An organic-inorganic hybrid perovskite solar cell and a preparation method thereof

Abstract

This invention belongs to the technical field of photovoltaic solar cells, specifically relating to an organic-inorganic hybrid perovskite solar cell and its preparation method. This invention proposes to passivate the perovskite surface using pyrazolone and its derivatives, thereby regulating the perovskite solar cell, improving its efficiency and stability, and ultimately obtaining a highly efficient and stable perovskite solar cell.

Description

Technical Field

[0001] This invention belongs to the technical field of photovoltaic solar cells, specifically relating to an organic-inorganic hybrid perovskite solar cell and its preparation method. Background Technology

[0002] In recent years, perovskite solar cells (PSCs) have achieved breakthroughs in photoelectric conversion efficiency. The latest certified time-varying photoelectric conversion efficiency has exceeded 26%, with organic-inorganic hybrid perovskite materials becoming a research hotspot due to their excellent photoelectric properties. These materials exhibit unique advantages: long carrier diffusion distances, tunable band structures, and superior light absorption. Studies have shown that perovskite compositions using formamidinium hydroiodate (FAI) mixed cations can achieve optimal performance. However, problems such as poor stability still exist. These problems are mainly due to the deposition and annealing processes during perovskite layer preparation, which inevitably generate defects within the perovskite, on its surface, and at grain boundaries. These defects lead to nonradiative recombination of carriers and increase the erosion sites for water molecules, thus affecting the efficiency and stability of PSCs. These defects are mainly classified into point defects, line defects, surface defects (grain boundaries), and volume defects. Intrinsic point defects (zero-dimensional) commonly found in organic-inorganic hybrid perovskites are mainly generated by doping and ion migration within the perovskite, including vacancy defects, interstitial atom defects, and antisite defects. In-depth research shows that effective defect passivation strategies can not only further improve device efficiency, but also significantly enhance its environmental stability (especially moisture resistance), which is of great significance for promoting the commercialization of perovskite solar cells.

[0003] To simultaneously improve the stability and efficiency of perovskite condensers (PSCs), researchers have developed various strategies, including surface / interface engineering, composition engineering, and surface morphology manipulation. Among these, surface / interface passivation engineering has attracted considerable attention due to its simplicity and efficiency. This method uses specific passivating agents to passivate surface defects in perovskites, modulating the energy levels between the perovskite and the charge carrier transport layer, thereby controlling the quality of the perovskite film. Currently used passivating agents can be categorized as: Lewis acids, Lewis bases, ionic liquids, inorganic compounds, amine salts, and polymers.

[0004] Specifically, for perovskites with the ABX3 structure, Lewis acids reduce electron-rich defects by eliminating free A-site cations in the precursor. Lewis bases then donate electron pairs to uncoordinated Pb. 2+ Coordination occurs, forming stable coordinate bonds and neutralizing electronegativity. The cations and anions in the ionic liquid simultaneously interact with the positive and negative electrical defects in the perovskite (e.g., anions passivate Pb). 2+ cations and halide ions or FA + / MA +Through interaction, "bipolar" passivation is achieved, reducing halide ion vacancy defects in perovskites. Inorganic compounds can fill the vacancies of A-site cations or grain boundaries, while anions can interact with Pb in the perovskite. 2+ This combination reduces A-site vacancies and Pb in perovskites. 2+ And it weakens interface defects. Amine salts, through hydrogen bonding with halide ions, effectively inhibit ion migration and can bind to uncoordinated Pb. 2+ Coordination reduces charged defects. The polymer's flexibility helps release the internal stress generated during perovskite grain annealing, reducing the formation of microcracks and minimizing defects at perovskite grain boundaries and crystal faces.

[0005] Patent CN119546140A discloses a method and structure for preparing a perovskite solar cell. The method involves mixing a piperazine carboxylic acid compound with an organic solvent in a predetermined ratio to form a passivation solution. This passivation solution is then coated onto the surface of a first perovskite light-absorbing layer and annealed to form a first interfacial passivation layer. By introducing this specific interfacial passivation layer, defects on the surface of the first perovskite light-absorbing layer and at its grain boundaries are effectively passivated, and the interfacial defect state density between the first perovskite light-absorbing layer and the first electron transport layer is reduced, thereby effectively suppressing nonradiative recombination. The core of the piperazine carboxylic acid compound in this patent is a six-membered heterocycle (piperazine ring) containing two nitrogen atoms, forming a carbon-nitrogen single bond structure, and connected to a carboxyl group (-COOH) or other bioisosteric organic compounds. The piperazine carboxylic acid compound primarily targets uncoordinated Pb. 2+ (Defects caused by lead vacancies or PbI2 residues).

[0006] Patent CN118973288A discloses a perovskite solar cell and its preparation method. It involves adding imidazole sulfonate to a perovskite precursor to passivate film defects and suppress non-radiative recombination, thereby improving cell performance. The method involves introducing imidazole ions and sulfonic acid groups into the perovskite precursor solution, ensuring uniform mixing, and achieving good crystallinity of the perovskite layer, thus enhancing cell performance. This patent involves simultaneously adding the perovskite components and imidazole sulfonate to a solvent, followed by spin-coating and annealing to obtain a perovskite film containing imidazole sulfonate, thus providing bulk passivation. Furthermore, the imidazole sulfonate used in this patent is composed of imidazole cations and sulfonate anions, and is obtained through the sulfonate group (-SO3). ﹣ ) and Pb 2+ Although coordination exhibits strong interactions, it is mostly single-point coordination, resulting in poor chelation strength and stability. Summary of the Invention

[0007] The purpose of this invention is to address the stability problem of perovskite solar cells in air by providing an organic-inorganic hybrid perovskite solar cell and its preparation method. This invention proposes to passivate the perovskite surface with pyrazolone and its derivatives to regulate the perovskite solar cell, thereby improving the efficiency and stability of the perovskite solar cell and obtaining a high-efficiency and stable perovskite solar cell.

[0008] The technical solution of this invention is as follows: an organic-inorganic hybrid perovskite solar cell, comprising, from bottom to top, an ITO conductive glass, a hole transport layer, a self-assembled molecular layer, a perovskite light-absorbing layer, a perovskite passivation layer, an electron transport layer, a hole-blocking layer, and a silver electrode; the passivating agent used to form the perovskite passivation layer is selected from any of the following:

[0009] Pyrazolone, bispyrazolone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, 1-(4'-sulfonylphenyl)-3-carboxy-5-pyrazolone, and sodium salt of 1-(4'-sulfonylphenyl)-3-carboxylate-5-pyrazolone. These passivating agents are strongly chelating, containing multiple strong coordinating groups in their molecules, exhibiting polydentate coordination.

[0010] 3-Methyl-1-p-tolyl-5-pyrazolone, 1-(3,4-dimethyl)-3-methyl-5-pyrazolone, 3,4-dimethyl-5-pyrazolone, 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate, and 3-pyrazolone hydrochloride. These passivating agents are bidentate coordination types.

[0011] 1-(4-nitrophenyl)-3-methyl-5-pyrazolone, 3-methyl-1-(3'-sulfonamide)-5-pyrazolone, sodium salt of 3-carboxy-1-(4-sulfonamide)-5-pyrazolone, and potassium salt of 3-carboxy-1-(4-sulfonamide)-5-pyrazolone. These passivating agents are multifunctional synergistic passivating agents.

[0012] Preferably, the passivating agent used to form the perovskite passivation layer is selected from any one of 3-carboxy-1-(4-sulfonic phenyl)-5-pyrazolone sodium salt, 3,4-dimethyl-5-pyrazolone, 1-(4-nitrophenyl)-3-methyl-5-pyrazolone, 1-(4'-sulfonic phenyl)-3-carboxy-5-pyrazolone, 3-methyl-1-(3'-sulfonic aminophenyl)-5-pyrazolone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate, or 1-(4'-sulfonic phenyl)-3-carboxylic acid ethyl ester-5-pyrazolone sodium salt.

[0013] The perovskite passivation layer of the perovskite solar cell described in this invention is formed using pyrazolone and its derivatives as the passivating agent. The passivating agent is a pyrazolone ring with a five-membered heterocyclic structure, wherein the carbonyl oxygen (C=O), imino nitrogen (-NH-), or nitrogen (=N-) on the pyrazolone ring is spatially ortho-positioned, and can simultaneously react with one Pb group. 2+ Coordination forms a more stable, rigid five- or six-membered ring structure, achieving stronger defect passivation, reducing non-radiative recombination losses, and effectively suppressing ion migration, which is crucial for improving device stability.

[0014] Furthermore, other groups in the passivating agent molecule (such as -NH2) can also react with I⁻ or FA in the perovskite lattice. + Hydrogen bonds are formed, enhancing the passivation effect.

[0015] It is evident that the passivation layer formed using the passivating agent described in this invention has stronger rigidity and a more stable structure, which helps to extend the battery's service life.

[0016] In this invention, the concentration of the passivating agent on the perovskite surface of the organic-inorganic hybrid perovskite solar cell is 0.001-10 mg / mL.

[0017] In this invention, the organic-inorganic hybrid perovskite solar cell has a hole transport layer with a thickness of 30-150 nm, a self-assembled molecular layer with a thickness of 5-50 nm, a perovskite light absorption layer with a thickness of 300-800 nm, a perovskite passivation layer with a thickness of 5-50 nm, an electron transport layer with a thickness of 3-130 nm, a hole blocking layer with a thickness of 3-30 nm, and a silver electrode with a thickness of 80-1200 nm.

[0018] The above-mentioned method for preparing organic-inorganic hybrid perovskite solar cells includes the following steps:

[0019] (1) Preparation of hole transport layer:

[0020] NiO is spin-coated onto ozone-treated ITO glass. x Aqueous solution, wherein NiO x The concentration of the aqueous solution is 5-50 mg / mL, and x is 1-2; a hole transport layer of 30-150 nm is formed, and it is annealed at 80-200 °C for 10-60 min. The resulting device structure is ITO / NiO. x NiO here x It indicates nickel oxide, which is a mixture of nickel oxides containing nickel in multiple valence states such as +2, +3, and +4. It is obtained by annealing nickel complexes and contains nickel in multiple valence states.

[0021] (2) Preparation of self-assembled molecular layers:

[0022] On the hole transport layer obtained in step (1), a self-assembled molecular layer is prepared by spin coating to form a 5-50 nm self-assembled molecular layer, and then annealed at 100-300℃ for 1-30 min. The resulting device structure is ITO / NiO. x / Self-assembled molecular layer.

[0023] The spin-coating solution is obtained by dissolving (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid in a mixed solvent composed of ethanol and DMF.

[0024] (3) Preparation of perovskite light-absorbing layer:

[0025] On the self-assembled molecular layer obtained in step (2), a perovskite light absorption layer with a thickness of 300-800 nm is prepared by spin coating and vacuum flash evaporation; and annealed at 80-200℃ for 1-100 min. The resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer.

[0026] The solute composition of the spin-coating solution is as follows: 0.01-1.50 mmol CsI, 0.01-2.00 mmol MAI, 0.10-4.00 mmol FAI, 0.50-3.00 mmol PbI2, 0.001-2.00 mmol MACl, and 0.001-0.15 mmol PbCl2; the solvent is a mixture of DMF and dimethyl sulfoxide in a volume ratio of (10-1):1.

[0027] The vacuum degree of vacuum flash evaporation is controlled at 1-20 Pa, and the pressure is maintained for 10-90 s.

[0028] (4) Preparation of perovskite passivation layer:

[0029] On the perovskite light absorption layer obtained in step (3), a perovskite passivation layer is prepared by spin coating; and annealed at 50-150℃ for 1-100 min. The structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer.

[0030] The spin-coating solution is an isopropanol solution of the passivating agent with a concentration of 0.001-10 mg / mL.

[0031] (5) Fabrication of the electron transport layer:

[0032] The device obtained in step (4) is placed in a thermal evaporation system to prepare an electron transport layer; 3-20 mg of C is weighed. 60 (Fullerene) powder was placed in a crucible, and the vacuum level was increased to 10. -9 -10 -4After Pa, 3-130 nm was deposited at an evaporation rate of 0.001-1.50 nm / s; the structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer.

[0033] (6) Preparation of hole-blocking layer:

[0034] The device obtained in step (5) is placed in a thermal evaporation system to prepare a hole-blocking layer; 0.5-10 mg of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) powder is weighed and placed in a crucible, and the vacuum degree is reached 10. -9 -10 -4 After Pa, 3-30 nm is deposited at an evaporation rate of 0.001-1.80 nm / s; the structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer.

[0035] (7) Preparation of silver electrodes:

[0036] The device obtained in step (6) is placed in a thermal evaporator, and the vacuum level is 10. -9 -10 -4 After Pa, an 80-1200 nm thick Ag electrode was deposited at an evaporation rate of 0.001-1.50 nm / s; the resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer / Ag.

[0037] The perovskite solar cell fabrication process of the present invention involves adding the constituent raw materials of perovskite to a solvent to first prepare a perovskite thin film; and then coating the surface of the perovskite thin film with the passivating agent of pyrazolone and its derivatives.

[0038] In this invention, the spin coating speed in step (1) of the method for preparing the organic-inorganic hybrid perovskite solar cell is 1000-5000 rpm.

[0039] In this invention, the method for preparing the organic-inorganic hybrid perovskite solar cell has a spin coating speed of 1000-6000 rpm and a spin coating time of 5-60 s in step (2).

[0040] In the present invention, the concentration of the spin-coating solution in step (2) of the preparation method of the organic-inorganic hybrid perovskite solar cell is 0.05-0.5 mg / mL.

[0041] In this invention, the method for preparing the organic-inorganic hybrid perovskite solar cell has a spin coating speed of 1000-5000 rpm and a spin coating time of 5-100 s in step (3).

[0042] In this invention, the method for preparing the organic-inorganic hybrid perovskite solar cell has a spin coating speed of 500-5000 rpm and a spin coating time of 5-100 s in step (4).

[0043] The beneficial effects of this invention are as follows: The organic-inorganic hybrid perovskite solar cell described in this invention is based on the regulation of pyrazolone and its derivatives. In the device structure of ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / electron transport layer / hole blocking layer / Ag, by introducing a perovskite passivation layer using pyrazolone and its derivatives as passivating agents, defects in the perovskite are reduced, thereby improving the stability and efficiency of the perovskite solar cell. After being placed in air (temperature 25±5℃, relative humidity 30±5%) for 1500 hours, it still maintains more than 80% of the original photoelectric conversion efficiency, expanding its application range. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the structure of the organic-inorganic hybrid perovskite solar cell described in this invention.

[0045] Among them, 1-1 is ITO conductive glass, 1-2 is hole transport layer, 1-3 is self-assembled molecular layer, 1-4 is perovskite light absorption layer, 1-5 is perovskite passivation layer, 1-6 is electron transport layer, 1-7 is hole blocking layer, and 1-8 is Ag electrode.

[0046] Figure 2 The JV (current-voltage) test curves of the perovskite solar cell devices obtained in Example 1 and Comparative Example 1 are shown.

[0047] Among them, curve 2-1 is the JV test curve of the uncontrolled perovskite solar cell in Comparative Example 1.

[0048] Curve 2-2 is the JV test curve of the perovskite solar cell regulated by sodium 3-carboxy-1-(4-sulfonylphenyl)-5-pyrazolone in Example 1.

[0049] Figure 3 The stability curves are for the perovskite solar cell devices obtained in Example 1 and Comparative Example 1.

[0050] Among them, curve 3-1 is the stability curve of the uncontrolled perovskite solar cell in Comparative Example 1.

[0051] Curve 3-2 is the stability curve of the perovskite solar cell regulated by sodium 3-carboxy-1-(4-sulfonylphenyl)-5-pyrazolone in Example 1. Detailed Implementation

[0052] The technical solution of the present invention will be described in detail below.

[0053] Example 1

[0054] The organic-inorganic hybrid perovskite solar cell comprises, from bottom to top, ITO conductive glass, a hole transport layer, a self-assembled molecular layer, a perovskite light-absorbing layer, a perovskite passivation layer, an electron transport layer, a hole-blocking layer, and a silver electrode; the perovskite passivation layer is formed using 3-carboxy-1-(4-sulfonylphenyl)-5-pyrazolone sodium salt as a passivating agent.

[0055] The specific steps for preparing the organic-inorganic hybrid perovskite solar cell are as follows:

[0056] (1) Preparation of hole transport layer:

[0057] NiO is spin-coated onto ozone-treated ITO glass. x Aqueous solution, spin-coated at 4000 rpm; wherein, NiO x The aqueous solution concentration was 10 mg / mL; a 50 nm hole transport layer was formed, and the mixture was annealed at 150 °C for 10 min, resulting in a device structure of ITO / NiO. x .

[0058] (2) Preparation of self-assembled molecular layers:

[0059] On the hole transport layer obtained in step (1), a self-assembled molecular layer was prepared by spin coating to form a 5 nm self-assembled molecular layer. The spin coating speed was 5000 rpm and the spin coating time was 30 s. After annealing at 100 °C for 15 min, the resulting device structure was ITO / NiO. x / Self-assembled molecular layer.

[0060] The spin-coating solution was prepared by dissolving (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid in a mixed solvent composed of ethanol and DMF. The concentration of the spin-coating solution was 0.5 mg / mL.

[0061] (3) Preparation of perovskite light-absorbing layer:

[0062] On the self-assembled molecular layer obtained in step (2), a perovskite light absorption layer with a thickness of 800 nm was prepared by spin coating and vacuum flash evaporation. First, spin coating was performed at a spin coating speed of 1000 rpm for 5 s; then spin coating was performed at a spin coating speed of 5000 rpm for 30 s, and then annealed at 150 °C for 1 min and then annealed at 100 °C for 15 min. The resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer.

[0063] The solute composition of the spin-coating solution is as follows: 0.091 mmol CsI, 0.091 mmol MAI, 1.638 mmol FAI, 1.82 mmol PbI2, 0.001 mmol MACl, and 0.001 mmol PbCl2; the solvent is a mixture of DMF and dimethyl sulfoxide in a volume ratio of 4:1.

[0064] The vacuum degree of vacuum flash evaporation is controlled at 1 Pa, and the pressure is maintained for 40 s.

[0065] (4) Preparation of perovskite passivation layer:

[0066] On the perovskite light absorption layer obtained in step (3), a perovskite passivation layer is prepared by spin coating at a spin coating speed of 5000 rpm and a spin coating time of 30 s; and then annealed at 100℃ for 1 min. The structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer.

[0067] The spin-coating solution is an isopropanol solution of the passivating agent with a concentration of 0.1 mg / mL.

[0068] (5) Fabrication of the electron transport layer:

[0069] The device obtained in step (4) was placed in a thermal evaporation system to prepare an electron transport layer; 5 mg of C was weighed. 60 (Fullerene) powder was placed in a crucible, and the vacuum degree was 1×10⁻⁶. -5 After Pa, 25 nm was deposited at an evaporation rate of 0.004 nm / s; the structure of the resulting device was ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer.

[0070] (6) Preparation of hole-blocking layer:

[0071] The device obtained in step (5) was placed in a thermal evaporation system to prepare a hole-blocking layer; 2 mg of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) powder was weighed and placed in a crucible, and the vacuum degree was 1×10 -5 Then, 8 nm was deposited at an evaporation rate of 0.002 nm / s; the structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer.

[0072] (7) Preparation of silver electrodes:

[0073] The device obtained in step (6) is placed in a thermal evaporator, and the vacuum level reaches 1×10⁻⁶. -5After Pa, a 100 nm thick Ag electrode was deposited at an evaporation rate of 0.005 nm / s; the resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer / Ag.

[0074] The photoelectric performance of the fabricated solar cell device was tested, such as... Figure 2 As shown, characterized by current-voltage curves, the perovskite solar cell without passivation agent regulation has an open-circuit voltage of 1.18V and a short-circuit current of 26.20mA / cm. 2 The fill factor is 81.74%, and the photoelectric conversion efficiency is 25.39%.

[0075] The perovskite solar cell regulated by sodium 3-carboxy-1-(4-sulfonylphenyl)-5-pyrazolone exhibits an open-circuit voltage of 1.19V and a short-circuit current of 26.29mA / cm². 2 The fill factor is 86.52%, and the photoelectric conversion efficiency is 27.25%.

[0076] As can be seen from the above, the photoelectric conversion efficiency of the perovskite solar cell device regulated by sodium 3-carboxy-1-(4-sulfonic acid phenyl)-5-pyrazolone is significantly higher than that of the unregulated perovskite solar cell.

[0077] like Figure 3 As shown, the unregulated perovskite solar cell device retains 80% of its initial efficiency after 500 hours, while the perovskite solar cell device regulated by sodium 3-carboxy-1-(4-sulfonylphenyl)-5-pyrazolone retains 80% of its initial efficiency after being placed in air for 1500 hours. Compared with the unregulated perovskite solar cell device, both efficiency and stability are improved.

[0078] Example 2

[0079] The difference from Example 1 lies in the preparation method of the organic-inorganic hybrid perovskite solar cell, which includes the following specific steps:

[0080] (1) Preparation of hole transport layer:

[0081] NiO is spin-coated onto ozone-treated ITO glass. x Aqueous solution, spin-coated at 3000 rpm; wherein, NiO x The aqueous solution concentration was 10 mg / mL; a 50 nm hole transport layer was formed, and the mixture was annealed at 150 °C for 10 min, resulting in a device structure of ITO / NiO. x .

[0082] (2) Preparation of self-assembled molecular layers:

[0083] On the hole transport layer obtained in step (1), a self-assembled molecular layer was prepared by spin coating to form a 5 nm self-assembled molecular layer. The spin coating speed was 5000 rpm and the spin coating time was 30 s. After annealing at 100 °C for 15 min, the resulting device structure was ITO / NiO. x / Self-assembled molecular layer.

[0084] The spin-coating solution was prepared by dissolving (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid in a mixed solvent composed of ethanol and DMF. The concentration of the spin-coating solution was 0.5 mg / mL.

[0085] (3) Preparation of perovskite light-absorbing layer:

[0086] On the self-assembled molecular layer obtained in step (2), a perovskite light absorption layer with a thickness of 800 nm was prepared by spin coating and vacuum flash evaporation. First, spin coating was performed at a spin coating speed of 1000 rpm for 5 s; then spin coating was performed at a spin coating speed of 5000 rpm for 30 s; and then annealed at 150 °C for 1 min. The resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer.

[0087] The solute composition of the spin-coating solution is as follows: 0.091 mmol CsI, 0.091 mmol MAI, 1.638 mmol FAI, 1.82 mmol PbI2, 0.001 mmol MACl, and 0.001 mmol PbCl2; the solvent is a mixture of DMF and dimethyl sulfoxide in a volume ratio of 4:1.

[0088] The vacuum degree of vacuum flash evaporation is controlled at 1 Pa, and the pressure is maintained for 40 s.

[0089] (4) Preparation of perovskite passivation layer:

[0090] On the perovskite light absorption layer obtained in step (3), a perovskite passivation layer is prepared by spin coating. The spin coating speed is 5000 rpm and the spin coating time is 30 s. The device is then annealed at 150 °C for 1 min. The structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer.

[0091] The spin-coating solution is an isopropanol solution of sodium salt of the passivating agent 3-carboxy-1-(4-sulfonic acid phenyl)-5-pyrazolone at a concentration of 0.05 mg / mL.

[0092] (5) Fabrication of the electron transport layer:

[0093] The device obtained in step (4) was placed in a thermal evaporation system to prepare an electron transport layer; 5 mg of C was weighed. 60 (Fullerene) powder was placed in a crucible, and the vacuum degree was 1×10⁻⁶.-5 After Pa, 25 nm was deposited at an evaporation rate of 0.004 nm / s; the structure of the resulting device was ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer.

[0094] (6) Preparation of hole-blocking layer:

[0095] The device obtained in step (5) was placed in a thermal evaporation system to prepare a hole-blocking layer; 2 mg of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) powder was weighed and placed in a crucible, and the vacuum degree was 1×10 -5 After Pa, 8 nm was deposited at an evaporation rate of 0.002 nm / s; the structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer.

[0096] (7) Preparation of silver electrodes:

[0097] The device obtained in step (6) is placed in a thermal evaporator, and the vacuum level reaches 1×10⁻⁶. -5 After Pa, a 100 nm thick Ag electrode was deposited at an evaporation rate of 0.005 nm / s; the resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer / Ag.

[0098] The perovskite solar cell regulated in this embodiment achieved an efficiency of 26.23%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0099] Example 3

[0100] The difference from Example 1 is that the perovskite passivation layer is formed using 3,4-dimethyl-5-pyrazolone as the passivating agent.

[0101] The others are the same as in Example 1.

[0102] The perovskite solar cell regulated by 3,4-dimethyl-5-pyrazolone achieved an efficiency of 26.15%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0103] The carbonyl oxygen (C=O) and imino nitrogen (-NH-) or nitrogen (=N-) of 3,4-dimethyl-5-pyrazolone are simultaneously reacted with Pb. 2+ Coordination forms a stable, rigid five-membered ring structure, reducing nonradiative recombination losses, while also improving stability compared to devices without pyrazolone derivatives.

[0104] Example 4

[0105] The difference from Example 1 is that the perovskite passivation layer is formed using 1-(4-nitrophenyl)-3-methyl-5-pyrazolone as the passivating agent.

[0106] The others are the same as in Example 1.

[0107] The perovskite solar cell regulated by 1-(4-nitrophenyl)-3-methyl-5-pyrazolone achieved an efficiency of 26.23%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0108] Compared to perovskites without pyrazolone derivatives, the stability is improved. Both the carbonyl oxygen atom (C=O) and the oxygen atom on the nitro group (-NO2) have lone pairs of electrons and uncoordinated Pb at the perovskite grain boundaries and surface. 2+ It forms stable coordination bonds, reduces defect sites, and inhibits the migration of halide ions.

[0109] Example 5

[0110] The difference from Example 1 is that the perovskite passivation layer is formed using 1-(4'-sulfonophenyl)-3-carboxy-5-pyrazolone as the passivating agent.

[0111] The others are the same as in Example 1.

[0112] The perovskite solar cell regulated by 1-(4'-sulfonylphenyl)-3-carboxy-5-pyrazolone achieved an efficiency of 26.29%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0113] Compared to perovskites without pyrazolone derivatives, the stability was improved. This may be because the carboxyl, sulfonic acid, carbonyl and nitrogen atoms form strong interactions with the perovskite, while the hydrophobicity of the phenyl group also improves the hydrophobicity of the perovskite surface, thereby enhancing stability.

[0114] Example 6

[0115] The difference from Example 1 is that the perovskite passivation layer is formed using 3-methyl-1-(3'-sulfonamide)-5-pyrazolone as the passivating agent.

[0116] The others are the same as in Example 1.

[0117] The perovskite solar cell regulated by 3-methyl-1-(3'-sulfonamide)-5-pyrazolone achieved an efficiency of 26.32%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0118] Compared to perovskite films without pyrazolone derivatives, 3-methyl-1-(3'-sulfonoaminophenyl)-5-pyrazolone contains a pyrazolone ring, a sulfonic acid group, and an amino group, which interact with uncoordinated Pb on the perovskite surface or grain boundaries. 2+ It forms stable complexes, effectively inhibits ion migration, and improves the stability of perovskite.

[0119] Example 7

[0120] The difference from Example 1 is that the perovskite passivation layer is formed using 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone as the passivating agent.

[0121] The others are the same as in Example 1.

[0122] The perovskite solar cell regulated by 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone achieved an efficiency of 26.72%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0123] Compared to perovskite films without pyrazolone derivatives, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone perovskite contains carbonyl oxygen and enol hydroxyl oxygen, both of which have lone pairs of electrons that can interact with uncoordinated Pb. 2+ Forming coordinate bonds reduces the activity of defect sites, inhibits ion migration and charge recombination, and helps stabilize the crystal structure.

[0124] Example 8

[0125] The difference from Example 1 is that the perovskite passivation layer is formed using 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate as the passivating agent.

[0126] The others are the same as in Example 1.

[0127] The perovskite solar cell regulated by 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate achieved an efficiency of 26.12%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0128] Compared to perovskite films without pyrazolone derivatives, the perovskite containing 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate has carbonyl oxygen and chlorine atoms, both of which have lone pairs of electrons that can form stable coordinate bonds with uncoordinated metal ions, inhibiting ion migration. At the same time, large benzene ring molecules are distributed at the perovskite grain boundaries. When molecules aggregate at the perovskite grain boundaries and surface, they can form an effective protective layer, improving the efficiency and stability of the perovskite.

[0129] Example 9

[0130] The difference from Example 1 is that the perovskite passivation layer is formed using 1-(4'-sulfonylphenyl)-3-carboxylic acid ethyl ester-5-pyrazolone sodium salt as the passivating agent.

[0131] The others are the same as in Example 1.

[0132] The perovskite solar cell regulated by sodium 1-(4'-sulfonylphenyl)-3-carboxylate-5-pyrazolone achieved an efficiency of 26.78%, which is an improvement compared to the efficiency of 25.39% of the perovskite solar cell without pyrazolone derivative regulation.

[0133] Compared to perovskite films without pyrazolone derivatives, the sulfonic acid group, the carbonyl oxygen on the pyrazolone ring, and the carbonyl oxygen on the ethyl carboxylate group in sodium 1-(4'-sulfonylphenyl)-3-carboxylate-5-pyrazolone all have lone pair electrons that form strong interactions with ions in the perovskite, which can improve the stability of the perovskite. At the same time, the phenyl group can also improve the hydrophobicity of the perovskite surface, thereby improving the stability of the perovskite.

[0134] Comparative Example 1

[0135] The difference between this comparative example and Example 1 is that no perovskite passivation layer was prepared.

[0136] A FA-based organic-inorganic hybrid perovskite solar cell, the preparation steps of which are as follows:

[0137] (1) Preparation of hole transport layer:

[0138] NiO is spin-coated onto ozone-treated ITO glass. x Aqueous solution, NiO x An aqueous solution with a concentration of 10 mg / mL and a rotation speed of 4000 rpm was used to form a 50 nm hole transport layer, which was then annealed at 150 °C for 10 min to obtain an ITO / NiO structure. x .

[0139] (2) Preparation of self-assembled molecular layers:

[0140] In NiO x A self-assembled molecular layer was prepared on the hole transport layer by spin coating, forming a 5 nm self-assembled molecular layer. The spin coating speed was 5000 rpm and the spin coating time was 30 s. After annealing at 100 °C for 15 min, the resulting device structure was ITO / NiO. x / Self-assembled molecular layer.

[0141] The spin-coating solution was prepared by dissolving (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid in a mixed solvent composed of ethanol and DMF. The concentration of the spin-coating solution was 0.5 mg / mL.

[0142] (3) Preparation of perovskite light-absorbing layer:

[0143] A perovskite light-absorbing layer with a thickness of 800 nm was prepared on the self-assembled molecular layer by spin coating and vacuum flash evaporation. First, spin coating was performed at a speed of 1000 rpm for 5 s, and then at a speed of 5000 rpm for 30 s. The resulting device was annealed at 150 °C for 1 min and then at 100 °C for 15 min. The structure of the device was ITO / NiOx / self-assembled molecular layer / perovskite light-absorbing layer.

[0144] The solute composition of the spin-coating solution is as follows: 0.091 mmol CsI, 0.091 mmol MAI, 1.638 mmol FAI, 1.82 mmol PbI2, 0.001 mmol MACl, and 0.001 mmol PbCl2; the solvent is a mixture of DMF and dimethyl sulfoxide in a volume ratio of 4:1.

[0145] The vacuum degree of vacuum flash evaporation is controlled at 1 Pa, and the pressure is maintained for 40 s.

[0146] (4) Fabrication of the electron transport layer:

[0147] The device obtained in step (3) was placed in a thermal evaporation system to prepare an electron transport layer, and 5 mg of C was weighed. 60 (Fullerene) powder was placed in a crucible, and the vacuum degree was 1×10⁻⁶. -5 After Pa, 25 nm was deposited at an evaporation rate of 0.004 nm / s; the structure of the resulting device was ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / electron transport layer.

[0148] (5) Preparation of hole-blocking layer:

[0149] Hole-blocking layers were prepared in a thermal evaporation system. 2 mg of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) powder was weighed and placed in a crucible, where a vacuum of 1 × 10⁻⁶ was applied. -5 Then, 8 nm was deposited at an evaporation rate of 0.002 nm / s; the structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / electron transport layer / hole blocking layer.

[0150] (6) Preparation of silver electrodes:

[0151] The device obtained in step (5) is placed in a thermal evaporator, and the vacuum level reaches 1×10⁻⁶. -5After Pa, a 100 nm thick Ag electrode was deposited at an evaporation rate of 0.005 nm / s; the resulting device structure was ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / electron transport layer / hole blocking layer / Ag.

[0152] pass Figure 3 It can be seen that the perovskite solar cell obtained in Comparative Example 1 retains 80% of its original photoelectric conversion efficiency after being placed in air for 500 hours. In contrast, the perovskite solar cell in Example 1, regulated by sodium 3-carboxy-1-(4-sulfonylphenyl)-5-pyrazolone, still retains 80% of its original photoelectric conversion efficiency after being placed in air for 1500 hours.

Claims

1. An organic-inorganic hybrid perovskite solar cell, comprising, from bottom to top, an ITO conductive glass, a hole transport layer, a self-assembled molecular layer, a perovskite light-absorbing layer, a perovskite passivation layer, an electron transport layer, a hole-blocking layer, and a silver electrode; characterized in that, The passivating agent used to form the perovskite passivation layer is selected from any of the following: Pyrazolone, bispyrazolone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, 1-(4'-sulfonic phenyl)-3-carboxy-5-pyrazolone or sodium salt of 1-(4'-sulfonic phenyl)-3-carboxylic acid ethyl ester-5-pyrazolone; 3-Methyl-1-p-tolyl-5-pyrazolone, 1-(3,4-dimethyl)-3-methyl-5-pyrazolone, 3,4-dimethyl-5-pyrazolone, 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate or 3-pyrazolone hydrochloride; 1-(4-nitrophenyl)-3-methyl-5-pyrazolone, 3-methyl-1-(3'-sulfonamide)-5-pyrazolone, sodium salt of 3-carboxy-1-(4-sulfonamide)-5-pyrazolone or potassium salt of 3-carboxy-1-(4-sulfonamide)-5-pyrazolone.

2. The organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that, The passivating agent used to form the perovskite passivation layer is selected from any one of the following: sodium 3-carboxy-1-(4-sulfonic phenyl)-5-pyrazolone, 3,4-dimethyl-5-pyrazolone, 1-(4-nitrophenyl)-3-methyl-5-pyrazolone, 1-(4'-sulfonic phenyl)-3-carboxy-5-pyrazolone, 3-methyl-1-(3'-sulfonic aminophenyl)-5-pyrazolone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, 1-(2-chlorophenyl)-3-methyl-5-pyrazolone hydrate, or sodium 1-(4'-sulfonic phenyl)-3-carboxylic acid ethyl ester-5-pyrazolone.

3. The organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that, The concentration of the passivating agent on the perovskite surface is 0.001-10 mg / mL.

4. The organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that, The hole transport layer has a thickness of 30-150 nm, the self-assembled molecular layer has a thickness of 5-50 nm, the perovskite light absorption layer has a thickness of 300-800 nm, the perovskite passivation layer has a thickness of 5-50 nm, the electron transport layer has a thickness of 3-130 nm, the hole blocking layer has a thickness of 3-30 nm, and the silver electrode has a thickness of 80-1200 nm.

5. A method for preparing an organic-inorganic hybrid perovskite solar cell as described in any one of claims 1-4, characterized in that, Includes the following steps: (1) Preparation of hole transport layer: NiO was spin-coated on the ITO glass treated by ozone x aqueous solution, wherein the concentration of NiO x aqueous solution is 5-50 mg / mL; a hole transport layer of 30-150 nm is formed, and the obtained device structure is ITO / NiO x ; (2) Preparation of self-assembled molecular layers: On the hole transport layer obtained in step (1), a self-assembled molecule layer is prepared by spin coating method, forming a 5-50 nm self-assembled molecule layer, and annealing at 100-300 °C for 1-30 min, obtaining a device structure of ITO / NiO x / self-assembled molecule layer; The spin-coating solution is obtained by dissolving (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid in a mixed solvent composed of ethanol and DMF; (3) Preparation of perovskite light-absorbing layer: On the self-assembled molecular layer obtained in step (2), a perovskite light absorption layer with a thickness of 300-800 nm is prepared by spin coating and vacuum flash evaporation; and annealed at 80-200℃ for 1-100 min. The resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer. The solute composition of the spin-coating solution is as follows: 0.01-1.50 mmol CsI, 0.01-2.00 mmol MAI, 0.10-4.00 mmol FAI, 0.50-3.00 mmol PbI2, 0.001-2.00 mmol MACl, and 0.001-0.15 mmol PbCl2; the solvent is a mixture of DMF and dimethyl sulfoxide in a volume ratio of (10-1):

1. The vacuum degree of vacuum flash evaporation is controlled at 1-20 Pa, and the pressure is maintained for 10-90 s; (4) Preparation of perovskite passivation layer: On the perovskite light absorption layer obtained in step (3), a perovskite passivation layer is prepared by spin coating; and annealed at 50-150℃ for 1-100 min. The structure of the resulting device is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer. The spin-coating solution is an isopropanol solution of the passivating agent with a concentration of 0.001-10 mg / mL; (5) Fabrication of the electron transport layer: The device obtained in step (4) is placed in a thermal evaporation system to prepare an electron transport layer; 3-20 mg of C 60 powder is weighed into a crucible, and the vacuum degree is reached to 10 -9 -10 -4 Pa, and 3-130 nm is deposited at an evaporation rate of 0.001-1.50 nm / s; the structure of the obtained device is ITO / NiOx / self-assembled monolayer / perovskite light absorption layer / perovskite passivation layer / electron transport layer; (6) Preparation of hole-blocking layer: The device obtained in step (5) is placed in a thermal evaporation system to prepare a hole blocking layer; 0.5-10 mg of BCP powder is weighed and placed in a crucible, and the vacuum degree is reached to 10 -9 -10 -4 After 10 Pa, 3-30 nm is deposited at an evaporation rate of 0.001-1.80 nm / s; the structure of the obtained device is ITO / NiOx / self-assembled monolayer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer; (7) Preparation of silver electrodes: The device obtained in step (6) is placed in a thermal evaporator, and the vacuum level is 10. -9 -10 -4 After Pa, an 80-1200 nm thick Ag electrode was deposited at an evaporation rate of 0.001-1.50 nm / s; the resulting device structure is ITO / NiOx / self-assembled molecular layer / perovskite light absorption layer / perovskite passivation layer / electron transport layer / hole blocking layer / Ag.

6. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that, The spin coating speed in step (1) is 1000-5000 rpm.

7. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that, The spin coating speed in step (2) is 1000-6000 rpm, and the spin coating time is 5-60 s.

8. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that, The concentration of the spin coating solution in step (2) is 0.05-0.5 mg / mL.

9. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that, The spin coating speed in step (3) is 1000-5000 rpm, and the spin coating time is 5-100 s.

10. The method for preparing an organic-inorganic hybrid perovskite solar cell according to claim 5, characterized in that, The spin coating speed in step (4) is 500-5000 rpm and the spin coating time is 5-100 s.

Images