Perovskite battery and preparation method thereof, and electric device

Abstract

The application provides a perovskite battery and a preparation method thereof and an electric device, and belongs to the technical field of thin film photoelectricity and interface engineering. In the preparation method of the perovskite battery, ink including self-assembled monomers and a passivation material (such as a polyacrylate compound) is used for inkjet printing, the passivation material is beneficial to adjusting the rheological property and dynamic surface tension of the ink, and the inkjet printing quality is improved. After the inkjet printing is completed, segmented annealing is performed, and a composite structure of a lower self-assembled monolayer and an upper passivation layer is spontaneously formed on the conductive substrate, the composite structure provides the functions of crystallization regulation and interface passivation for a subsequent perovskite layer, reduces interface recombination and non-radiation loss, and thus the device efficiency of the perovskite battery is improved.

Description

Technical Field

[0001] This application relates to the field of thin-film optoelectronics and interface engineering technology, and in particular to perovskite solar cells and their preparation methods and electrical devices. Background Technology

[0002] Self-assembled monolayers (SAMs) can control the work function and wettability of conductive oxide electrode substrates (such as FTO and ITO) at the nanoscale, suppress interface defects and non-radiative recombination, and are an important interface layer for novel thin-film optoelectronic devices.

[0003] Traditional methods for preparing shale air-embedded atomized metallized metallized (SAM) include dip coating, spin coating, and blade coating. These methods have limitations in terms of patterned deposition, material utilization, production efficiency, and mass production consistency. Inkjet printing, with its advantages of non-contact, on-demand deposition, and patternability, is an ideal path for achieving large-scale and flexible manufacturing of SAM. However, SAM inks often use alcohol solvents (such as ethanol and isopropanol), which have low viscosity, making it difficult to control jetting stability and linewidth. Adding high-viscosity solvents to adjust viscosity prolongs drying time, and residual solvents are difficult to remove completely, thus interfering with the orderly formation of SAM. Furthermore, in perovskite solar cell device structures, a passivation layer is usually deposited on the SAM surface to further suppress interfacial recombination. However, this step often requires secondary coating and secondary annealing processes, leading to uncontrollable interfacial disturbances and affecting the overall device performance.

[0004] Therefore, how to systematically optimize the fabrication process of perovskite solar cells to improve the photoelectric conversion efficiency, open-circuit voltage, and fill factor of the devices has become an urgent technical problem to be solved. Summary of the Invention

[0005] Based on this, the main objective of this application is to provide perovskite solar cells and their fabrication methods and electrical devices, so as to improve the photoelectric conversion efficiency, open-circuit voltage and fill factor of perovskite solar cell devices.

[0006] The first aspect of this application provides a method for preparing a perovskite solar cell, comprising the following steps:

[0007] Using an ink comprising self-assembled monomolecules and passivation materials, inkjet printing is performed on a conductive substrate, followed by segmented annealing to prepare a self-assembled monomolecule layer and a passivation layer; the self-assembled monomolecule layer is located between the conductive substrate and the passivation layer;

[0008] A perovskite layer is prepared on the passivation layer;

[0009] The passivation material includes polyacrylate compounds;

[0010] The thickness of the passivation layer is 2nm-10nm;

[0011] The conditions for segmented annealing include: first annealing at 50℃-70℃, and then second annealing at 100℃-150℃.

[0012] In some embodiments, the polyacrylate compound includes at least one selected from polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polyethyl methacrylate, polytert-butyl methacrylate, and polyisobutyl methacrylate.

[0013] In some embodiments, the self-assembled monomolecule includes phosphonic acid self-assembled monomolecules; the phosphonic acid self-assembled monomolecules include [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl- ... At least one of H-carbazole-9-yl)butyl]phosphonic acid, [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid, [2-(9-bromocarbazole-9-yl)ethyl]phosphonic acid, [2-(9-chlorocarbazole-9-yl)ethyl]phosphonic acid, [4-(9-bromocarbazole-9-yl)butyl]phosphonic acid, and [4-(9-fluorocarbazole-9-yl)butyl]phosphonic acid.

[0014] In some embodiments, the ink further includes a solvent; the solvent includes ethanol and / or ethyl acetate.

[0015] In some embodiments, the concentration of self-assembled monomers in the ink is 0.1 mg / mL to 0.4 mg / mL.

[0016] In some embodiments, the passivating material in the ink has a mass fraction of 0.1%-1%.

[0017] In some embodiments, the solvent in the ink includes ethanol and ethyl acetate, wherein the volume ratio of ethanol to ethyl acetate is 5:5-9:1.

[0018] In some embodiments, the viscosity of the ink is 5.0 mPa·s-10.0 mPa·s.

[0019] In some embodiments, the surface tension of the ink is 20.0 mN / m to 30.0 mN / m.

[0020] In some implementations, the first annealing time is 3-8 minutes.

[0021] In some implementations, the second annealing time is 5-10 minutes.

[0022] In some implementations, the conditions for inkjet printing include: a resolution of 720×360 DPI; a printhead drive voltage of 10V-20V; a printing speed of 300mm / s-800mm / s; and a printhead temperature of 25℃-35℃.

[0023] In some embodiments, an ink comprising self-assembled monomolecules and passivating materials is used. Before inkjet printing on a conductive substrate, a pretreatment step is also included, in which the conductive substrate is pretreated. The pretreatment method includes at least one of cleaning treatment, ultraviolet ozone treatment, and plasma activation treatment.

[0024] In some embodiments, the conductive substrate includes one of an inorganic conductive substrate and an organic-inorganic composite conductive substrate;

[0025] The inorganic conductive substrate includes fluorine-doped tin oxide glass and / or indium tin oxide glass;

[0026] The organic-inorganic composite conductive substrate includes an organic film layer and indium tin oxide glass disposed on the surface of the organic film layer; the organic film layer includes polyethylene terephthalate and / or polyethylene naphthalate.

[0027] In some embodiments, the perovskite layer comprises a perovskite material having the structural formula ABX3; wherein A is selected from at least one of formamidinium cation, methylamine cation, and cesium cation, B is selected from lead cation and / or tin cation, and X is selected from at least one of fluoride anion, chloride anion, bromide anion, and iodide anion.

[0028] In some embodiments, after preparing a perovskite layer on the passivation layer, the method further includes the step of sequentially preparing an electron transport layer, a barrier layer, and an electrode layer on the perovskite layer.

[0029] In some embodiments, the material of the electron transport layer includes at least one of C60, methyl [6,6]-phenyl-C61-butyrate, and zinc oxide.

[0030] In some embodiments, the barrier layer is made of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and / or tin dioxide.

[0031] In some embodiments, the electrode layer is made of at least one of silver, copper, gold, and carbon.

[0032] In a second aspect, this application provides a perovskite solar cell prepared by the method for preparing a perovskite solar cell described in the first aspect.

[0033] In a third aspect of this application, an electrical device is provided, comprising a perovskite battery prepared by the method described in the first aspect or a perovskite battery described in the second aspect.

[0034] Compared with traditional technologies, this application has at least the following beneficial effects:

[0035] This application utilizes inkjet printing with an ink comprising self-assembled monomolecules and passivation materials (such as polyacrylate compounds) for inkjet printing, followed by segmented annealing at different temperature ranges within a single thermal path. This spontaneously forms a composite structure of a lower self-assembled monomolecule layer and an upper passivation layer on a conductive substrate. The resulting perovskite solar cell exhibits excellent performance in terms of photoelectric conversion efficiency, open-circuit voltage, and fill factor, demonstrating good overall performance. Specifically, in the inkjet printing process, the passivation material can be used to adjust the rheological properties and dynamic surface tension of the ink, improving phenomena such as droplet instability, satellite droplets, droplet deflection, linewidth fluctuations, and uneven wet film edges generated during ink jetting, thereby enhancing the quality of inkjet printing. In the segmented annealing process, the self-assembled monomolecules are promoted to adsorb and assemble on the conductive substrate, forming a self-assembled monomolecule layer. Simultaneously, the thermally driven surface energy difference promotes the segregation of the passivation material towards the air side, forming a passivation layer on the self-assembled monomolecule layer. This provides crystallization regulation and interface passivation for the subsequent perovskite layer, reducing interfacial recombination and non-radiative losses, and improving the device efficiency of the perovskite solar cell. Attached Figure Description

[0036] To better describe and illustrate the embodiments or examples provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments or examples, or the best mode of conduct of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings.

[0037] Figure 1 This is a schematic diagram comparing the JV curves of the perovskite solar cells of Example 1 and Comparative Example 1.

[0038] Figure 2 This is a schematic diagram comparing the JV curves of the perovskite solar cells in Example 1 and Comparative Example 2. Detailed Implementation

[0039] The present application will be further described in detail below with reference to the embodiments and examples. These embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to enable a more thorough and comprehensive understanding of the disclosure of the present application. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0041] Traditional SAM inks often use alcohol solvents (such as ethanol and isopropanol), which have low viscosity, making it difficult to control the spraying stability and linewidth. Adding high-viscosity solvents to adjust the viscosity prolongs the drying time, and the residual solvent is difficult to remove completely, thus interfering with the orderly formation of SAM. In addition, depositing a passivation layer on the SAM surface often requires a secondary coating and secondary annealing process, which brings uncontrollable interface disturbances and affects the overall performance of the device. This application addresses these issues by using inkjet printing with inks that include self-assembled monomolecules and passivation materials (such as polyacrylate compounds), followed by segmented annealing in a single thermal path according to different temperature ranges. This spontaneously forms a composite structure of a lower self-assembled monomolecule layer and an upper passivation layer on a conductive substrate. The resulting perovskite solar cell exhibits excellent performance in terms of photoelectric conversion efficiency, open-circuit voltage, and fill factor, demonstrating good overall performance. In the inkjet printing process, the passivation material can be used to adjust the rheological properties and dynamic surface tension of the ink, improving phenomena such as droplet instability, satellite droplets, droplet deflection, linewidth fluctuations, and uneven wet film edges generated during ink jetting, thereby improving the quality of inkjet printing. In the segmented annealing process, it promotes the adsorption of self-assembled monomolecules on the conductive substrate for self-assembly, forming a self-assembled monolayer. At the same time, the thermally driven surface energy difference promotes the segregation of the passivation material towards the air side, forming a passivation layer on the self-assembled monolayer. This provides crystallization regulation and interface passivation for the subsequent perovskite layer, reducing interfacial recombination and non-radiative losses, and improving the device efficiency of perovskite solar cells.

[0042] The first aspect of this application provides a method for preparing a perovskite solar cell, comprising the following steps:

[0043] Using an ink comprising self-assembled monomolecules and passivation materials, inkjet printing is performed on a conductive substrate, followed by segmented annealing to prepare a self-assembled monomolecule layer and a passivation layer; the self-assembled monomolecule layer is located between the conductive substrate and the passivation layer;

[0044] A perovskite layer is prepared on the passivation layer;

[0045] The passivation material includes polyacrylate compounds;

[0046] The thickness of the passivation layer is 2nm-10nm;

[0047] The conditions for segmented annealing include: first annealing at 50℃-70℃, and then second annealing at 100℃-150℃.

[0048] This application employs inkjet printing using ink comprising self-assembled monomolecules and passivating materials (such as polyacrylate compounds). The passivating material helps regulate the ink's rheological properties and dynamic surface tension, improving inkjet printing quality. After inkjet printing, segmented annealing is performed, allowing the self-assembled monomolecules to self-assemble on a conductive substrate, forming a self-assembled monomolecule layer. The passivating material floats upwards through thermally driven surface energy differences, forming a passivation layer that provides crystallization regulation and interface passivation for the subsequent perovskite layer, reducing interfacial recombination and non-radiative losses, and improving the device efficiency of the perovskite solar cell. Furthermore, the perovskite solar cell fabrication method of this application features a wide process window, excellent thin-film uniformity, and ease of patterning design and large-area process scale-up. Notably, the anchoring ability between the passivating material (such as polyacrylate compounds) and the conductive substrate (such as a metal oxide substrate) is weaker than that between the self-assembled monomolecules and the conductive substrate (such as a metal oxide substrate). Therefore, the passivating material does not strongly compete for coordination with the conductive substrate, minimizing interference with the self-assembly process of the self-assembled monomolecules. Meanwhile, the carbonyl group in polyacrylate compounds can act as a mild Lewis base, interacting weakly with defect sites at the perovskite interface, thereby passivating interface defects.

[0049] In some embodiments, the polyacrylate compound includes at least one of polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polybutyl methacrylate (PnBA), polyethyl methacrylate (PEA), polytert-butyl methacrylate (PtBA), and polyisobutyl methacrylate (PiBMA).

[0050] In some embodiments, the polyacrylate compound satisfies the following condition: a weight-average molecular weight (Mw) of 20,000 Da to 150,000 Da, which can be 20,000 Da, 30,000 Da, 40,000 Da, 50,000 Da, 60,000 Da, 70,000 Da, 80,000 Da, 90,000 Da, 100,000 Da, 110,000 Da, 120,000 Da, 130,000 Da, 140,000 Da, or 150,000 Da.

[0051] In this application, the passivation layer formed by the passivation material has the function of passivating the interface and regulating the crystallization of perovskite, which can improve the device efficiency of perovskite solar cells.

[0052] In some embodiments, the conditions for segmented annealing include: first annealing at 50°C-70°C, or at 60°C; and then second annealing at 100°C-150°C, or at 120°C.

[0053] In some embodiments, the self-assembled monomolecule includes phosphonic acid self-assembled monomolecules; the phosphonic acid self-assembled monomolecules include [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(3,6-dimethyl- ... At least one of H-carbazole-9-yl)butyl]phosphonic acid, [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid, [2-(9-bromocarbazole-9-yl)ethyl]phosphonic acid, [2-(9-chlorocarbazole-9-yl)ethyl]phosphonic acid, [4-(9-bromocarbazole-9-yl)butyl]phosphonic acid, and [4-(9-fluorocarbazole-9-yl)butyl]phosphonic acid.

[0054] In some embodiments, the ink further includes a solvent; the solvent includes ethanol and / or ethyl acetate.

[0055] In some embodiments, the concentration of self-assembled monomers in the ink is 0.1 mg / mL to 0.4 mg / mL, and can be 0.1 mg / mL, 0.2 mg / mL, 0.3 mg / mL or 0.4 mg / mL.

[0056] In some embodiments, the passivating material in the ink has a mass fraction of 0.1%-1%, which can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.75%, 0.8%, 0.9% or 1%.

[0057] In some embodiments, the solvent in the ink includes ethanol and ethyl acetate, wherein the volume ratio of ethanol to ethyl acetate is 5:5-9:1, and can be 5:5, 6:4, 7:3, 8:2, or 9:1. The presence of ethanol in the solvent of the ink is beneficial for accelerating the deprotonation of self-assembled monomolecules and their adsorption on the substrate surface, thus facilitating the preparation of high-quality self-assembled monolayers.

[0058] In some embodiments, the solvent in the ink is composed of ethanol and ethyl acetate, with a volume ratio of ethanol to ethyl acetate of 5:5-9:1, specifically 5:5, 6:4, 7:3, 8:2, or 9:1. The solvent in the ink, composed of ethanol and ethyl acetate, exhibits good volatility and a low risk of residual solubility. Ethanol, as the primary solvent, further accelerates the deprotonation of self-assembled monolayers and their adsorption on the substrate surface, which is beneficial for preparing high-quality self-assembled monolayers. The ink achieves surface densification and interface functionalization through a single inkjet printing and single-pass annealing process, producing a self-assembled monolayer and a passivation layer. The use of ethanol and ethyl acetate as the solvent avoids the residual problems associated with high-boiling-point solvents and eliminates the need for complex vacuum flash evaporation and high-precision anti-solvent timing control. Furthermore, the use of passivation materials overcomes the limitations imposed by insufficient solvent viscosity on the inkjet printing process. In the single-pass annealing process, the self-assembled monomolecules in the ink spontaneously form a layered structure of an upper passivation layer and a lower self-assembled monomolecule layer with the passivation material (such as polyacrylate compounds). This enhances the subsequent perovskite crystallization and interface passivation, simultaneously achieving viscosity control and performance improvement. The process is simple, can improve production efficiency, and has the manufacturability to smoothly scale up from small-batch R&D to large-area mass production.

[0059] In some embodiments, the viscosity of the ink is 5.0 mPa·s-10.0 mPa·s, and can be 5.0 mPa·s, 6.0 mPa·s, 6.2 mPa·s, 6.5 mPa·s, 6.6 mPa·s, 6.9 mPa·s, 7.0 mPa·s, 8.0 mPa·s, 9.0 mPa·s, or 10.0 mPa·s.

[0060] In some embodiments, the surface tension of the ink is 20.0 mN / m to 30.0 mN / m, and can be 20.0 mN / m, 21.0 mN / m, 22.0 mN / m, 23.0 mN / m, 23.1 mN / m, 23.3 mN / m, 23.5 mN / m, 23.8 mN / m, 24.0 mN / m, 25.0 mN / m, 26.0 mN / m, 27.0 mN / m, 28.0 mN / m, 29.0 mN / m, or 30.0 mN / m.

[0061] The viscosity and surface tension of the ink described in this application are controlled within a certain range, which is beneficial to further improve the quality of inkjet printing.

[0062] In some implementations, the first annealing time is 3-8 minutes, which can be 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes or 8 minutes.

[0063] In some implementations, the second annealing time is 5-10 minutes, which can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes.

[0064] In some embodiments, the inkjet printing conditions include: a resolution of 720×360 DPI; a printhead drive voltage of 10V-20V (e.g., 10V, 12V, 15V, 18V, or 20V); a printing speed of 300mm / s-800mm / s (e.g., 300mm / s, 400mm / s, 500mm / s, 600mm / s, 700mm / s, or 800mm / s); and a printhead temperature of 25℃-35℃ (e.g., 25℃, 27℃, 30℃, 32℃, or 35℃). The printhead drive voltage is the voltage amplitude of the main pulse segment in the drive waveform.

[0065] In some embodiments, the inkjet printing conditions further include: a driving waveform that is a single-pulse trapezoidal waveform with a pulse width of 4μs-12μs (e.g., 4μs, 5μs, 8μs, 10μs, or 12μs), and a nozzle diameter of 20μm-30μm (e.g., 20μm, 22μm, 25μm, 27μm, or 30μm). The inkjet printing waveform described in this application is adjusted according to Newtonian fluid characteristics, which can widen the inkjet printing process window, improve inkjet stability, and thus ensure inkjet printing quality.

[0066] In some embodiments, the inkjet printing step on the conductive substrate involves one to two inkjet printing passes, either one or two. This application achieves patterned deposition through single or double overprinting. After inkjet printing is completed, segmented annealing is performed directly.

[0067] In some embodiments, an ink comprising self-assembled monomolecules and passivating materials is used. Before inkjet printing on a conductive substrate, a pretreatment step is also included, in which the conductive substrate is pretreated. The pretreatment method includes at least one of cleaning treatment, ultraviolet ozone treatment, and plasma activation treatment.

[0068] In some embodiments, the cleaning process includes cleaning with at least one of detergent, deionized water, acetone, and isopropanol.

[0069] In some embodiments, the cleaning process includes ultrasonic cleaning in sequence with detergent, deionized water, acetone and isopropanol.

[0070] In some embodiments, during the cleaning process, the ultrasonic cleaning time for each of the detergent, deionized water, acetone, and isopropanol is ≥10 min, and can be 15 min.

[0071] In some embodiments, the pretreatment step of the conductive substrate specifically includes: ultrasonic cleaning in sequence with detergent, deionized water, acetone and isopropanol, followed by ultraviolet ozone treatment.

[0072] The detergent is a glass detergent.

[0073] In some embodiments, before ultrasonic cleaning with detergent, deionized water, acetone and isopropanol in sequence, a step of scribing the conductive substrate with P1 lines is included.

[0074] In some implementations, the conditions for ultraviolet ozone treatment include a time of ≥20 min, which can be 30 min.

[0075] The pretreatment of the conductive substrate helps to increase the hydroxyl density on its surface, which improves the anchoring, ordered self-assembly, and uniform coverage of the self-assembled monolayer during the subsequent formation process.

[0076] In some embodiments, the conductive substrate includes one of an inorganic conductive substrate and an organic-inorganic composite conductive substrate;

[0077] The inorganic conductive substrate includes fluorine-doped tin oxide glass (FTO glass) and / or indium tin oxide glass (ITO glass).

[0078] The organic-inorganic composite conductive substrate includes an organic film layer and an indium tin oxide glass disposed on the surface of the organic film layer; the organic film layer includes polyethylene terephthalate (PET) and / or polyethylene naphthalate (PEN).

[0079] In some embodiments, the organic-inorganic composite conductive substrate includes at least one of indium tin oxide glass / polyethylene terephthalate (ITO / PET) and indium tin oxide glass / polyethylene naphthalate (ITO / PEN). The indium tin oxide glass / polyethylene terephthalate (ITO / PET) refers to a transparent conductive substrate with a flexible PET film as the substrate and an ITO film deposited on the substrate surface. The indium tin oxide glass / polyethylene naphthalate (ITO / PEN) refers to a transparent conductive substrate with a flexible PEN film as the substrate and an ITO film deposited on the substrate surface. During the preparation of the self-assembled monolayer and passivation layer, phosphonic acid self-assembled monomolecules form POM bonds (M representing metal) with the FTO or ITO surface through phosphonic acid groups, which is beneficial for improving interface defects and non-radiative recombination between the conductive substrate and the self-assembled monolayer.

[0080] In some embodiments, the perovskite layer comprises a perovskite material having the structural formula ABX3; wherein A is selected from formamidinium cations (FA). + ), Methylamine cation (MA) + ) and cesium cations (Cs + B is selected from lead cation and / or tin cation, and X is selected from at least one of fluoride anion, chloride anion, bromide anion and iodide anion.

[0081] In some embodiments, the step of preparing a perovskite layer on the passivation layer specifically includes:

[0082] The perovskite precursor solution is deposited onto the passivation layer and annealed to prepare the perovskite layer.

[0083] In some embodiments, the perovskite precursor solution comprises a perovskite precursor and a solvent, wherein the solvent comprises N,N-dimethylformamide (DMF) and N-methylpyrrolidone (NMP).

[0084] In some embodiments, the solvent in the perovskite precursor solution is composed of DMF and NMP, and the volume ratio of DMF to NMP is 1:1 to 9:1, which can be 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 9:1.

[0085] In some embodiments, the perovskite precursor includes Cs 0.05 FA 0.95 PbI3 and MACl.

[0086] In some embodiments, in the perovskite precursor, Cs 0.05 FA 0.95The concentration of PbI3 is 1.0M-1.8M, which can be 1M, 1.3M, 1.5M, or 1.8M; the concentration of MACl is 0.1M-0.2M, which can be 0.1M, 0.13M, 0.15M, or 0.2M. Adding MACl to the perovskite precursor is beneficial for further improving the crystallinity and morphology of the perovskite layer.

[0087] In some embodiments, the step of depositing the perovskite precursor solution onto the passivation layer specifically includes: depositing the perovskite precursor solution onto the passivation layer using a slot coating process. The slot coating process conditions include: a spacing between the slot head and the substrate of 50 μm-200 μm, which can be 50 μm, 75 μm, 100 μm, 125 μm, 150 μm, 175 μm, or 200 μm; a coating speed of 2 mm / s-20 mm / s, which can be 2 mm / s, 5 mm / s, 10 mm / s, 15 mm / s, or 20 mm / s; and a liquid supply rate of 2 μL / s-20 μL / s, which can be 2 μL / s, 5 μL / s, 10 μL / s, 15 μL / s, or 20 μL / s.

[0088] In some embodiments, the perovskite precursor solution is deposited onto the passivation layer, and the annealing step includes annealing conditions of: a temperature of 100°C-120°C, which can be 100°C, 105°C, 110°C, 115°C or 120°C; and a time of 10 min-20 min, which can be 10 min, 15 min or 20 min.

[0089] In some embodiments, the perovskite layer comprises a perovskite material with the structural formula APbX3; wherein A is selected from at least one of formamidinium cation, methylamine cation, and cesium cation, and X is selected from at least one of fluoride anion, chloride anion, bromide anion, and iodide anion. The polyacrylate compound in the passivation layer contains a carbonyl group, which can act as a mild Lewis base to coordinate with uncoordinated lead ions in the perovskite, thus improving the interfacial defect density and reducing non-radiative recombination.

[0090] In some embodiments, after preparing a perovskite layer on the passivation layer, the method further includes the step of sequentially preparing an electron transport layer, a barrier layer, and an electrode layer on the perovskite layer.

[0091] In some embodiments, the material of the electron transport layer includes at least one of C60, methyl [6,6]-phenyl-C61-butyrate (PCBM), and zinc oxide.

[0092] In some embodiments, the barrier layer is made of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and / or tin dioxide.

[0093] In some embodiments, the electrode layer is made of at least one of silver, copper, gold, and carbon.

[0094] In some embodiments, the step of preparing the electron transport layer specifically includes depositing the electron transport layer on the perovskite layer by thermal evaporation under vacuum conditions.

[0095] In some embodiments, the deposition rate in the step of preparing the electron transport layer is 0.1 Å / s to 0.5 Å / s, which can be 0.1 Å / s, 0.2 Å / s, 0.3 Å / s, 0.4 Å / s, or 0.5 Å / s.

[0096] In some embodiments, the vacuum conditions in the step of fabricating the electron transport layer satisfy: a vacuum degree of 5 × 10⁻⁶. - 4 Pa.

[0097] In some embodiments, the step of preparing the barrier layer specifically includes depositing the barrier layer on the electron transport layer by thermal evaporation under vacuum conditions.

[0098] In some embodiments, the deposition rate in the step of preparing the barrier layer is 0.1 Å / s to 0.3 Å / s, and can be 0.1 Å / s, 0.15 Å / s, 0.2 Å / s, 0.25 Å / s or 0.3 Å / s.

[0099] In some embodiments, the vacuum conditions in the step of preparing the barrier layer are: a vacuum degree of 5 × 10⁻⁶. -4 Pa.

[0100] In some embodiments, after the barrier layer is prepared, a step of scribing P2 lines using a picosecond laser system is also included.

[0101] In some embodiments, the step of preparing the electrode layer specifically includes depositing the electrode layer on the barrier layer by thermal evaporation under vacuum conditions.

[0102] In some embodiments, the deposition rate in the electrode layer preparation step is 0.5 Å / s to 5 Å / s, which can be 0.5 Å / s, 1 Å / s, 2 Å / s, 3 Å / s, 4 Å / s or 5 Å / s.

[0103] In some embodiments, the vacuum conditions in the electrode layer fabrication step satisfy: a vacuum degree of 5 × 10⁻⁶. -4 Pa.

[0104] In some embodiments, after fabricating the electrode layer, a step of scribing P3 lines using a picosecond laser system is also included.

[0105] In a second aspect, this application provides a perovskite solar cell prepared by the method for preparing a perovskite solar cell described in the first aspect.

[0106] In some embodiments, the thickness of the self-assembled monolayer in the perovskite solar cell is 0.5 nm to 5 nm, and can be 0.5 nm, 1.0 nm, 1.5 nm, 2.0 nm, 2.5 nm, 3.0 nm, 3.5 nm, 4.0 nm, 4.5 nm or 5 nm.

[0107] In the perovskite solar cell described in this application, the thickness of the passivation layer is 2nm-10nm, which can be 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm. In this application, the carbonyl groups of the polyacrylate compounds in the passivation layer can interact mildly with the bottom interface defects of the perovskite layer, thereby effectively passivating the interface. The relatively small thickness of the passivation layer, within the 2nm-10nm range, results in a shorter tunneling path for charge carriers at the interface, thus ensuring lower contact resistance and interface extraction resistance.

[0108] In some embodiments, the thickness of the perovskite layer in the perovskite solar cell is 300nm-800nm, and can be 300nm, 400nm, 500nm, 600nm, 700nm or 800nm.

[0109] In some embodiments, the thickness of the electron transport layer in the perovskite solar cell is 15nm-30nm, which can be 15nm, 20nm, 25nm or 30nm.

[0110] In some embodiments, the thickness of the barrier layer in the perovskite solar cell is 5nm-10nm, which can be 5nm, 6nm, 7nm, 8nm, 9nm or 10nm.

[0111] In some embodiments, the thickness of the electrode layer in the perovskite solar cell is 80nm-150nm, and can be 80nm, 100nm, 150nm or 200nm.

[0112] In a third aspect of this application, an electrical device is provided, comprising a perovskite battery prepared by the method described in the first aspect or a perovskite battery described in the second aspect.

[0113] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this application, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0114] In this application, the raw materials used in the various embodiments and comparative examples are as follows:

[0115] Polymethyl methacrylate (PMMA): purchased from Agilent, catalog number PSS-MM70K, weight average molecular weight (Mw) is approximately 70,000 Da;

[0116] Polyethyl methacrylate (PEMA): purchased from Polymer Source, catalog number P8335-EMA, with a weight-average molecular weight (Mw) of approximately 70,000 Da;

[0117] Polybutyl methacrylate (PBMA): purchased from Alfa Chemistry, catalog number ACM9003638-1, with a weight-average molecular weight (Mw) of approximately 100,000 Da;

[0118] Polybutyl acrylate (PnBA): Purchased from Wanna Juhe, catalog number PLH006, with a weight-average molecular weight (Mw) of approximately 100,000 Da;

[0119] Polyethyl acrylate (PEA): purchased from Alfa Chemistry, catalog number ACM9003321, with a weight-average molecular weight (Mw) of approximately 100,000 Da;

[0120] tert-butyl polyacrylate (PtBA): purchased from Wanna Juhe, catalog number PLH008, with a weight-average molecular weight (Mw) of approximately 70,000 Da;

[0121] Polyisobutyl methacrylate (PiBMA): purchased from Sigma, catalog number 181544, with a weight-average molecular weight (Mw) of approximately 70,000 Da.

[0122] Example 1

[0123] The fabrication method of perovskite solar cells is as follows:

[0124] (1) Substrate pretreatment: Using 200mm thick FTO conductive glass as the conductive substrate, P1 lines were etched on the surface of the conductive substrate using a nanosecond laser. Then, the FTO substrate was placed in detergent, deionized water, acetone and isopropanol in sequence, and ultrasonically cleaned for 15min in each. After cleaning, the conductive substrate was subjected to ultraviolet ozone treatment for 30min.

[0125] (2) Preparation of self-assembled molecular layer and passivation layer: Using ethanol and ethyl acetate in a volume ratio of 7:3 as solvents, a solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) with a concentration of 0.2 mg / mL was prepared. Then PMMA was added to the solution to make the mass fraction of PMMA in the system 0.5%. After stirring at 1000 rpm and 35℃ for 60 min, the solution was allowed to stand to remove bubbles and prepare ink (viscosity of 6.0 mPa·s, surface tension of 24.0 mN / m).

[0126] Inkjet printing was used to coat the ink. The printing conditions were set as follows: resolution of 720×360 DPI, printhead drive voltage of 18V, printing speed of 500mm / s, printhead temperature of 30℃, drive waveform of single-pulse trapezoidal waveform with a pulse width of 10μs, and nozzle diameter of 25μm. After printing, segmented annealing was performed: first annealing at 60℃ for 5min, followed by a second annealing at 120℃ for 8min to prepare a self-assembled molecular layer (2nm thick) and a passivation layer (5nm thick) on the self-assembled monolayer.

[0127] (3) Preparation of perovskite layer: Using DMF and NMP in a volume ratio of 4:1 as solvents, prepare Cs with a concentration of 1.3M. 0.05 FA 0.95 A PbI3 solution was prepared by adding 10 mol% MACl to prepare a perovskite precursor solution, wherein the concentration of MACl was 0.13 M.

[0128] The perovskite precursor solution was deposited onto the passivation layer using a slot coating process. The slot coating process conditions were: a slot head spacing of 100 μm between the slot head and the substrate, a coating speed of 10 mm / s, and a liquid supply rate of 10 μL / s. After coating, the formed film was annealed on a hot plate at 100 °C for 10 min to prepare a perovskite layer (500 nm thick).

[0129] (4) Fabrication of electron transport layer and barrier layer: under vacuum conditions (5×10⁻⁶) -4 At a depth of 0.2 Å / s, C60 was deposited on the perovskite layer using a thermal evaporation method to prepare an electron transport layer (25 nm thick). Then, BCP was deposited on the electron transport layer at a deposition rate of 0.2 Å / s to prepare a barrier layer (8 nm thick). Subsequently, P2 lines were scribed using a picosecond laser system.

[0130] (5) Electrode layer preparation: in a vacuum environment (5×10 -4A 100 nm thick copper electrode was thermally evaporated and deposited on the barrier layer at a deposition rate of 2 Å / s in a picosecond laser, forming the electrode layer. P3 lines were then scribed using a picosecond laser system to complete the fabrication of the perovskite solar cell. The perovskite solar cell integrates 24 tandem sub-cells, and each cell has a side length of 200 mm.

[0131] Example 2

[0132] The preparation method of the perovskite solar cell in Example 2 is basically the same as that in Example 1, except that "the mass fraction of PMMA in the system is 0.5%" is replaced with "the mass fraction of PMMA in the system is 0.75%". The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 7.8 mPa·s, the surface tension was 24.1 mN / m, and the passivation layer thickness was 7.5 nm.

[0133] Example 3

[0134] The preparation method of the perovskite solar cell in Example 3 is basically the same as that in Example 1, except that inkjet printing is repeated twice under the conditions of inkjet printing in Example 1, and segmented annealing is performed after printing. The perovskite solar cell is prepared according to the method of Example 1. The thickness of the self-assembled molecular layer is 3.2 nm, and the thickness of the passivation layer is 9.5 nm.

[0135] Example 4

[0136] The preparation method of the perovskite solar cell in Example 4 is basically the same as that in Example 1, except that PMMA is replaced with an equal mass of PEMA. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.2 mPa·s, and the surface tension was 24.0 mN / m.

[0137] Example 5

[0138] The preparation method of the perovskite solar cell in Example 5 is basically the same as that in Example 1, except that PMMA is replaced with an equal mass of PBMA. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.9 mPa·s, and the surface tension was 23.5 mN / m.

[0139] Example 6

[0140] The preparation method of the perovskite solar cell in Example 6 is basically the same as that in Example 1, except that PMMA is replaced with an equal mass of PnBA. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.5 mPa·s, and the surface tension was 23.3 mN / m.

[0141] Example 7

[0142] The preparation method of the perovskite solar cell in Example 7 is basically the same as that in Example 1, except that PMMA is replaced with an equal mass of PEA. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.6 mPa·s, and the surface tension was 23.8 mN / m.

[0143] Example 8

[0144] The preparation method of the perovskite solar cell in Example 8 is basically the same as that in Example 1, except that PMMA is replaced with an equal mass of PtBA. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.2 mPa·s, and the surface tension was 23.1 mN / m.

[0145] Example 9

[0146] The preparation method of the perovskite solar cell in Example 9 is basically the same as that in Example 1, except that PMMA is replaced with an equal mass of PiBMA. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.0 mPa·s, and the surface tension was 23.5 mN / m.

[0147] Example 10

[0148] The preparation method of the perovskite solar cell in Example 10 is basically the same as that in Example 1, except that "the first annealing is performed at 60°C for 5 min, and then the second annealing is performed at 120°C for 8 min" is replaced with "the first annealing is performed at 50°C for 5 min, and then the second annealing is performed at 150°C for 8 min". The perovskite solar cell was prepared according to the method of Example 1.

[0149] Example 11

[0150] The preparation method of the perovskite solar cell in Example 11 is basically the same as that in Example 1, except that "the first annealing is performed at 50°C for 5 min, and then the second annealing is performed at 120°C for 8 min" is replaced with "the first annealing is performed at 50°C for 5 min, and then the second annealing is performed at 100°C for 8 min". The perovskite solar cell was prepared according to the method of Example 1.

[0151] Comparative Example 1

[0152] The preparation method of the perovskite solar cell in Comparative Example 1 is basically the same as that in Example 1, except that PMMA was not added and no passivation layer was prepared. The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 2.0 mPa·s and the surface tension was 23.0 mN / m.

[0153] Comparative Example 2

[0154] The preparation method of the perovskite solar cell in Comparative Example 2 is basically the same as that in Example 1, except that PMMA was not added, a passivation layer was not prepared, and the solvent ratio of ethanol and ethyl acetate (7:3 by volume) was replaced with a solvent ratio of ethanol, ethyl acetate, and propylene glycol (50:30:20 by volume). The perovskite solar cell was prepared according to the method in Example 1. The ink viscosity was 6.0 mPa·s, and the surface tension was 25.5 mN / m.

[0155] Comparative Example 3

[0156] The preparation method of the perovskite solar cell in Comparative Example 3 is basically the same as that in Example 1, except that the self-assembled molecular layer and passivation layer are prepared stepwise. The perovskite solar cell was prepared according to the method in Example 1.

[0157] Specifically, step (2) of preparing the self-assembled molecular layer and passivation layer is as follows:

[0158] A 0.2 mg / mL MeO-2PACz solution was prepared using ethanol and ethyl acetate in a 7:3 volume ratio as solvents. After stirring at 1000 rpm and 35°C for 60 min, the solution was allowed to stand to remove bubbles, resulting in MeO-2PACz ink (viscosity 2.0 mPa·s, surface tension 23.0 mN / m). The ink was then coated using inkjet printing with the following parameters: resolution 720 × 360 DPI, printhead drive voltage 12 V, print speed 500 mm / s, printhead temperature 30°C, single-pulse trapezoidal waveform with a pulse width of 10 μs, and nozzle diameter 25 μm. After printing, segmented annealing was performed: first at 60°C for 5 min, then at 120°C for 8 min, to prepare a self-assembled molecular layer (2 nm thick).

[0159] A 0.5% PMMA solution was prepared using ethanol and ethyl acetate in a volume ratio of 7:3 as solvents. The PMMA solution was stirred at 1000 rpm and 35°C for 60 min, then allowed to stand to remove bubbles, resulting in an ink (viscosity 6.0 mPa·s, surface tension 24.0 mN / m). The ink was then coated using inkjet printing with the following parameters: resolution 720×360 DPI, printhead drive voltage 18.0 V, print speed 500 mm / s, printhead temperature 30°C, single-pulse trapezoidal waveform with a pulse width of 10 μs, and nozzle diameter 25 μm. After printing, the ink was annealed at 120°C for 13 min to prepare a passivation layer (5 nm thick) on the self-assembled monolayer.

[0160] Comparative Example 4

[0161] The preparation method of the perovskite solar cell in Comparative Example 4 is basically the same as that in Example 1, except that "annealing at 60°C for 5 min and then annealing at 120°C for 8 min" is replaced with "annealing at 60°C for 13 min". The perovskite solar cell was prepared according to the method in Example 1.

[0162] Comparative Example 5

[0163] The preparation method of the perovskite solar cell in Comparative Example 5 is basically the same as that in Example 1, except that "annealing at 60°C for 5 min and then annealing at 120°C for 8 min" is replaced with "annealing at 120°C for 13 min". The perovskite solar cell was prepared according to the method in Example 1.

[0164] Experimental Example 1

[0165] (1) During the preparation of perovskite solar cells according to the methods of Examples 1-11 and Comparative Examples 1-5, the thickness of each layer was measured using an ellipsometry, and the water contact angle of the passivation layer and the self-assembled molecular layer was measured using a contact angle meter. Specifically, the determination of the thickness of the self-assembled molecular layer and the passivation layer, as well as the water contact angle, in Examples 1-11, Comparative Examples 1-2, and Comparative Examples 4-5 was performed after step (2). First, the total thickness of the self-assembled molecular layer and the passivation layer (referred to as the thickness before film removal) and the water contact angle of the passivation layer surface (referred to as the contact angle before film removal) were measured. Then, the upper polymer passivation layer was selectively removed or swollen by ethyl acetate rinsing for 30 seconds. Subsequently, the layer was dried with nitrogen gas, and after drying, the thickness of the self-assembled molecular layer (referred to as the thickness after film removal) and the water contact angle of the self-assembled molecular layer surface (referred to as the contact angle after film removal) were measured. The results are shown in Table 1.

[0166] Table 1 Thickness and contact angle tests before and after film removal

[0167]

[0168] As shown in Table 1, this application uses co-ink inkjet printing and segmented annealing processes to form a two-layer structure on the surface of a conductive substrate, consisting of a lower self-assembled monolayer and an upper passivation layer.

[0169] (2) The perovskite solar cells prepared in Examples 1-11 and Comparative Examples 1-5 were subjected to JV testing using an AM1.5G standard solar simulator calibrated with a KG2 standard silicon solar cell. The starting voltage was set to 27V, the cutoff voltage to -0.5V, and the scan rate to 500mV / s. The JV curves of the perovskite solar cells were obtained, and their open-circuit voltage (Voc), short-circuit current (Jsc), fill factor (FF), and photoelectric conversion efficiency (PCE) were tested. The test results are shown in Table 2 and... Figures 1-2 As shown.

[0170] Table 2 Performance of perovskite solar cells

[0171]

[0172] Table 2 shows that, compared with Comparative Examples 1-5, the Jsc of the perovskite solar cells in Examples 1-11 of this application increased from 0.911 mA / cm². 2 -0.996mA / cm 2 Increased to 0.984 mA / cm 2 -1.013mA / cm 2 The Voc increased from 15.844V-24.575V to 24.830V-25.600V, the PCE increased from 9.937%-17.736% to 18.742%-20.163%, and the FF increased from 64.477-74.214 to 75.645-79.252, resulting in a significant improvement in device performance. Figure 1 This is a schematic diagram comparing the JV curves of the perovskite solar cells of Example 1 and Comparative Example 1, based on Table 1 and... Figure 1 As can be seen, compared with Comparative Example 1 which did not use a passivating material, polyacrylate compounds, in Examples 1 and 4-9 of this application, a passivating layer was introduced between the self-assembled monolayer and the perovskite layer by inkjet printing with a passivating material, polyacrylate compounds (PMMA, PEMA, PBMA, PnBA, PEA, PtBA, or PiBMA), thereby increasing the Jsc of the perovskite solar cell from 0.971 mA / cm. 2 Increased to 1.010 mA / cm 2 The Voc increased from 23.117V to 25.462V, PCE increased from 15.648% to 20.163%, and FF increased from 69.681 to 78.379. This indicates that by introducing a passivation layer using polyacrylate compounds as passivating materials, this application can passivate the chemistry and morphology of the device's bottom interface, improve interfacial recombination, and increase carrier lifetime, thereby significantly improving the short-circuit current, open-circuit voltage, fill factor, and photoelectric conversion efficiency of the perovskite solar cell. In Comparative Example 1, the ink used for inkjet printing only employed MeO-2PACz and a solvent. The ink's viscosity and dynamic surface tension regulation were insufficient, leading to droplet instability, satellite droplets, droplet deflection, linewidth fluctuations, and uneven wet film edges during the inkjet process. This resulted in a significant decrease in inkjet printing quality (including the continuity of the overall film layer, in-plane uniformity, and local surface energy consistency), further affecting the subsequent spreading and nucleation uniformity of the perovskite precursor and impacting interfacial recombination.

[0173] Figure 2 This is a schematic diagram comparing the JV curves of perovskite solar cells in Example 1 and Comparative Example 2, based on Table 1 and... Figure 2It can be seen that, compared with Comparative Example 2, which introduced propylene glycol as a solvent in its ink but did not use a passivating material, polyacrylate compounds, Example 1 of this application uses ethanol and ethyl acetate as solvents and uses a passivating material, polyacrylate compound (PMMA), and self-assembled monomolecules for inkjet printing. A passivation layer is introduced between the self-assembled monolayer and the perovskite layer. The Voc of this perovskite solar cell increased from 18.200V to 25.462V, PCE increased from 12.807% to 20.163%, and FF increased from 70.605 to 78.379. This indicates that the introduction of a passivation layer using polyacrylate compounds in this application can significantly improve the performance of perovskite solar cells. Although Comparative Example 2 uses propylene glycol to adjust the ink viscosity and improve its jetting stability, it does not use a passivating material, polyacrylate compounds. After annealing, it cannot form a passivation layer with additional interfacial passivation and crystallization control effects, and the open-circuit voltage, photoelectric conversion efficiency, and fill factor of its perovskite solar cell are still significantly reduced. Propylene glycol has a high boiling point, slow volatilization, and high residue, which disrupts the self-assembly kinetics of self-assembled single molecules. Simultaneously, it interferes with subsequent perovskite deposition and crystallization, exacerbating interfacial recombination and non-radiative losses. This indicates that simply using the high-boiling-point, small-molecule thickener propylene glycol to improve the ink jetting rheological window cannot replace polyacrylate compounds as passivation materials.

[0174] Compared to the stepwise preparation of self-assembled monolayers and passivation layers in Comparative Example 3, Example 1 of this application uses ink containing self-assembled monolayers and passivation materials for inkjet printing. The Voc of the perovskite solar cell increased from 24.575V to 25.462V, the PCE increased from 17.736% to 20.163%, and the FF increased from 74.214 to 78.379. This indicates that, compared to the stepwise preparation of self-assembled monolayers and passivation layers, this application, by using ink containing self-assembled monolayers and passivation materials for inkjet printing followed by co-annealing, achieves the simultaneous introduction of self-assembled monolayers and passivation layers, significantly improving the device performance of perovskite solar cells. This is because in stepwise inkjet printing, the first step, using ink containing MeO-2PACz, still faces problems of poor jetting stability and insufficient wet film uniformity. While the second step, inkjet printing with PMMA-containing ink, can compensate for some interface defects, it cannot completely repair the unevenness of the underlying layer caused by the poor film quality of the first step's self-assembled monolayer. In addition, the second inkjet printing and the second annealing process will bring additional solvent and thermal history to the self-assembled monolayer, causing a certain degree of local rearrangement or interface disturbance.

[0175] Compared to Comparative Examples 4-5, which were annealed at the same temperature, Example 1 of this application employed segmented annealing, resulting in a Jsc of 0.911 mA / cm² for its perovskite solar cell. 2 -0.974mA / cm 2 Increased to 1.010 mA / cm 2The Voc increased from 15.844V-24.056V to 25.462V, the PCE increased from 9.937%-15.115% to 20.163%, and the FF increased from 64.477-68.851 to 78.379. This indicates that the segmented annealing process used in this application can significantly improve the performance of perovskite solar cells. Specifically, Comparative Example 4 underwent annealing only at 60℃, which affected the density and stability of the passivation layer formed by the PMMA passivation material, thus affecting the passivation layer's regulatory function on the subsequent perovskite crystallization process. Comparative Example 5 underwent annealing only at 120℃, which shortened the time window for the migration and ordered rearrangement of self-assembled monomolecules to the substrate interface, thus affecting the uniformity and orientation order of the self-assembled monolayer.

[0176] Comparing Examples 1-2 of this application, it can be seen that perovskite solar cells with a PMMA mass fraction in the ink ranging from 0.5% to 0.75% all exhibit high Voc levels. With the increase in passivation layer thickness, the thickness of the insulating organic layer that charge carriers need to traverse during interfacial transport in Example 2 also increases accordingly, leading to a longer interfacial tunneling path, increased interfacial contact resistance and charge extraction impedance, resulting in a decrease in the PCE and FF of the perovskite solar cell.

[0177] Comparing Examples 1 and 4-9 of this application, it can be seen that the perovskite solar cells using polyacrylate compounds such as PMMA, PEMA, PBMA, PnBA, PEA, PtBA, or PiBMA as passivation materials all exhibit excellent device performance. Among them, the performance of PMMA used in Example 1 is the best. The main difference between the PEMA used in Example 4 and the PMMA used in Example 1 lies in its side chain structure and corresponding thermal properties. Under annealing conditions, PEMA is generally more prone to rearrangement and densification. The passivation layer formed by PEMA may be slightly better than that of PMMA in terms of continuity, uniformity, and surface smoothness. However, compared with Example 1, the PCE of the perovskite solar cell in Example 4 is slightly lower. Compared with PMMA used in Example 1, the chain segments of PBMA used in Example 5, PnBA used in Example 6, PEA used in Example 7, PtBA used in Example 8, and PiBMA used in Example 9 are softer, making the passivation layer formed more flexible and more prone to interface rearrangement. This affects the subsequent wetting and nucleation of the perovskite precursor, increases the charge extraction resistance to a certain extent, and leads to a decrease in the photoelectric conversion efficiency of the perovskite solar cell.

[0178] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0179] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A method for preparing a perovskite solar cell, characterized in that, Includes the following steps: Using inks that include self-assembled monomolecules and passivation materials, inkjet printing is performed on a conductive substrate, followed by segmented annealing to prepare self-assembled monomolecule layers and passivation layers. The self-assembled monolayer is located between the conductive substrate and the passivation layer; A perovskite layer is prepared on the passivation layer; The passivation material includes polyacrylate compounds; The thickness of the passivation layer is 2nm-10nm; The conditions for segmented annealing include: first annealing at 50℃-70℃, and then second annealing at 100℃-150℃.

2. The method for preparing a perovskite solar cell according to claim 1, characterized in that, The polyacrylate compounds include at least one of polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybutyl methacrylate, polyethyl methacrylate, polytert-butyl methacrylate, and polyisobutyl methacrylate.

3. The method for preparing a perovskite solar cell according to claim 1, characterized in that, The self-assembled monomolecules include phosphonic acid self-assembled monomolecules; The phosphonic acid self-assembled monomers include [2-(9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid, [2-(3,6-dimethyl-9H-carbazole-9-yl)ethyl]phosphonic acid, [4-(9H-carbazole-9-yl)ethyl]phosphonic acid, and [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid. At least one of [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid, [4-(7H-dibenzocarbazole-7-yl)butyl]phosphonic acid, [2-(9-bromocarbazole-9-yl)ethyl]phosphonic acid, [2-(9-chlorocarbazole-9-yl)ethyl]phosphonic acid, [4-(9-bromocarbazole-9-yl)butyl]phosphonic acid, and [4-(9-fluorocarbazole-9-yl)butyl]phosphonic acid.

4. The method for preparing a perovskite solar cell according to any one of claims 1-3, characterized in that, The ink also includes a solvent; The solvent includes ethanol and / or ethyl acetate.

5. The method for preparing a perovskite solar cell according to claim 4, characterized in that, It meets at least one of the following characteristics: (1) The concentration of self-assembled monomers in the ink is 0.1 mg / mL to 0.4 mg / mL; (2) The passivating material in the ink has a mass fraction of 0.1%-1%; (3) The solvent in the ink includes ethanol and ethyl acetate, and the volume ratio of ethanol to ethyl acetate is 5:5-9:1; (4) The viscosity of the ink is 5.0 mPa·s-10.0 mPa·s; (5) The surface tension of the ink is 20.0mN / m-30.0mN / m.

6. The method for preparing a perovskite solar cell according to claim 1, characterized in that, It meets at least one of the following characteristics: (1) The first annealing time is 3-8 minutes; (2) The second annealing time is 5 min-10 min; (3) The conditions for inkjet printing include: resolution 720×360 DPI; printhead drive voltage 10V-20V; printing speed 300mm / s-800mm / s; printhead temperature 25℃-35℃; (4) Before inkjet printing on a conductive substrate using ink comprising self-assembled monomolecules and passivating materials, the conductive substrate is further subjected to a pretreatment step, wherein the pretreatment method includes at least one of cleaning treatment, ultraviolet ozone treatment and plasma activation treatment. (5) The conductive substrate includes one of an inorganic conductive substrate and an organic-inorganic composite conductive substrate; The inorganic conductive substrate includes fluorine-doped tin oxide glass and / or indium tin oxide glass; The organic-inorganic composite conductive substrate includes an organic film layer and indium tin oxide glass disposed on the surface of the organic film layer; the organic film layer includes polyethylene terephthalate and / or polyethylene naphthalate. (6) The perovskite layer comprises a perovskite material, the structural formula of which is ABX3; Wherein, A is selected from at least one of formamidinium cation, methylamine cation and cesium cation, B is selected from lead cation and / or tin cation, and X is selected from at least one of fluorine anion, chloride anion, bromide anion and iodide anion.

7. The method for preparing a perovskite solar cell according to claim 1, characterized in that, After preparing a perovskite layer on the passivation layer, the process further includes the step of sequentially preparing an electron transport layer, a barrier layer, and an electrode layer on the perovskite layer.

8. The method for preparing a perovskite solar cell according to claim 7, characterized in that, It meets at least one of the following characteristics: (1) The material of the electron transport layer includes at least one of C60, methyl [6,6]-phenyl-C61-butyrate and zinc oxide; (2) The material of the barrier layer includes 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and / or tin dioxide; (3) The material of the electrode layer includes at least one of silver, copper, gold and carbon.

9. A perovskite battery, characterized in that, The perovskite solar cell is prepared by the method described in any one of claims 1-8.

10. An electrical device, characterized in that, The perovskite battery includes the perovskite battery prepared by the method of any one of claims 1-8 or the perovskite battery of claim 9.

Images