 is shown; in Figure b, dynamic light scattering (DLS) diagram of the perovskite precursor solution in Example 1 is shown. Figure 6 In Figure a, SEM image of the perovskite film surface in the comparative example is shown; in Figure b, SEM image of the perovskite film surface in Example 1 is shown. Figure 7 In Figure a, SEM image of the cross-section of the device in Comparative Example 1 is shown; in Figure b, SEM image of the cross-section of the device in Example 1 is shown. Figure 8 In Figure a, GIXRD pattern of the perovskite film surface in Comparative Example 1 is shown; in Figure b, GIXRD pattern of the perovskite film surface in Example 1 is shown. Figure 9 In Figure a, the perovskite film in Comparative Example 1 (Control) and Example 1 (P1) is a PL diagram; in Figure b, the perovskite film in Comparative Example 1 (Control) and Example 1 (P1) is a TRPL diagram. Figure 10 Linear graphs showing the stability of 1.53 eV bandgap inverted perovskite solar cells prepared by antisolvent method in Comparative Example 1 (Control) and Example 1 (P1) under dark conditions and at room temperature with a relative humidity of 20-30%. Figure 11 Linear graphs showing the operational stability of 1.53 eV bandgap inverted perovskite solar cells prepared by antisolvent method in Comparative Example 1 (Control) and Example 1 (P1) at maximum power point tracking. Figure 12 The reverse scanning current density-voltage curves are for the 1.53 eV bandgap inverted perovskite solar cells prepared by the anti-solvent method in Comparative Example 1 (Control) and Example 1 (P1). Figure 13 The reverse scanning current density-voltage curves are for 1.53 eV bandgap inverted perovskite solar cells prepared by the antisolvent method in Comparative Example 1 (Control) and Example 2 (P2). Figure 14 The reverse scanning current density-voltage curves are for 1.53 eV bandgap inverted perovskite solar cells prepared by the antisolvent method in Comparative Example 1 (Control) and Example 3 (P3). Figure 15 Reverse scanning current density-voltage curves for 1.53 eV bandgap inverted perovskite solar cells prepared by vacuum flash evaporation for Comparative Example 2 (Control) and Example 4 (P1); Figure 16Reverse scanning current density-voltage curves for 1.53 eV bandgap inverted perovskite solar cells prepared by vacuum flash evaporation for Comparative Example 2 (Control) and Example 5 (P2); Figure 17 Reverse scanning current density-voltage curves for 1.53 eV bandgap inverted perovskite solar cells prepared by vacuum flash evaporation in Comparative Example 2 (Control) and Example 6 (P3); Figure 18 Reverse scanning current density-voltage curves for 1.68 eV bandgap inverted perovskite solar cells prepared by antisolvent method in Comparative Example 3 (Control) and Example 7 (P1); Figure 19 Reverse scanning current density-voltage curves for 1.78 eV bandgap inverted perovskite solar cells prepared by the antisolvent method in Comparative Example 4 (Control) and Example 8 (P1). Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] Example 1 A 1.53 eV bandgap inverted perovskite solar cell modified with P1, a multi-active-site acylhydrazine molecule, was prepared using an anti-solvent method. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The ITO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, and then dried with nitrogen gas. After that, the cleaned ITO conductive substrate was treated with ultraviolet ozone for 15 min to obtain a conductive substrate layer for later use.

[0036] (2) Take 30 mg of NiO x Nanoparticles were dispersed in 1 mL of deionized water, ultrasonically vibrated for 10 min, and then filtered through PVDF to obtain NiO. x Nanoparticle dispersion; take 60 μL of NiO x The nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2 NiO was prepared by spin-coating an ITO conductive substrate at 5000 rpm for 30 s, followed by annealing at 150 °C for 10 min. x layer.

[0037] (3) Dissolve 0.15 mg Me-4PACz and 0.15 mg MeO-2PACz in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a mixed solution of self-assembled molecules; next, take 50 μL of the mixed solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin coating at 5000 rpm for 30 s on the layer and then annealing at 100 °C for 10 min.

[0038] (4) Dissolve 19.49 mg CsI, 245.06 mg FAI and 691.5 mg PbI2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.5 mol / L Cs was prepared. 0.05 FA 0.95 PbI3 perovskite precursor solution; 0.5 mg of multi-active-site hydrazide molecule P1 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site hydrazide molecule P1 was dropped onto the self-assembled molecular layer described in step (3); then stepwise spin coating was performed, the first step was spin-coated at 2000 rpm for 10 s, the second step was spin-coated at 4000 rpm for 40 s; at the 5th s, 150 μL of chlorobenzene was dropped, and the perovskite wet film was annealed at 100 ℃ for 20 min to prepare a perovskite light-absorbing layer modified with multi-active-site hydrazide molecule P1; (5) Take 23 mg PC 61 BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer modified with the multi-active site acylhydrazine molecule P1 described in step (4), and spin-coated at a speed of 2500 rpm for 40 s to obtain the electron transport layer. (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer. (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0039] Example 1: A conductive substrate layer (ITO thin film) and a hole transport layer (NiO) were prepared by the above steps, consisting of, from bottom to top, a conductive substrate layer (ITO thin film) and a hole transport layer (NiO). x Thin film, Me-4PACz thin film, MeO-2PACz thin film), perovskite light-absorbing layer (perovskite thin film modified with multi-active-site acylhydrazine molecule P1), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0040] Performance tests were conducted on Example 1, and the results were compared with those of Comparative Example 1. The results are as follows: according to Figure 1 It can be seen that P1 has a strong interaction with these six defects in the perovskite film, which can passivate various defects in the perovskite and effectively reduce the defect density of the perovskite film.

[0041] according to Figure 2 It can be seen that the NH peak in P1 + FAI broadens, and the stretching vibration peak changes from 3452.3 cm⁻¹. -1 Moved to 3395.5 cm -1 This proves that an NH···I hydrogen bond is formed between P1 and FAI; simultaneously, with P1 (1702.1 cm -1 Compared to P1 + PbI2, the C=O stretching vibration peak in P1 + PbI2 shifts to a higher wavenumber (1704.7 cm⁻¹). -1 This indicates that C=O can interact with Pb. 2+ Coordination occurs, thereby enhancing the interaction between P1 and perovskite.

[0042] according to Figure 3 As can be seen, compared with Comparative Example 1, after modification with P1 in Example 1, the Fermi level of the perovskite film shifts upward, which reduces the carrier transport barrier between the perovskite and the electron transport layer, thus facilitating electron extraction and transfer.

[0043] according to Figure 4 It can be seen that the electron trap density of Example 1 is 4.7 × 10⁻⁶ compared to Comparative Example 1. 15 cm -3 Reduced to 3.7 × 10 15 cm -3 This indicates that the introduction of P1 can effectively passivate defects, thereby reducing nonradiative recombination.

[0044] according to Figure 5As can be seen, compared with Comparative Example 1, the perovskite precursor solution modified by P1 in Example 1 showed large colloidal particles with a particle size of nearly 1000 nanometers. This phenomenon may be due to the interaction between P1 and the precursor components, thereby promoting the formation and growth of prenuclear clusters.

[0045] according to Figure 6 As can be seen, compared with Comparative Example 1, the perovskite film modified by P1 in Example 1 exhibits a larger average grain size and a more uniform distribution.

[0046] according to Figure 7 As can be seen, compared with Comparative Example 1, after modification with P1 in Example 1, the grain orientation is more perpendicular to the substrate, the grain distribution is more uniform and the structure is more compact. This regular orientation and compact grain structure helps to promote the vertical transport of charge, thereby improving the device performance.

[0047] according to Figure 8 It can be seen that, compared with Comparative Example 1, the residual strain of the perovskite film modified by P1 in Example 1 is reduced, which is due to the reduction of bulk defects, the promotion of perovskite crystallization and the improvement of perovskite film morphology.

[0048] according to Figure 9 As can be seen, compared with Comparative Example 1, the perovskite light-absorbing layer modified with P1 in Example 1 has a stronger PL intensity and a longer carrier lifetime. This is because P1 has multiple active sites, which can effectively passivate defects in the perovskite film and suppress nonradiative recombination.

[0049] according to Figure 10 It can be seen that after 2500 h of humidity aging, the device modified by P1 in Example 1 still retains 90.0% of the initial efficiency, while the device in Comparative Example 1 only retains 76.2% of the original efficiency.

[0050] according to Figure 11 It can be seen that after 1027 h of photothermal aging, the device modified by P1 in Example 1 maintained 90.1% of its initial PCE, while the device in Comparative Example 1 decayed to 78.2% of its initial efficiency after only 700 h. This indicates that the device modified by P1 has higher operating stability.

[0051] according to Figure 12 It can be seen that, compared with Comparative Example 1, the photovoltaic performance of the device modified by P1 in Example 1 is improved. The modified inverted perovskite solar cell achieves a PCE of 26.17%, of which the short-circuit current density ( J SC The value was 26.69 mA / cm². 2 Open circuit voltage ( VOC The voltage is 1.166 V and the fill factor (FF) is 84.13%.

[0052] Comparative Example 1 A 1.53 eV bandgap inverted perovskite solar cell was prepared using the antisolvent method. Comparative Example 1 was identical to Example 1 except that the multi-active-site hydrazide molecule P1 was not added to the perovskite precursor solution. The specific preparation steps are as follows: (1) The ITO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, and then dried with nitrogen gas. After that, the cleaned ITO conductive substrate was treated with ultraviolet ozone for 15 min to obtain a conductive substrate layer for later use.

[0053] (2) Take 30 mg of NiO x Nanoparticles were dispersed in 1 mL of deionized water, ultrasonically vibrated for 10 min, and then filtered through PVDF to obtain NiO. x Nanoparticle dispersion; take 60 μL of NiO x The nanoparticle dispersion was dropwise added to the ITO conductive substrate layer described in step (1), and spin-coated at 5000 rpm for 30 s, followed by annealing at 150 ℃ for 10 min to obtain NiO. x layer.

[0054] (3) Dissolve 0.15 mg Me-4PACz and 0.15 mg MeO-2PACz in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a mixed solution of self-assembled molecules; next, take 50 μL of the mixed solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin coating at 5000 rpm for 30 s on the layer and then annealing at 100 °C for 10 min.

[0055] (4) Dissolve 19.49 mg CsI, 245.06 mg FAI and 691.5 mg PbI2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.5 mol / L Cs was prepared. 0.05 FA 0.95PbI3 perovskite precursor solution; 55 μL of perovskite precursor solution was dropped onto the self-assembled molecular layer described in step (3); then stepwise spin coating was performed, firstly at a speed of 2000 rpm for 10 s, and secondly at a speed of 4000 rpm for 40 s; 150 μL of chlorobenzene was dropped at the 5th s, and the perovskite wet film was annealed at 100 ℃ for 30 min to obtain the perovskite light-absorbing layer; (5) Take 23 mg PC 61 BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer described in step (4), and the layer was spin-coated at 2500 rpm for 40 s to obtain the electron transport layer. (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer. (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0056] Comparative Example 1 prepared a film consisting of a conductive substrate layer (ITO thin film) and a hole transport layer (NiO) from bottom to top using the above steps. x Thin film, Me-4PACz thin film, MeO-2PACz thin film), perovskite light-absorbing layer (perovskite thin film without multi-active-site acylhydrazine molecule modification), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0057] Example 2 A 1.53 eV bandgap inverted perovskite solar cell modified with multi-active-site acylhydrazine molecule P2 was prepared based on the anti-solvent method. Example 2 is identical to Example 1 except that the multi-active-site acylhydrazine molecule P1 in Example 1 is replaced with multi-active-site acylhydrazine molecule P2. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2The ITO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, and then dried with nitrogen gas. After that, the cleaned ITO conductive substrate was treated with ultraviolet ozone for 15 min to obtain a conductive substrate layer for later use.

[0058] (2) Take 30 mg of NiO x Nanoparticles were dispersed in 1 mL of deionized water, ultrasonically vibrated for 10 min, and then filtered through PVDF to obtain NiO. x Nanoparticle dispersion; take 60 μL of NiO x The nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2 NiO was prepared by spin-coating an ITO conductive substrate at 5000 rpm for 30 s, followed by annealing at 150 °C for 10 min. x layer.

[0059] (3) Dissolve 0.15 mg Me-4PACz and 0.15 mg MeO-2PACz in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a mixed solution of self-assembled molecules; next, take 50 μL of the mixed solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin coating at 5000 rpm for 30 s on the layer and then annealing at 100 °C for 10 min.

[0060] (4) Dissolve 19.49 mg CsI, 245.06 mg FAI and 691.5 mg PbI2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.5 mol / L Cs was prepared. 0.05 FA 0.95 PbI3 perovskite precursor solution; 0.5 mg of multi-active-site hydrazide molecule P2 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site hydrazide molecule P2 was dropped onto the self-assembled molecular layer described in step (3); then stepwise spin coating was performed, the first step was spin-coated at 2000 rpm for 10 s, the second step was spin-coated at 4000 rpm for 40 s; at the 5th s, 150 μL of chlorobenzene was dropped, and the perovskite wet film was annealed at 100 ℃ for 20 min to prepare a perovskite light-absorbing layer modified with multi-active-site hydrazide molecule P2; (5) Take 23 mg PC 61BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer modified with the multi-active site acylhydrazine molecule P2 described in step (4), and spin-coated at a speed of 2500 rpm for 40 s to obtain the electron transport layer. (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer. (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0061] Example 2: A conductive substrate layer (ITO thin film) and a hole transport layer (NiO) were prepared by the above steps, consisting of, from bottom to top, a conductive substrate layer (ITO thin film) and a hole transport layer (NiO). x Thin film, Me-4PACz thin film, MeO-2PACz thin film), perovskite light-absorbing layer (perovskite thin film modified with P2 multi-active-site acylhydrazine molecules), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0062] Performance tests were performed on Example 2 and compared with those of Comparative Example 1. The results are as follows: Figure 13 As shown: Compared to Comparative Example 1, the photovoltaic performance of the device modified with P2 in Example 2 is improved. The modified inverted perovskite solar cell achieves a PCE of 25.44%, of which... J SC 26.31 mA / cm 2 , V OC The voltage is 1.158 V, and the FF is 83.52%.

[0063] Example 3 A 1.53 eV bandgap inverted perovskite solar cell modified with multi-active-site acylhydrazine molecule P3 was prepared based on the antisolvent method. Example 3 is identical to Example 1 except that the multi-active-site acylhydrazine molecule P1 in Example 1 is replaced with multi-active-site acylhydrazine molecule P3. The specific preparation steps are as follows: (1) Take 1.5×1.5cm2 The ITO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, and then dried with nitrogen gas. After that, the cleaned ITO conductive substrate was treated with ultraviolet ozone for 15 min to obtain a conductive substrate layer for later use.

[0064] (2) Take 30 mg of NiO x Nanoparticles were dispersed in 1 mL of deionized water, ultrasonically vibrated for 10 min, and then filtered through PVDF to obtain NiO. x Nanoparticle dispersion; take 60 μL of NiO x The nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2 NiO was prepared by spin-coating an ITO conductive substrate at 5000 rpm for 30 s, followed by annealing at 150 °C for 10 min. x layer.

[0065] (3) Dissolve 0.15 mg Me-4PACz and 0.15 mg MeO-2PACz in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a mixed solution of self-assembled molecules; next, take 50 μL of the mixed solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin coating at 5000 rpm for 30 s on the layer and then annealing at 100 °C for 10 min.

[0066] (4) Dissolve 19.49 mg CsI, 245.06 mg FAI and 691.5 mg PbI2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.5 mol / L Cs was prepared. 0.05 FA 0.95 PbI3 perovskite precursor solution; 0.5 mg of multi-active-site hydrazide molecule P3 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site hydrazide molecule P3 was dropped onto the self-assembled molecular layer described in step (3); then stepwise spin coating was performed, the first step was spin-coated at 2000 rpm for 10 s, the second step was spin-coated at 4000 rpm for 40 s; at the 5th s, 150 μL of chlorobenzene was dropped, and the perovskite wet film was annealed at 100 ℃ for 20 min to prepare a perovskite light-absorbing layer modified with multi-active-site hydrazide molecule P3; (5) Take 23 mg PC 61BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer modified with the multi-active site acylhydrazine molecule P3 described in step (4), and spin-coated at a speed of 2500 rpm for 40 s to obtain the electron transport layer. (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer. (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0067] Example 3: A conductive substrate layer (ITO thin film) and a hole transport layer (NiO) were prepared by the above steps, consisting of, from bottom to top, a conductive substrate layer (ITO thin film) and a hole transport layer (NiO). x Thin film, Me-4PACz thin film, MeO-2PACz thin film), perovskite light-absorbing layer (perovskite thin film modified with P3 multi-active-site acylhydrazine molecule), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0068] Performance tests were performed on Example 3 and compared with those of Comparative Example 1. The results are as follows: Figure 14 As shown: Compared to Comparative Example 1, the photovoltaic performance of the device modified with P3 in Example 2 is improved. The modified inverted perovskite solar cell achieves a PCE of 25.42%, of which... J SC 26.22 mA / cm 2 , V OC It is 1.155 V, and the FF is 83.99%.

[0069] Example 4 A 1.53 eV bandgap inverted perovskite solar cell modified with P1, a multi-active-site acylhydrazide molecule, was prepared using a vacuum flash evaporation method. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2The FTO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, dried with pure nitrogen, and then treated with ultraviolet ozone for 30 min to obtain a conductive substrate layer for later use.

[0070] (2) Dissolve 0.5 mg of 4PADCB in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a 4PADCB solution; then, take 50 μL of the 4PADCB solution and add it dropwise to the 1.5 × 1.5 cm solution described in step (1). 2 A self-assembled molecular layer was prepared by spin-coating the FTO conductive substrate at 3000 rpm for 30 s and annealing at 100 °C for 10 min.

[0071] (3) Dissolve 23.64 mg CsI, 297.22 mg FAI, 880.97 mg PbI2 and 12.29 mg MACl (methylamine hydrochloride) in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.82 mol / L Cs was prepared. 0.05 MA 0.05 FA 0.9 PbI3 perovskite precursor solution; 0.4 mg of multi-active-site hydrazide molecule P1 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site hydrazide molecule P1 was dropped onto the self-assembled molecular layer described in step (2); spin-coating was performed stepwise, firstly at a speed of 1000 rpm for 10 s, and secondly at a speed of 3000 rpm for 30 s; then, the perovskite wet film was placed in a vacuum chamber and evacuated at a vacuum degree of 10 Pa for 30 s; next, it was annealed at 150 ℃ for 10 min to prepare a perovskite light-absorbing layer modified with multi-active-site hydrazide molecule P1.

[0072] (4) Take 500 mg C 60 The powder was placed in a vacuum evaporation crucible and evaporated at a rate of 0.1 Å / s. 60 An electron transport layer with a thickness of 30 nm is obtained by depositing on the perovskite light-absorbing layer described in step (3).

[0073] (5) Place 500 mg of BCP powder in a vacuum evaporation crucible and deposit BCP on the electron transport layer described in step (4) at an evaporation rate of 0.1 Å / s to obtain a hole blocking layer with a thickness of 30 nm.

[0074] (6) Place 1g of Ag particles in a vacuum of 3×10 -4 In an evaporating tungsten boat, Ag is deposited on the hole blocking layer described in step (5) at an evaporation rate of 0.5 Å / s to obtain an Ag back electrode film with a thickness of 100 nm.

[0075] Example 4: Following the above steps, a perovskite light-absorbing layer (a perovskite film modified with multi-active-site acylhydrazide molecules P1) was prepared, consisting of, from bottom to top, a conductive substrate layer (FTO thin film), a hole transport layer (a self-assembled molecule 4PADCB thin film), a perovskite light-absorbing layer (a perovskite thin film modified with multi-active-site acylhydrazide molecules P1), and an electron transport layer (C... 60 An inverted perovskite solar cell consists of a thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0076] Performance tests were performed on Example 4 and compared with those of Comparative Example 2. The results are as follows: Figure 15 As shown: Compared to Comparative Example 2, the inverted perovskite solar cell modified with P1 in Example 2 achieved a higher PCE. The modified perovskite solar cell achieved a PCE of 26.96%, of which... J SC 26.41 mA / cm 2 , V OC The voltage is 1.181 V, and the FF is 86.43%.

[0077] Comparative Example 2 A 1.53 eV bandgap inverted perovskite solar cell was prepared using a vacuum flash evaporation method. Comparative Example 2 and Example 4 were identical except that the multi-active-site hydrazide molecule P1 was not added to the perovskite precursor solution. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The FTO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, dried with pure nitrogen, and then treated with ultraviolet ozone for 30 min to obtain a conductive substrate layer for later use.

[0078] (2) Dissolve 0.5 mg of 4PADCB in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a 4PADCB solution; then, take 50 μL of the 4PADCB solution and add it dropwise to the 1.5 × 1.5 cm solution described in step (1). 2 A self-assembled molecular layer was prepared by spin-coating the FTO conductive substrate at 3000 rpm for 30 s and annealing at 100 °C for 10 min.

[0079] (3) Dissolve 23.64 mg CsI, 297.22 mg FAI, 880.97 mg PbI2 and 12.29 mg MACl (methylamine hydrochloride) in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.82 mol / L Cs was prepared. 0.05 MA 0.05 FA 0.9 PbI3 perovskite precursor solution; next, 55 μL of perovskite precursor solution was dropped onto the self-assembled molecular layer described in step (2); spin-coating was performed stepwise, firstly at a speed of 1000 rpm for 10 s, and secondly at a speed of 3000 rpm for 30 s; then, the perovskite wet film was placed in a vacuum chamber and evacuated at a vacuum degree of 10 Pa for 30 s; next, it was annealed at 150 ℃ for 10 min to obtain the perovskite light-absorbing layer.

[0080] (4) Take 500 mg C 60 The powder was placed in a vacuum evaporation crucible and evaporated at a rate of 0.1 Å / s. 60 An electron transport layer with a thickness of 30 nm is obtained by depositing on the perovskite light-absorbing layer described in step (3).

[0081] (5) Place 500 mg of BCP powder in a vacuum evaporation crucible and deposit BCP on the electron transport layer described in step (4) at an evaporation rate of 0.1 Å / s to obtain a hole blocking layer with a thickness of 30 nm.

[0082] (6) Place 1g of Ag particles in a vacuum evaporation tungsten boat and deposit Ag on the hole blocking layer described in step (5) at an evaporation rate of 0.5 Å / s to obtain an Ag back electrode film with a thickness of 100 nm.

[0083] Comparative Example 2 prepared a perovskite light-absorbing layer (FTO thin film), a hole transport layer (self-assembled 4PADCB thin film), an electron transport layer (C) consisting of, from bottom to top, a conductive substrate layer (FTO thin film), a hole transport layer (self-assembled 4PADCB thin film), a perovskite light-absorbing layer (perovskite thin film without multi-active-site acylhydrazine molecule modification), and an electron transport layer (C) using the above steps. 60 An inverted perovskite solar cell consists of a thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0084] Example 5 A 1.53 eV bandgap inverted perovskite solar cell modified with multi-active-site acylhydrazine molecule P2 was prepared using vacuum flash evaporation technology. Example 5 is identical to Example 4 except that the multi-active-site acylhydrazine molecule P1 in Example 4 is replaced with multi-active-site acylhydrazine molecule P2. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The FTO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, dried with pure nitrogen, and then treated with ultraviolet ozone for 30 min to obtain a conductive substrate layer for later use.

[0085] (2) Dissolve 0.5 mg of 4PADCB in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a 4PADCB solution; then, take 50 μL of the 4PADCB solution and add it dropwise to the 1.5 × 1.5 cm solution described in step (1). 2 A self-assembled molecular layer was prepared by spin-coating the FTO conductive substrate at 3000 rpm for 30 s and annealing at 100 °C for 10 min.

[0086] (3) Dissolve 23.64 mg CsI, 297.22 mg FAI, 880.97 mg PbI2 and 12.29 mg MACl (methylamine hydrochloride) in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.82 mol / L Cs was prepared. 0.05 MA 0.05 FA 0.9 PbI3 perovskite precursor solution; 0.4 mg of multi-active-site acylhydrazine molecule P2 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site acylhydrazine molecule P2 was dropped onto the self-assembled molecular layer described in step (2); spin-coating was performed stepwise, firstly at a speed of 3000 rpm for 5 s, and secondly at a speed of 6000 rpm for 60 s; then, the perovskite wet film was placed in a vacuum chamber and evacuated for 5 s under a vacuum of 20 Pa; next, it was annealed at 150 ℃ for 10 min to prepare a perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecule P2.

[0087] (4) Take 500 mg C 60 The powder was placed in a vacuum evaporation crucible and evaporated at a rate of 0.1 Å / s. 60An electron transport layer with a thickness of 30 nm is obtained by depositing on the perovskite light-absorbing layer described in step (3).

[0088] (5) Place 500 mg of BCP powder in a vacuum evaporation crucible and deposit BCP on the electron transport layer described in step (4) at an evaporation rate of 0.1 Å / s to obtain a hole blocking layer with a thickness of 30 nm.

[0089] (6) Place 1g of Ag particles in a vacuum evaporation tungsten boat and deposit Ag on the hole blocking layer described in step (5) at an evaporation rate of 0.5 Å / s to obtain an Ag back electrode film with a thickness of 100 nm.

[0090] Example 5: Following the steps described above, a perovskite light-absorbing layer was prepared, consisting of, from bottom to top, a conductive substrate (FTO thin film), a hole transport layer (self-assembled 4PADCB thin film), a perovskite light-absorbing layer (a perovskite thin film modified with multi-active-site acylhydrazide molecules P2), and an electron transport layer (C...). 60 An inverted perovskite solar cell consists of a thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0091] Performance tests were performed on Example 5 and compared with those of Comparative Example 2. The results are as follows: Figure 16 As shown: In Example 5, the inverted perovskite solar cell modified with P2 achieved a PCE of 26.51%, of which... J SC 26.35 mA / cm 2 , V OC The voltage is 1.178 V and the FF is 85.39%, which is significantly higher than the device performance in Comparative Example 2.

[0092] Example 6 A 1.53 eV bandgap inverted perovskite solar cell modified with multi-active-site acylhydrazine molecule P3 was prepared using vacuum flash evaporation technology. Example 6 is identical to Example 4 except that the multi-active-site acylhydrazine molecule P1 in Example 4 is replaced with multi-active-site acylhydrazine molecule P3. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The FTO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, dried with pure nitrogen, and then treated with ultraviolet ozone for 30 min to obtain a conductive substrate layer for later use.

[0093] (2) Dissolve 0.5 mg of 4PADCB in 1 mL of anhydrous ethanol, shake for 30 min, and filter using PTFE to obtain a 4PADCB solution; then, take 50 μL of the 4PADCB solution and add it dropwise to the 1.5 × 1.5 cm solution described in step (1). 2 A self-assembled molecular layer was prepared by spin-coating the FTO conductive substrate at 3000 rpm for 30 s and annealing at 100 °C for 10 min.

[0094] (3) Dissolve 23.64 mg CsI, 297.22 mg FAI, 880.97 mg PbI2 and 12.29 mg MACl (methylamine hydrochloride) in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.82 mol / L Cs was prepared. 0.05 MA 0.05 FA 0.9 PbI3 perovskite precursor solution; 0.4 mg of multi-active-site acylhydrazine molecule P3 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site acylhydrazine molecule P3 was dropped onto the self-assembled molecular layer described in step (2); spin-coating was performed stepwise, firstly at a speed of 1000 rpm for 10 s, and secondly at a speed of 3000 rpm for 30 s; then, the perovskite wet film was placed in a vacuum chamber and evacuated at a vacuum degree of 10 Pa for 30 s; next, it was annealed at 150 ℃ for 10 min to prepare a perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecule P3.

[0095] (4) Take 500 mg C 60 The powder was placed in a vacuum evaporation crucible and evaporated at a rate of 0.1 Å / s. 60 An electron transport layer with a thickness of 30 nm is obtained by depositing on the perovskite light-absorbing layer described in step (3).

[0096] (5) Place 500 mg of BCP powder in a vacuum evaporation crucible and deposit BCP on the electron transport layer described in step (4) at an evaporation rate of 0.1 Å / s to obtain a hole blocking layer with a thickness of 30 nm.

[0097] (6) Place 1g of Ag particles in a vacuum evaporation tungsten boat and deposit Ag on the hole blocking layer described in step (5) at an evaporation rate of 0.5 Å / s to obtain an Ag back electrode film with a thickness of 100 nm.

[0098] Example 6: Following the steps described above, a perovskite light-absorbing layer (a perovskite film modified with multi-active-site acylhydrazide molecules P3) was prepared, consisting of, from bottom to top, a conductive substrate layer (FTO thin film), a hole transport layer (a self-assembled 4PADCB thin film), a perovskite light-absorbing layer (a perovskite thin film modified with multi-active-site acylhydrazide molecules P3), and an electron transport layer (C...). 60 An inverted perovskite solar cell consists of a thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0099] Performance tests were performed on Example 6 and compared with those of Comparative Example 2. The results are as follows: Figure 17 As shown: In Example 6, the perovskite solar cell modified with P3 achieved a PCE of 26.37%, of which... J SC 26.37 mA / cm 2 , V OC The voltage is 1.174 V and the FF is 85.25%, which is significantly higher than the device performance in Comparative Example 2.

[0100] Example 7 A 1.68 eV bandgap inverted perovskite solar cell modified with P1, a multi-active-site acylhydrazide molecule, was prepared using an anti-solvent method. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The ITO conductive substrate was sequentially ultrasonically cleaned with detergent solution, deionized water, and anhydrous ethanol for 15 min each, and then dried with pure nitrogen gas. Subsequently, the cleaned 1.5 × 1.5 cm substrate was treated with ultraviolet ozone. 2 Treat the ITO conductive substrate for 30 minutes and set aside.

[0101] (2) Take 10 mg of NiO x Nanoparticles were dispersed in a mixed solvent of 1 mL deionized water and IPA. V 水 : V IPA In a 3:1 ratio, NiO was obtained by ultrasonic vibration for 10 min and then filtered through PVDF. x Nanoparticle dispersion; take 60 μL NiO x The nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2 NiO was prepared by spin-coating a perovskite film on an ITO conductive substrate at 2000 rpm for 30 s, followed by annealing at 150 °C for 10 min. x layer.

[0102] (3) Dissolve 0.3 mg Me-4PACz in 1 mL of ethanol, shake for 30 min, and filter using PTFE to obtain Me-4PACz solution; then, take 50 μL of Me-4PACz solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin-coating at 3000 rpm for 30 s and annealing at 100 ℃ for 10 min.

[0103] (4) Dissolve 10.48 mg CsI, 188.69 mg FAI, 132.37 mg PbBr2, 36.69 mg MABr, 528.49 mg PbI2 and 4.85 mg Pb(SCN)2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.5 mol / L Cs was prepared. 0.05 MA 0.15 FA 0.8 PbI 2.25 Perovskite precursor solution; 0.4 mg of multi-active-site acylhydrazine molecule P1 was added to 1 mL of the prepared perovskite precursor solution; next, 55 μL of the perovskite precursor solution containing multi-active-site acylhydrazine molecule P1 was dropped onto the self-assembled molecular layer described in step (3); spin-coating was performed stepwise, firstly at a speed of 3000 rpm for 60 s, secondly at a speed of 2000 rpm for 10 s, and 200 μL of anisole was dropped at the 20th s. The mixture was then annealed at 100 ℃ for 60 min to prepare a perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecule P1.

[0104] (5) Take 23 mg PC 61 BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer modified with the multi-active-site acylhydrazine molecule P1 described in step (4), and spin-coated at 2500 rpm for 40 s. The layer was then annealed at 70 ℃ for 5 min to obtain the electron transport layer.

[0105] (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer.

[0106] (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0107] Example 7: A conductive substrate layer (ITO thin film) and a hole transport layer (NiO) were prepared by the above steps, consisting of, from bottom to top, a conductive substrate layer (ITO thin film) and a hole transport layer (NiO). x Thin film, Me-4PACz thin film), perovskite light-absorbing layer (perovskite thin film modified with multi-active-site acylhydrazine molecule P1), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0108] Performance tests were performed on Example 7 and compared with those of Comparative Example 3. The results are as follows: Figure 18 As shown: In Example 7, the perovskite solar cell modified with P1 achieved a PCE of 24.02%, where J SC 21.86 mA / cm 2 , V OC The voltage is 1.291 V and the FF is 85.13%, which is significantly higher than the device performance in Comparative Example 3.

[0109] Comparative Example 3 An inverted perovskite solar cell with a band gap of 1.68 eV was prepared based on the antisolvent method. Comparative Example 3 is identical to Example 7 except that the multi-active-site hydrazide molecule P1 was not added to the perovskite precursor solution. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The ITO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, and then dried with pure nitrogen gas. Subsequently, the cleaned ITO conductive substrate was treated with ultraviolet ozone for 30 min and then set aside for use.

[0110] (2) Take 10 mg of NiO x Nanoparticles were dispersed in a mixed solvent of 1 mL deionized water and IPA. V 水 : V IPA In a 3:1 ratio, NiO was obtained by ultrasonic vibration for 10 min and then filtered through PVDF. x Nanoparticle dispersion; take 60 μL NiO xThe nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2 NiO was prepared by spin-coating a perovskite film on an ITO conductive substrate at 2000 rpm for 30 s, followed by annealing at 150 °C for 10 min. x layer.

[0111] (3) Dissolve 0.3 mg Me-4PACz in 1 mL of ethanol, shake for 30 min, and filter using PTFE to obtain Me-4PACz solution; then, take 50 μL of Me-4PACz solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin-coating at 3000 rpm for 30 s and annealing at 100 ℃ for 10 min.

[0112] (4) Dissolve 10.48 mg CsI, 188.69 mg FAI, 132.37 mg PbBr2, 36.69 mg MABr, 528.49 mg PbI2 and 4.85 mg Pb(SCN)2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 4:1, 1.5 mol / L Cs was prepared. 0.05 MA 0.15 FA 0.8 PbI 2.25 Perovskite precursor solution; Next, 55 μL of perovskite precursor solution was dropped onto the self-assembled molecular layer described in step (3); Stepwise spin coating: First, spin coating at 3000 rpm for 60 s; Second, spin coating at 2000 rpm for 10 s; 200 μL of anisole was dropped at 20 s; Annealing was performed at 100 ℃ for 60 min to obtain the perovskite light-absorbing layer.

[0113] (5) Take 23 mg PC 61 BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer described in step (4), and spin-coated at 2500 rpm for 40s. The layer was then annealed at 70 °C for 5 min to obtain the electron transport layer.

[0114] (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer.

[0115] (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0116] Comparative Example 3 prepared a film consisting of a conductive substrate layer (ITO thin film) and a hole transport layer (NiO) from bottom to top through the above steps. x Thin film, Me-4PACz thin film), perovskite light-absorbing layer (perovskite thin film without multi-active-site acylhydrazine molecule modification), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0117] Example 8 A 1.78 eV bandgap inverted perovskite solar cell modified with P1, a multi-active-site acylhydrazide molecule, was prepared using an anti-solvent method. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The ITO conductive substrate was sequentially ultrasonically cleaned with detergent solution, deionized water, and anhydrous ethanol for 15 min each, and then dried with pure nitrogen gas. Subsequently, the cleaned 1.5 × 1.5 cm substrate was treated with ultraviolet ozone. 2 The ITO conductive substrate was treated for 15 minutes and then set aside.

[0118] (2) Take 20 mg of NiO x Nanoparticles were dispersed in 1 mL of deionized water, ultrasonically vibrated for 10 min, and then filtered through PVDF to obtain NiO. x Nanoparticle dispersion; take 60 μL NiO x The nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2 NiO was prepared by spin-coating a perovskite film on an ITO conductive substrate at 2000 rpm for 60 s, followed by annealing at 150 °C for 20 min. x layer.

[0119] (3) Dissolve 0.33 mg Me-4PACz in 1 mL of ethanol, shake for 30 min, and filter using PTFE to obtain Me-4PACz solution; then, take 50 μL of Me-4PACz solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin-coating at 4000 rpm for 40 s and annealing at 100 ℃ for 10 min.

[0120] (4) Dissolve 62.35 mg CsI, 165.09 mg FAI, 264.25 mg PbBr2, 7.76 mg Pb(SCN)2 and 221.28 mg PbI2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 3:1, 1.2 mol / L Cs was prepared. 0.2 FA 0.8 Pb(I 0.6 Br 0.4 ) Perovskite precursor solution; Add 0.1 mg of multi-active-site acylhydrazine molecule P1 to 1 mL of the prepared perovskite precursor solution; Next, take 55 μL of the perovskite precursor solution containing multi-active-site acylhydrazine molecule P1 and drop it onto the self-assembled molecular layer described in step (3); Spin-coat in steps, first spin-coat at 1000 rpm for 5 s, second spin-coat at 5000 rpm for 60 s; Add 700 μL of diethyl ether at 20 s, and anneal at 100 ℃ for 30 min to prepare a perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecule P1.

[0121] (5) Take 23 mg PC 61 BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer modified with the multi-active-site acylhydrazine molecule P1 described in step (4), and spin-coated at 2500 rpm for 40 s to obtain the electron transport layer.

[0122] (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer.

[0123] (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0124] Example 8: A conductive substrate layer (ITO thin film) and a hole transport layer (NiO) were prepared by the above steps, consisting of, from bottom to top, a conductive substrate layer (ITO thin film) and a hole transport layer (NiO). x Thin film, Me-4PACz thin film), perovskite light-absorbing layer (perovskite thin film modified with multi-active-site acylhydrazine molecule P1), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0125] Performance tests were performed on Example 8 and compared with those of Comparative Example 4. The results are as follows: Figure 19 As shown: In Example 8, the perovskite solar cell modified with P1 achieved a PCE of 20.27%, of which... J SC 18.65 mA / cm 2 , V OC The voltage is 1.288 V and the FF is 84.51%, which is significantly higher than the performance of the device in Comparative Example 4.

[0126] Comparative Example 4 An inverted perovskite solar cell with a band gap of 1.78 eV was prepared based on the antisolvent method. Comparative Example 4 and Example 8 were identical except that the multi-active-site hydrazide molecule P1 was not added to the perovskite precursor solution. The specific preparation steps are as follows: (1) Take 1.5×1.5cm 2 The ITO conductive substrate was ultrasonically cleaned sequentially with detergent solution, deionized water and anhydrous ethanol for 15 min each, and then dried with pure nitrogen gas. Subsequently, the cleaned ITO conductive substrate was treated with ultraviolet ozone for 15 min and then set aside for use.

[0127] (2) Take 20 mg of NiO x Nanoparticles were dispersed in 1 mL of deionized water, ultrasonically vibrated for 10 min, and then filtered through PVDF to obtain NiO. x Nanoparticle dispersion; take 60 μL NiO x The nanoparticle dispersion was added dropwise to the 1.5 × 1.5 cm [structure / area] described in step (1). 2NiO was prepared by spin-coating a perovskite film on an ITO conductive substrate at 2000 rpm for 60 s, followed by annealing at 150 °C for 20 min. x layer.

[0128] (3) Dissolve 0.33 mg Me-4PACz in 1 mL of ethanol, shake for 30 min, and filter using PTFE to obtain Me-4PACz solution; then, take 50 μL of Me-4PACz solution and add it dropwise to the NiO obtained in step (2). x The self-assembled molecular layer was obtained by spin-coating at 4000 rpm for 40 s and annealing at 100 ℃ for 10 min.

[0129] (4) Dissolve 62.35 mg CsI, 165.09 mg FAI, 264.25 mg PbBr2, 7.76 mg Pb(SCN)2 and 221.28 mg PbI2 in a mixed solvent of 1 mL DMF and DMSO. V DMF : V DMSO In a mixture of 3:1, 1.2 mol / L Cs was prepared. 0.2 FA 0.8 Pb(I 0.6 Br 0.4 (3) Perovskite precursor solution; Next, take 55 μL of perovskite precursor solution and drop it onto the self-assembled molecular layer described in step (3); Spin-coat in steps, first spin-coat at 1000 rpm for 5 s, second spin-coat at 5000 rpm for 60 s; 700 μL of diethyl ether is added at 20 s, and anneal at 100 ℃ for 30 min to obtain the perovskite light-absorbing layer.

[0130] (5) Take 23 mg PC 61 BM was dissolved in 1 mL of chlorobenzene, shaken for 1 h, and PC was obtained by filtration using PTFE. 61 BM solution; add 30 μL PC 61 The BM solution was dropped onto the perovskite light-absorbing layer described in step (4), and spin-coated at a speed of 2500 rpm for 40 s to obtain the electron transport layer.

[0131] (6) Dissolve 0.5 mg BCP in 1 mL of isopropanol and heat at 60 °C for 1 h to completely dissolve it. Filter with PTFE to obtain BCP solution. Take 50 μL of BCP solution and add it dropwise onto the electron transport layer described in step (5). Spin coat at 5000 rpm for 30 s to obtain hole blocking layer.

[0132] (7) Place 1 g of Ag particles in a vacuum evaporation tungsten boat and evaporate them under high vacuum (10 rpm). -4 Under the condition of Pa), thermal evaporation is carried out at a constant rate of 0.5 Å / s to deposit Ag on the hole blocking layer described in step (6) to obtain an Ag back electrode film with a thickness of 100 nm.

[0133] Comparative Example 4 prepared a film consisting of a conductive substrate layer (ITO thin film) and a hole transport layer (NiO) from bottom to top using the above steps. x Thin film, Me-4PACz thin film), perovskite light-absorbing layer (perovskite thin film without multi-active-site acylhydrazine molecule modification), electron transport layer (PC) 61 An inverted perovskite solar cell consists of a BM thin film, a hole blocking layer (BCP thin film), and a metal back electrode layer (Ag back electrode thin film).

[0134] Table 1 shows the photovoltaic performance results of each embodiment and comparative example in this invention.

[0135] Table 1. Photovoltaic performance of perovskite solar cells As can be seen from Table 1, the devices corresponding to each embodiment are... J SC , V OC In terms of optical fiber spectroscopy (FF) and optical PCE, it outperforms the corresponding comparative examples; among them, Example 4 exhibits the best overall performance, with a PCE of 26.96%, significantly higher than Comparative Example 2; simultaneously, the P1-modified devices in different band gaps also outperform their comparative examples. V OC The improvement in FF indicates that the optimization strategy has universality, which also shows that the technical solution provided by the present invention can effectively improve the optoelectronic performance of the device and has significant technical advantages.

[0136] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. The application of a multi-active-site acylhydrazine molecule in an inverted perovskite solar cell, characterized in that: Multi-site active site hydrazide molecules are used as additives in inverted perovskite precursor solutions.

2. The application according to claim 1, characterized in that: The multi-active-site acylhydrazide molecule is one of P1 to P8; the specific structural formulas of P1 to P8 are as follows: 。 3. The application according to claim 1 or 2, characterized in that: The amount of the multi-active-site hydrazide molecule added to the inverted perovskite precursor solution is 0.1 mg / mL to 0.5 mg / mL.

4. The application according to claim 1 or 2, characterized in that: The inverted perovskite solar cell is composed of, from bottom to top, a conductive substrate layer, a hole transport layer, a perovskite light-absorbing layer modified with multi-active-site hydrazide molecules, an electron transport layer, a hole blocking layer, and a metal back electrode layer.

5. The application according to claim 4, characterized in that: The method for preparing the perovskite light-absorbing layer modified with multi-active-site acylhydrazine molecules is as follows: an inverted perovskite precursor solution containing multi-active-site acylhydrazine molecules is spin-coated onto the hole transport layer using an antisolvent method or a vacuum flash evaporation method, followed by annealing.

6. The application according to claim 5, characterized in that: The steps of the anti-solvent method are as follows: first spin-coat at a speed of 1000 rpm to 3000 rpm for 5 s to 60 s, then spin-coat at a speed of 2000 rpm to 5000 rpm for 10 s to 60 s, and add the anti-solvent dropwise at the 5th to 20th s.

7. The application according to claim 6, characterized in that: The antisolvent is any one or more of diethyl ether, chlorobenzene, toluene, dichloromethane, or chloroform.

8. The application according to claim 5, characterized in that: The steps of the vacuum flash evaporation method are as follows: first spin-coat at a speed of 1000 rpm to 3000 rpm for 5 to 10 s, then spin-coat at a speed of 3000 rpm to 6000 rpm for 30 to 60 s, and then place it in a vacuum chamber with a vacuum degree of 10 Pa to 20 Pa for 5 to 30 s.

9. The application according to claim 5, characterized in that: The annealing conditions are as follows: annealing temperature is 100 ℃~150 ℃, and annealing time is 10 min~60 min.

Images