Large-area uniform strong bonding hole transport layer and preparation method, perovskite solar cell

Abstract

The application discloses a large-area uniform strong bonding hole transport layer and a preparation method thereof and a perovskite solar cell. The strong bonding hole transport layer composed of a nickel oxide layer and a composite interface layer is constructed by mixing a conductive polymer dodecyl benzene sulfonate doped polyaniline and Me-4PACz, the composite interface layer exhibits excellent wettability, compactness and adsorption stability, and the perovskite module prepared based on the strong bonding hole transport layer has significantly improved photoelectric conversion efficiency and can also present uniform and bright light emitting characteristics on a large-area substrate. The application realizes uniform coating and strong bonding adsorption of a self-assembled monolayer at a component level, and comprehensively solves industrialization key problems such as large-area film forming difficulty, insufficient interface adsorption force, disordered molecular arrangement and poor buried interface crystalline quality, thereby providing a stable and scalable material and process basis for industrial application of perovskite photovoltaic technology.

Description

Technical Field

[0001] This invention belongs to the field of perovskite solar cell technology, and more specifically, relates to a large-area uniform strongly bonded hole transport layer and its preparation method, as well as perovskite solar cells. Background Technology

[0002] Inverted perovskite solar cells (PSCs) and modules have attracted widespread attention due to their advantages such as low processing temperature, compatibility with large-area fabrication, and suitability for integration into tandem devices. The interface between the hole transport layer and the perovskite thin film plays a crucial role in the overall performance of inverted PSCs. Nickel oxide (NiO) x Due to its good stability, low cost, and adjustable conductivity, NiO has become one of the most commonly used inorganic hole transport layers in inverted PSCs structures. x The surface has a large number of defect sites, which reduces the NiO content. x To address surface defects, improve energy level matching, and suppress interfacial nonradiative recombination, self-assembled monolayers (SAMs) are typically introduced onto the NiOx surface. Me-4PACZ, as a typical SAM material, has been widely studied due to its good hole extraction and interfacial manipulation capabilities.

[0003] SAM, as a small molecule material, is used in large-area NiO. x When applying coatings to a substrate using scraping or slot coating methods, uneven wetting, localized buildup, coffee ring effect, and dewetting are common, making it difficult to achieve uniform coating at the module level. Patent CN120379498A proposes introducing nitrogen-containing polymers as additives into the hole transport layer to reduce the aggregation of self-assembled molecules. However, the nitrogen-containing polymers introduced in this approach are insulators. While they can suppress SAM aggregation, the presence of these insulating polymers hinders interfacial charge transport, thus increasing interfacial resistance. Insufficient uniformity of the SAM layer prevents the provision of uniform nucleation sites for the upper perovskite layer, resulting in poor crystal quality at the perovskite-buried interface and the formation of excessive insulating lead iodide phase at the interface, severely hindering localized charge transport. Furthermore, small-molecule SAMs lack skeletal support and are prone to aggregation in NiO. x The surface tends to aggregate randomly, making it impossible to achieve the desired directional arrangement of "phosphate groups anchoring downwards to the substrate and carbazole groups extracting cavities upwards." Patent CN119604167A proposes to prepare a uniform and compact self-assembled monolayer by optimizing the spin-coating solution formulation of MeO-2PACz and isopropanol. However, this approach fails to fundamentally solve the problem of small molecule SAM lacking skeletal support, nor can it enhance the adsorption stability between SAM molecules and the substrate.

[0004] Furthermore, small molecule SAM relies solely on phosphate groups and NiO xThe surface bonds to SAM through physical or weak chemical adsorption. When perovskite modules face high temperatures and continuous light exposure, small molecules are highly susceptible to thermal or photo-induced desorption, leading to increased interfacial transport barriers and rapid performance degradation. Current technologies do not adequately address the adsorption stability of SAM molecules, failing to provide effective techniques to enhance their adsorption stability under high-temperature and light-exposed conditions, nor do they resolve the fundamental issue of easy thermal or photo-induced desorption of small-molecule SAM. Summary of the Invention

[0005] To address the aforementioned deficiencies or improvement needs of existing technologies, this invention provides a large-area, uniform, strongly bonded hole transport layer, its preparation method, and a perovskite solar cell. By co-mixing conductive polymer dodecylbenzenesulfonate-doped polyaniline with Me-4PACz, a strongly bonded hole transport layer composed of a nickel oxide layer and a composite interface layer is constructed. This composite interface layer exhibits excellent wettability, density, and adsorption stability. Furthermore, perovskite modules prepared based on this strongly bonded hole transport layer show significantly improved photoelectric conversion efficiency and exhibit uniform and bright luminescence characteristics even on large-area substrates. This invention achieves uniform coating and strong bonded adsorption of self-assembled monolayers at the module level, comprehensively solving key industrialization problems such as difficulties in large-area film formation, insufficient interfacial adsorption force, disordered molecular arrangement, and poor crystallization quality of the buried interface. It provides a stable and scalable material and process foundation for the industrial application of perovskite photovoltaic technology.

[0006] To achieve the above objectives, according to one aspect of the present invention, a large-area uniform strongly bonded hole transport layer is provided, characterized in that the strongly bonded hole transport layer comprises a nickel oxide layer and a composite interface layer disposed on the nickel oxide layer; wherein the composite interface layer comprises Me-4PACz and dodecylbenzenesulfonate-doped polyaniline.

[0007] Preferably, the mass ratio of Me-4PACz to the dodecylbenzenesulfonate-doped polyaniline is 1:1 to 1:10.

[0008] Preferably, the surface molecular coverage of the composite interface layer is ≥6×10⁻⁶. 13 Number of molecules / cm 2 .

[0009] According to a second aspect of the present invention, a perovskite solar cell is provided, comprising the aforementioned strongly bonded hole transport layer.

[0010] Preferably, the perovskite solar cell comprises, from bottom to top, the following layers stacked sequentially: a transparent conductive substrate, a strongly bonded hole transport layer, a perovskite light absorption layer, an electron transport layer, and a back electrode.

[0011] Preferably, multiple perovskite solar cells are connected in series to form a perovskite solar module, and the effective illumination area of ​​the module is 100 cm². 2 above.

[0012] According to a third aspect of the present invention, a method for preparing a large-area uniform strongly bonded hole transport layer is provided, comprising the following steps: Me-4PACz and dodecylbenzenesulfonate-doped polyaniline were dissolved together in an organic solvent of dimethyl sulfoxide and isopropanol and stirred to obtain a homogeneous mixed solution. The mixed solution is deposited on a nickel oxide substrate by a blade coating method, followed by annealing to form a composite interface layer on the nickel oxide substrate. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0013] Preferably, the volume ratio of isopropanol to dimethyl sulfoxide is 0:1 to 2:5, the total concentration of Me-4PACz and dodecylbenzenesulfonate-doped polyaniline in the mixed solution is 0.6 mg / mL to 3.5 mg / mL, and the stirring time is 8 to 10 hours.

[0014] Preferably, the coating speed of the blade coating method is 5 mm / s to 25 mm / s.

[0015] Preferably, the annealing temperature is 80 ℃~150 ℃, the time is 3 minutes~20 minutes, and the thickness of the composite interface layer is 3 nm~20 nm.

[0016] In summary, compared with the prior art, the above-described technical solutions conceived by this invention can achieve the following beneficial effects: 1. This invention creatively co-mixes the self-assembled monomolecular material Me-4PACz with dodecylbenzenesulfonate-doped polyaniline (SPANI) to construct a strongly bonded hole transport layer consisting of a nickel oxide layer and a composite interface layer. The long-chain conjugated structure of SPANI forms a physical constraint network, effectively suppressing small molecule aggregation and solving the process problem of uniform coating of traditional small molecule SAM materials on large-area substrates; simultaneously, the sulfonate groups on the SPANI molecular chain and NiO xA strong chemical anchoring is formed on the substrate surface. The amine groups form hydrogen bonds with the phosphate groups of Me-4PACz, and the aromatic conjugated framework forms π-π stacks with the carbazole groups of Me-4PACz. These three elements synergistically endow the composite interface layer with excellent wettability, density, and adsorption stability. Based on the above synergistic mechanism, this invention achieves a significant reduction in contact angle, a substantial increase in surface coverage, and strong bonding characteristics with almost no attenuation after solvent rinsing. It systematically improves the three major technical challenges of small molecule SAMs—uniform coating, disordered molecular arrangement, and weak interfacial adsorption—at the molecular level, laying a solid interfacial foundation for the subsequent fabrication of high-performance perovskite devices.

[0017] 2. In this invention, the multiple interactions between SPANI and Me-4PACz induce the vertically ordered arrangement of Me-4PACz molecules on the substrate, achieving ideal energy level matching and interface compatibility between the strongly bonded hole transport layer and the perovskite absorber layer. Perovskite solar cells fabricated based on this strongly bonded hole transport layer exhibit significantly improved open-circuit voltage and fill factor, greatly enhanced carrier extraction efficiency, effective suppression of interfacial recombination, and comprehensive optimization of charge transport characteristics. Especially under high-temperature and light-irradiation conditions, the incorporation of SPANI enables Me-4PACz to achieve optimal energy level matching and interface compatibility between the strongly bonded hole transport layer and the perovskite absorber layer. x Desorption on the substrate was effectively suppressed, and the high-temperature light-induced stability of the interface layer was significantly enhanced. Simultaneously, the perovskite buried interface porosity was eliminated, grain size increased, and PbI2 impurity peaks disappeared, resulting in a significant improvement in crystal quality, accelerated carrier transport, and overall improved device electrical quality. In contrast, the performance of battery devices using Me-4PACz or SPANI alone was far inferior to that of this invention, fully demonstrating the synergistic effect of "1+1>2" between SPANI and Me-4PACz.

[0018] 3. The perovskite module prepared based on the aforementioned strongly bonded hole transport layer of this invention achieves excellent photoelectric conversion efficiency over a large area, with significantly better open-circuit voltage and fill factor than the control. Large-area photoluminescence characterization shows that the perovskite film prepared by this invention is uniformly bright on a large-area substrate, while the control sample fails to emit light in most areas. Further analysis of the large-area film by region reveals that the performance indicators of the sample prepared by this invention are highly consistent, while the control sample exhibits large fluctuations and low overall performance, proving that this invention has good uniformity and repeatability over a large area. Electroluminescence testing of the module further verifies that the luminescence uniformity and intensity of the module prepared by this invention are significantly better than the control, and carrier extraction is effectively accelerated. This invention successfully achieves module-level (>100 cm⁻¹) 2 The uniform coating of small-molecule SAM comprehensively improves key industrialization problems such as difficulty in large-area uniform film formation, insufficient interfacial adsorption force, disordered molecular arrangement, and poor crystallization quality of perovskite buried interface, providing a stable and scalable material and process foundation for the industrial application of perovskite photovoltaic technology. Attached Figure Description

[0019] Figure 1 These are contact angle test diagrams of the interface layer obtained in Embodiment 1 and Comparative Example 1 of the present invention; Figure 2 These are cyclic voltammetry test diagrams of the interface layer obtained in Example 1 and Comparative Example 1 of the present invention. Figure 3 These are grazing incidence wide-angle X-ray scattering test images of the interface layers prepared in Embodiment 1 and Comparative Example 1 of the present invention; Figure 4 The X-ray photoelectron spectra of the interface layer obtained in Example 1 and Comparative Example 1 of this invention before and after DMF rinsing are shown. Figure 5 The Fourier transform infrared spectra of the interface layer obtained in Example 1, Comparative Example 1, and Comparative Example 2 of this invention are shown below. Figure 6 These are Kelvin probe atomic force microscopy images of the interface layers prepared in Example 1 and Comparative Example 1. Figure 7 The energy dispersive X-ray spectra of the interface layers prepared in Example 1 and Comparative Example 1 are shown below. Figure 8 Atomic force microscopy-infrared spectra of the interface layers obtained in Example 1 and Comparative Example 1; Figure 9 The images show the AFM and AFM-IR images of the perovskite film obtained in Comparative Example 1 of this invention after exfoliation. Figure 10 The images shown are AFM and AFM-IR images of the perovskite film obtained in Example 1 of this invention after exfoliation. Figure 11 These are scanning electron microscope (SEM) images of the perovskite thin films prepared in Example 1 and Comparative Example 1 of the present invention. Figure 12 X-ray diffraction and grazing incidence wide-angle X-ray scattering patterns of the perovskite thin films prepared in Example 1 and Comparative Example 1 of this invention; Figure 13 The in-situ ultraviolet-visible spectrum and in-situ photoluminescence spectrum of the perovskite thin films prepared in Example 1 and Comparative Example 1 of this invention are shown below. Figure 14 The images show the UV-Vis absorption spectrum, steady-state photoluminescence spectrum, and time-resolved photoluminescence decay curves of the perovskite films prepared in Example 1 and Comparative Example 1 of this invention. Figure 15 These are laser confocal fluorescence lifetime images of the perovskite thin films prepared in Example 1 and Comparative Example 1 of the present invention. Figure 16Photoluminescence mapping diagrams of perovskite thin films prepared on a 14 cm × 14 cm large-area substrate in Example 1 and Comparative Example 1 of the present invention, and statistical diagrams of PLQY and TRPL of 25 slices. Figure 17 The figures show the photovoltaic performance and carrier dynamics test results of the perovskite solar modules prepared in Example 1 and Comparative Example 1 of this invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0021] This invention provides a large-area, uniform, strongly bonded hole transport layer, comprising a nickel oxide layer and a composite interface layer disposed on the nickel oxide layer; wherein the composite interface layer is formed by a co-mixture of Me-4PACz and dodecylbenzenesulfonate-doped polyaniline, the mass ratio of Me-4PACz to the dodecylbenzenesulfonate-doped polyaniline being 1:1 to 1:10, preferably, the surface molecular coverage of the composite interface layer is ≥6×10⁻⁶. 13 Number of molecules / cm 2 The Me-4PACz mentioned is [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, a self-assembled monolayer material commonly used in perovskite solar cells. Dodecylbenzenesulfonate-doped polyaniline (SPANI) refers to a conductive polymer composite with polyaniline as the main chain backbone and dodecylbenzenesulfonate as the dopant ion. The polyaniline backbone consists of alternating benzene and quinone rings, and dodecylbenzenesulfonate forms ionic bonds with the imine groups on the polyaniline backbone through sulfonic acid groups, achieving doping. In the aggregated structure, the polyaniline backbone typically forms a conductive layer, while the dodecylbenzenesulfonate ions act as an "isolation layer," arranged orderly between the backbones. This regular, ordered structure is highly conducive to charge transport and is the basis for the material's high electrical conductivity.

[0022] This invention also provides a perovskite solar cell including the strongly bonded hole transport layer, wherein the perovskite solar cell has an inverted structure and comprises, from bottom to top, the following layers stacked sequentially: a transparent conductive substrate, a nickel oxide layer disposed on the transparent conductive substrate, a composite interface layer disposed on the nickel oxide layer, a perovskite light-absorbing layer, an electron transport layer, and a back electrode. Preferably, multiple perovskite solar cells are connected in series to form a perovskite solar module, and the effective illumination area of ​​the module is 100 cm².2 above.

[0023] It should be noted that a battery refers to the smallest unit capable of independent photoelectric conversion, typically a small-area device (e.g., 0.1 cm²), used for testing material performance and optimizing process parameters. A module refers to a power generation product consisting of multiple batteries connected in series internally (laser etching P1 / P2 / P3) and packaged together, typically a large-area device (e.g., 100 cm² or more), which can be directly used for actual power generation.

[0024] This invention also provides a method for preparing a large-area uniform strongly bonded hole transport layer, characterized by comprising the following steps: Me-4PACz and dodecylbenzenesulfonate-doped polyaniline were dissolved together in an organic solvent of dimethyl sulfoxide and isopropanol in a volume ratio of 0:1 to 2:5 and stirred for 8 to 10 hours until the solution was homogeneous. The total concentration of Me-4PACz and dodecylbenzenesulfonate-doped polyaniline in the mixed solution was 0.6 mg / mL to 3.5 mg / mL. The mixed solution was deposited on a nickel oxide substrate by a blade coating method at a coating speed of 5 mm / s to 25 mm / s. The deposited substrate was annealed at 80 °C to 150 °C for 3 to 20 minutes to form a composite interface layer with a thickness of 3 nm to 20 nm on the nickel oxide substrate. The composite interface layer and the nickel oxide substrate together constitute a strongly bonded hole transport layer.

[0025] The present invention will be described in detail below with reference to specific embodiments.

[0026] Example 1 This embodiment provides a method for preparing a strongly bonded hole transport layer, the specific steps of which are as follows: (1) Take 3 mg of dodecylbenzenesulfonate-doped polyaniline (SPANI) and 9 mg of Me-4PACZ and add them together to 10 mL of a mixed solution of dimethyl sulfoxide and isopropanol (volume ratio of 0.5:9.5), and stir at 25 °C for 9 h.

[0027] (2) Prepare NiO x The fluorine-doped tin oxide (FTO) conductive glass substrate was cleaned with a nitrogen gun and placed on a doctor blade coater. The resulting mixed solution was then coated onto the NiO substrate using a doctor blade coater at a speed of 15 mm / s. x A 10nm composite interface layer was prepared by annealing the substrate on a hot plate at 100°C for 5 minutes. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0028] Secondly, this embodiment provides a perovskite solar cell, which includes a strongly bonded hole transport layer. The specific steps are as follows: (1) The FTO glass substrate was cleaned with deionized water, anhydrous ethanol and acetone and then dried. Subsequently, it was subjected to UV treatment to obtain a clean FTO conductive glass substrate.

[0029] (2) NiO was prepared on an FTO substrate by a blade coating method. x Electron transport layer.

[0030] (3) According to the preparation method of the strongly bonded hole transport layer in this embodiment, in NiO x A composite interface layer is prepared on the electron transport layer to obtain a strongly bonded hole transport layer.

[0031] (4) The FAPbI3 perovskite precursor solution was coated onto the strongly bonded hole transport layer at a speed of 15 mm / s, vacuum flashed for 30 s, and annealed at 120 °C for 30 minutes to obtain the FAPbI3 perovskite active layer. The concentration of the FAPbI3 perovskite precursor solution was 1 M, and the solvent was a mixture of NMP and DMF with a volume ratio of 1:9.

[0032] (5) A C60 layer with a thickness of 25 nm is deposited on the perovskite active layer.

[0033] (6) A 20 nm tin oxide layer is prepared on the C60 layer using atomic layer deposition technology.

[0034] (7) A Cu electrode layer with a thickness of 100 nm is deposited on the tin oxide layer to obtain a complete perovskite cell.

[0035] Furthermore, this embodiment also provides a perovskite module, the preparation method of which differs from the above-mentioned perovskite solar cell in that a laser scribing step is added during the preparation process to form an internal series structure. The specific steps are as follows: (1) The 14 cm × 14 cm FTO glass substrate was cleaned with deionized water, anhydrous ethanol and acetone and then dried. It was then subjected to UV treatment to obtain a clean FTO conductive glass substrate.

[0036] (2) Use a laser scribing device to scribing cut the FTO conductive glass substrate with P1 lines.

[0037] (3) NiO was prepared on an FTO substrate by a blade coating method. x Electron transport layer.

[0038] (4) Following the same method as the above-mentioned battery, in NiO x A strongly bonded hole transport layer is fabricated on the electron transport layer.

[0039] (5) Following the same method as the battery described above, a FAPbI3 perovskite active layer was prepared on the strongly bonded hole transport layer.

[0040] (6) A C60 layer with a thickness of 25 nm is deposited on the perovskite active layer.

[0041] (7) A 20 nm tin oxide layer was prepared on the C60 layer using atomic layer deposition technology (thus, a complete perovskite multilayer thin film structure was prepared on a 14 cm × 14 cm substrate, which can be used for large-area uniformity testing).

[0042] (8) Use a laser scribing device to scribing and cutting the material obtained in step (7) with P2 lines.

[0043] (9) A Cu electrode layer with a thickness of 100 nm is deposited on the tin oxide layer.

[0044] (10) Use a laser scribing device to perform P3 scribing on the material obtained in step (9) to obtain a complete perovskite module.

[0045] Example 2 The difference between this embodiment and Embodiment 1 is that it provides a method for preparing a strongly bonded hole transport layer, the specific steps of which are as follows: 3 mg of SPANI and 3 mg of Me-4PACZ were added together to 10 mL of isopropanol solution and stirred at 25 °C for 8 h. The resulting solution contained NiO was then prepared. x After the FTO conductive glass substrate was cleaned with a nitrogen gun, it was placed on a doctor blade coater. The resulting mixed solution was then coated onto the NiO substrate using a doctor blade coater at a speed of 5 mm / s. x A 3 nm composite interface layer was prepared by annealing the substrate on a hot plate at 80 °C for 3 minutes. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0046] Example 3 The difference between this embodiment and Embodiment 1 is that it provides a method for preparing a strongly bonded hole transport layer, the specific steps of which are as follows: 3 mg SPANI and 6 mg Me-4PACZ were added to 10 mL of a mixed solution of dimethyl sulfoxide and isopropanol (volume ratio 1:4), and stirred at 25 °C for 8 h. The solution containing NiO was then prepared. x After the FTO conductive glass substrate was cleaned with a nitrogen gun, it was placed on a doctor blade coater. The resulting mixed solution was then coated onto the NiO substrate at a speed of 10 mm / s using a doctor blade coating method. xAn 8 nm composite interface layer was prepared by annealing the substrate on a hot plate at 100 °C for 10 minutes. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0047] Example 4 The difference between this embodiment and Embodiment 1 is that it provides a method for preparing a strongly bonded hole transport layer, the specific steps of which are as follows: 3 mg of SPANI and 15 mg of Me-4PACZ were added to 10 mL of a mixed solution of dimethyl sulfoxide and isopropanol (volume ratio 1:5), and stirred at 25 °C for 10 h. The resulting NiO product was then prepared. x After the FTO conductive glass substrate was cleaned with a nitrogen gun, it was placed on a doctor blade coater. The resulting mixed solution was then coated onto the NiO substrate at a speed of 15 mm / s using a doctor blade coating method. x A 10 nm composite interface layer was prepared by annealing the substrate on a hot plate at 120 °C for 15 minutes. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0048] Example 5 The difference between this embodiment and Embodiment 1 is that it provides a method for preparing a strongly bonded hole transport layer, the specific steps of which are as follows: 3 mg SPANI and 24 mg Me-4PACZ were added to 10 mL of a mixed solution of dimethyl sulfoxide and isopropanol (volume ratio 2:3), and stirred at 25 °C for 10 h. The resulting NiO product was then... x After the FTO conductive glass substrate was cleaned with a nitrogen gun, it was placed on a doctor blade coater. The resulting mixed solution was then coated onto the NiO substrate using a doctor blade coater at a speed of 20 mm / s. x A 15 nm composite interface layer was prepared by annealing the substrate on a hot plate at 150 °C for 15 minutes. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0049] Example 6 The difference between this embodiment and Embodiment 1 is that it provides a method for preparing a strongly bonded hole transport layer, the specific steps of which are as follows: 3 mg of SPANI and 30 mg of Me-4PACZ were added to 10 mL of a mixed solution of dimethyl sulfoxide and isopropanol (volume ratio 2:5), and stirred at 25 °C for 10 h. The resulting NiO product was then... x After the FTO conductive glass substrate was cleaned with a nitrogen gun, it was placed on a doctor blade coater. The resulting mixed solution was then coated onto the NiO substrate using a doctor blade coater at a speed of 25 mm / s. xA 20 nm composite interface layer was prepared by annealing the substrate on a hot plate at 150 °C for 20 minutes. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

[0050] Comparative Example 1 The difference between this comparative example and Example 1 is that SPANI is not added to the dimethyl sulfoxide and isopropanol mixed solution; that is, only Me-4PACz is dissolved in the dimethyl sulfoxide and isopropanol mixed solution. The remaining steps are the same as in Example 1.

[0051] Comparative Example 2 The difference between this comparative example and Example 1 is that Me-4PACZ is not added to the dimethyl sulfoxide and isopropanol mixed solution; that is, only SPANI is dissolved in the dimethyl sulfoxide and isopropanol mixed solution. The remaining steps are the same as in Example 1.

[0052] Comparative Example 3 The difference between this comparative example and Example 1 is that the mass ratio of Me-4PACz to SPANI in the dimethyl sulfoxide and isopropanol mixed solution is 1:11.

[0053] Comparative Example 4 The difference between this comparative example and Example 1 is that the mass ratio of Me-4PACz to SPANI in the dimethyl sulfoxide and isopropanol mixed solution is 2:1.

[0054] Device performance testing Photovoltaic performance tests were conducted on the perovskite modules prepared in all the above embodiments and comparative examples. The open-circuit voltage (VOC), short-circuit current density (JSC), fill factor (FF), and photoelectric conversion efficiency (PCE) were tested, and the results are shown in Table 1.

[0055] Table 1. Photovoltaic performance test results of the perovskite modules in each embodiment and comparative example. As shown in Table 1, the perovskite modules of Examples 1-6 of this invention significantly outperform the comparative examples in terms of open-circuit voltage, short-circuit current density, fill factor, and photoelectric conversion efficiency. Example 1 exhibits the best performance. Comparing Example 1 with Comparative Examples 1-2, the PCE of the device using Me-4PACz alone is only 18.72%, and the PCE of the device using SPANI alone is only 9.39%. However, the PCE increases to 22.52% after the two are combined. This indicates a significant synergistic effect between SPANI and Me-4PACz, rather than a simple performance additive effect. Comparative Examples 1-6 with Comparative Examples 3-4 further demonstrate that the mass ratio of Me-4PACz to SPANI needs to be controlled within a specific range; exceeding this range significantly degrades device performance.

[0056] To further reveal the intrinsic mechanism of the optimal performance of Example 1 and the microscopic nature of the synergistic effect between SPANI and Me-4PACz, the composite interface layer prepared according to step (4) of Example 1 and the individual Me-4PACz interface layer prepared according to step (4) of Comparative Example 1 were characterized from the perspectives of wettability, surface coverage, molecular orientation, adsorption stability, chemical bonding mechanism, and large-area uniformity. The results show that... Figures 1-8 .

[0057] Figure 1 The images show contact angle test diagrams of the interface layers obtained in Example 1 and Comparative Example 1. Figure 1 (a) shows the contact angle test results of the DMF with a single Me-4PACz interface layer prepared in Comparative Example 1. Figure 1 (b) shows the contact angle test results of the composite interface layer prepared in Example 1 with DMF. Figure 1 (c) shows the contact angle test results of the NMP with a single Me-4PACz interface layer prepared in Comparative Example 1. Figure 1 (d) shows the contact angle test results of the sample obtained in Example 1 with NMP. It can be seen that the contact angles of the single Me-4PACz interface layer prepared in Comparative Example 1 with DMF and NMP are 83.8° and 90.7°, respectively; while the contact angles of the composite interface layer prepared in Example 1 with DMF and NMP are reduced to 50.0° and 58.4°, respectively. The significant reduction in contact angle indicates that the introduction of SPANI effectively improves the hydrophilicity of the composite interface layer, which is beneficial for the uniform spreading of the perovskite precursor solution on a large-area substrate.

[0058] Figure 2 The images show the cyclic voltammetry test results of the interface layers obtained in Example 1 and Comparative Example 1. The test results were obtained using the cyclic voltammetry method. Figure 2 In Figure (a), the CV curve of the isolated Me-4PACz interface layer obtained in Comparative Example 1 is shown. Figure 2 (b) shows the CV curve of the composite interface layer obtained in Example 1. Figure 2 In the middle (c), the surface coverage fitting curve of the prepared composite interface layer is shown. Figure 2 Figure (d) shows the surface coverage fitting curve of the prepared composite interface layer. It can be seen that the surface coverage of the single Me-4PACz interface layer prepared in Comparative Example 1 is 3.91 × 10⁻⁶. 13 Number of molecules / cm 2 The surface coverage of the composite interface layer prepared in Example 1 was increased to 6.38 × 10⁻⁶. 13 Number of molecules / cm 2 This indicates that the present invention effectively enhances the SAM molecule's performance in NiO by co-mixing SPANI with Me-4PACz.x The coverage of the substrate surface is beneficial to the efficient transport of charge, thereby increasing the open-circuit voltage.

[0059] Figure 3 The images shown are grazing incidence wide-angle X-ray scattering test patterns of the interface layers prepared in Example 1 and Comparative Example 1, wherein... Figure 3 In the middle (a), the GIWAXS diagram of the individual Me-4PACz interface layer obtained in Comparative Example 1 is shown. Figure 3 (b) is the GIWAXS diagram of the composite interface layer prepared in Example 1. It can be seen that, compared to the disordered molecular arrangement on the surface of the individual Me-4PACz interface layer prepared in Comparative Example 1, the Me-4PACz molecules in the composite interface layer prepared in Example 1 exhibit a more ordered and better oriented distribution in the direction perpendicular to the sample surface. This indicates that a π-π interaction occurs between the aromatic conjugated structure of SPANI and the carbazole backbone of Me-4PACz in this invention, inducing the orderly arrangement of Me-4PACz molecules on the interface, which is beneficial for the efficient extraction of holes.

[0060] Figure 4 The X-ray photoelectron spectra of the interface layer prepared in Example 1 and Comparative Example 1 before and after DMF rinsing are shown below. Figure 4 (a) shows the N element XPS spectra of the Me-4PACz interface layer obtained in Comparative Example 1 before and after rinsing. Figure 4 (b) shows the XPS spectra of P element in the isolated Me-4PACz interface layer prepared in Comparative Example 1 before and after rinsing. Figure 4 (c) shows the N element XPS spectra of the composite interface layer prepared in Example 1 before and after rinsing. Figure 4 Image (d) shows the XPS spectra of P elements before and after rinsing of the composite interface layer prepared in Example 1. It can be seen that for the single Me-4PACz interface layer obtained in Comparative Example 1, the content of N and P elements on its surface significantly decreased after DMF rinsing; while for the composite interface layer obtained in Example 1, no significant decrease in the content of N and P elements on its surface was observed after DMF rinsing. This indicates that the introduction of SPANI in this invention can significantly enhance the N and P content of Me-4PACz in NiO. x The adsorption capacity on the substrate is enhanced, thereby preventing thermal or photo-induced desorption of Me-4PACz under high temperature and light conditions.

[0061] Figure 5 The Fourier transform infrared spectra of the interface layers prepared in Example 1, Comparative Examples 1 and 2 are shown below. Figure 5 In the middle (a), the FTIR spectrum of Me-4PACz is compared with that of the single Me-4PACz interface layer in Comparative Example 1 and the composite interface layer in Example 1. Figure 5(b) shows the FTIR spectrum of SPANI-based composite interface layer, comparing the single SPAIN interface layer of Comparative Example 2 with the composite interface layer prepared in Example 1. It can be seen that, compared to the interface layers with only Me-4PACz or only SPANI, the characteristic peaks of phosphate groups and CN bonds in the composite interface layer blended with Me-4PACz show significant shifts. This indicates that there are hydrogen bonds and π-π interactions between SPANI and Me-4PACz. This multiple chemical bonding effectively reduces the local aggregation of Me-4PACz and enhances its performance in NiO. x Adsorption capacity on the substrate.

[0062] To further verify the large-area uniformity of the composite interface layer from multiple dimensions, this invention systematically characterized the surface potential uniformity, elemental distribution uniformity, and phosphate group distribution uniformity of the composite interface layer using Kelvin probe atomic force microscopy (KPFM), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy-infrared spectroscopy (AFM-IR).

[0063] Figure 6 These are Kelvin probe atomic force microscopy images of the interface layers prepared in Example 1 and Comparative Example 1. Figure 6 In Figure (a), KPFM two-dimensional and three-dimensional images of the individual Me-4PACz interface layer obtained in Comparative Example 1 are shown. Figure 6 (b) shows the two-dimensional and three-dimensional KPFM images of the composite interface layer prepared in Example 1. It can be seen that the surface potential of the individual Me-4PACz interface layer prepared in Comparative Example 1 is uneven and the potential difference is large; while the composite interface layer prepared in Example 1 exhibits higher film surface potential uniformity and a significantly reduced potential difference. This indicates that the introduction of SPANI allows Me-4PACz to form a more compact and uniformly distributed SAM layer, eliminating exposed NiO. x This enhances the coverage of SAM molecules, while the reduced contact potential difference is more conducive to carrier extraction.

[0064] Figure 7 The images show the energy-dispersive X-ray spectra of the interface layers obtained in Example 1 and Comparative Example 1. Figure 7 (a) shows the EDS element distribution of a single Me-4PACz interface layer obtained in Comparative Example 1. Figure 7 Figure (b) shows the EDS elemental distribution of the composite interface layer prepared in Example 1. It can be seen that the O, P, N, and S elemental distribution of the individual Me-4PACz interface layer prepared in Comparative Example 1 is uneven; while the O, P, N, and S elemental distribution of the composite interface layer prepared in Example 1 is more uniform. This indicates that blending SPANI with Me-4PACz molecules can enhance the uniformity of the SAM coating.

[0065] Figure 8 Atomic force microscopy-infrared spectra of the interface layers obtained in Example 1 and Comparative Example 1 are shown. Figure 8 (a) shows the AFM morphology of the isolated Me-4PACz interface layer obtained in Comparative Example 1. Figure 8 (b) shows the isolated Me-4PACz interface layer prepared in Comparative Example 1 at 940 cm⁻¹. -1 AFM-IR phosphate group distribution diagram at the location, Figure 9 Image (c) shows the AFM morphology of the composite interface layer obtained in Example 1. Figure 8 (d) shows the composite interface layer prepared in Example 1 at 940 cm⁻¹. -1 The AFM-IR phosphate group distribution diagram shows that the phosphate group distribution in the isolated Me-4PACz interface layer prepared in Comparative Example 1 is uneven, with obvious local aggregation; while the phosphate group distribution in the composite interface layer prepared in Example 1 is more uniform, without obvious local aggregation. This directly proves that SPANI effectively inhibits the local aggregation of Me-4PACz at the molecular scale.

[0066] To further verify the effect of SPANI on Me-4PACz in NiO x The enhanced adsorption capacity on the substrate was investigated by conducting high-temperature photoaging tests on the perovskite films prepared on the composite interface layer of Example 1 and the interface layer of Comparative Example 1, respectively. The perovskite films before and after aging were separated from the substrate using a traceless exfoliation technique, and then subjected to 940 cm⁻¹ aging. -1 The characteristic absorption of phosphate groups was analyzed, and AFM-IR tests were performed on the substrate side and the buried perovskite side, respectively.

[0067] Figure 9 The images show the AFM and AFM-IR spectra of the perovskite films obtained in Example 1 and Comparative Example 1 after peeling. Figure 9 In the middle (a)-(d), the samples are fresh samples of Comparative Example 1 (Me-4PACz substrate alone). Figure 9 (e)-(h) are the aged samples of Comparative Example 1. Figure 9 (a) and Figure 9 (b) shows the AFM morphology and AFM-IR (940 cm⁻¹) image of the basal side of the fresh sample after peeling in Comparative Example 1. -1 ) phosphate group distribution diagram, Figure 9 (c) and Figure 10In the middle (d), the AFM morphology and AFM-IR phosphate group distribution diagrams of the corresponding perovskite buried side are shown respectively. It can be seen that after the fresh sample of Comparative Example 1 was peeled off, uneven phosphate group signals were detected on both the substrate side and the perovskite side, indicating that some Me-4PACz had already desorbed from the substrate and transferred to the perovskite buried interface in the fresh state. Figure 9 (e) and Figure 9 (f) shows the AFM morphology and AFM-IR phosphate group distribution of the substrate side of the aged sample in Comparative Example 1 after peeling. Figure 9 (g) and Figure 9 The images (h) show the AFM morphology and AFM-IR phosphate group distribution of the corresponding perovskite substrate side, respectively. It can be seen that after high-temperature photoaging, a large number of unevenly distributed phosphate groups were detected on the perovskite side of the Comparative Example 1 sample after exfoliation, while only a small number of phosphate groups remained on the substrate side. This indicates that Me-4PACz alone is extremely prone to detachment from NiO under high-temperature photoaging conditions. x A large amount of substrate detached and migrated to the perovskite buried interface.

[0068] Figure 10 The images show the AFM and AFM-IR spectra of the perovskite films obtained in Example 1 and Comparative Example 1 after peeling. Figure 10 In the middle (a)-(d), the samples are fresh samples of Example 1 (Me-4PACz+SPANI substrate). Figure 10 (e)-(h) are the aging samples of Example 1. Figure 10 (a) and Figure 10 (b) shows the AFM morphology and AFM-IR (940 cm⁻¹) image of the substrate side of the fresh sample after peeling in Example 1. -1 ) phosphate group distribution diagram, Figure 10 (c) and Figure 10 Image (d) shows the AFM morphology and AFM-IR phosphate group distribution on the corresponding perovskite substrate side, respectively. It can be seen that after exfoliation of the fresh sample from Example 1, a uniform phosphate group distribution was observed only on the substrate side, with almost no phosphate group signal detected on the perovskite side. This indicates that the incorporation of SPANI significantly enhances the incorporation of Me-4PACz in NiO. x Initial adsorption capacity on the substrate. Figure 10 (e) and Figure 10 Image (f) shows the AFM morphology and AFM-IR phosphate group distribution of the substrate side of the aged sample after peeling in Example 1. Figure 10 (g) and Figure 10The images (h) show the AFM morphology and AFM-IR phosphate group distribution on the corresponding perovskite substrate side, respectively. It can be seen that after high-temperature photoaging, the substrate side of the sample from Example 1 still retains a large and uniform distribution of phosphate groups after exfoliation, while no obvious phosphate group signal was observed on the perovskite side. This fully demonstrates that the incorporation of SPANI can significantly enhance the performance of Me-4PACz on NiO under high-temperature photoaging conditions. x The adsorption forces on the substrate effectively suppress thermal or photo-induced desorption, thereby improving the high-temperature light-induced stability of the perovskite module.

[0069] To further investigate the impact of improved uniformity and wettability of the composite interface layer on the crystallization quality of the perovskite buried interface, this invention uses a traceless exfoliation technique to prepare perovskite film buried samples and characterizes the morphology of the perovskite bottom surface using scanning electron microscopy (SEM).

[0070] Figure 11 These are scanning electron microscope (SEM) images of the perovskite thin films prepared in Example 1 and Comparative Example 1. Figure 11 (a) is a SEM image of the perovskite buried interface in the perovskite film prepared in Comparative Example 1. Figure 11 (b) is a SEM image of the perovskite buried interface in the perovskite film prepared in Example 1. Figure 11 Image (c) shows a SEM image of the top of the perovskite in the perovskite film prepared in Comparative Example 1. Figure 11 Image (d) shows a SEM image of the top of the perovskite layer in the perovskite film prepared in Example 1. It can be seen that in the perovskite film prepared in Comparative Example 1, due to the strong hydrophobicity of the Me-4PACz substrate to the perovskite precursor solution, the buried interface of the perovskite film exhibits numerous nanopores, and the perovskite grains are relatively small. In contrast, in the perovskite film prepared in Example 1, no obvious nanopores were observed at the buried interface, and it exhibited a more uniform morphology with larger grains. This indicates that SPANI has a passivating effect on the buried interface of the perovskite film, effectively promoting the growth of the perovskite film.

[0071] The crystallinity of the perovskite film on different SAM substrates was then investigated by X-ray diffraction (XRD) and grazing incidence wide-angle X-ray scattering (GIWAXS).

[0072] Figure 12 The images show X-ray diffraction and grazing-incidence wide-angle X-ray scattering patterns of the perovskite films prepared in Example 1 and Comparative Example 1. Figure 12 (a) shows the full XRD patterns of perovskite films prepared on different substrates. Figure 12 (b) is the full width at half maximum (FWHM) plot of the corresponding (100) crystal plane peak. Figure 12 (c) shows the GIWAXS plot of the perovskite thin film prepared in Comparative Example 1. Figure 12 The middle (d) image is the GIWAXS diagram of the perovskite thin film prepared in Example 1. Figure 12 (e) shows the orientation integral intensity distribution of the (100) crystal plane of perovskite thin films prepared on different substrates. Figure 12 In Figure (f), the GIWAXS integrals along the qz direction are shown for perovskite films prepared on different substrates. It can be seen that the (100) crystal plane of the perovskite film prepared on the substrate of Example 1 exhibits a stronger diffraction intensity, indicating that it has better crystallinity, and no PbI2 diffraction peaks were observed. Figure 12 The integral full width at half maximum (FWHM) of the (100) crystal plane peak in (b) further confirms the above conclusion. This indicates that the interfacial passivation effect of amine groups in SPANI effectively suppresses NiO. x Interface-induced PbI2 generation.

[0073] The crystallization process of perovskite films was monitored using in-situ ultraviolet-visible spectrophotometry (UV-Vis) and in-situ photoluminescence (PL) techniques to explore the reasons for the better crystallinity of perovskite films on mixed substrates.

[0074] Figure 13 The images show the in-situ UV-Vis and in-situ photoluminescence spectra of the perovskite films prepared in Example 1 and Comparative Example 1. Figure 13 (a) shows the in-situ UV-Vis spectrum of the perovskite film prepared in Comparative Example 1 during annealing at 120℃. Figure 13 (b) shows the in-situ UV-Vis spectrum of the perovskite film prepared in Example 1 during annealing at 120°C. Figure 13 (c) shows the in-situ PL spectrum of the perovskite thin film prepared in Comparative Example 1. Figure 13 Image (d) shows the in-situ photoluminescence (PL) spectrum of the perovskite film prepared in Example 1. It can be seen that under annealing conditions at 120°C, the absorbance intensity near 800 nm (a marker of α-FAPbI3 phase formation) exhibits similar characteristics in the first 8 seconds. However, from the 3rd to the 8th second, the perovskite film prepared on the substrate of Example 1 shows a higher intensity during annealing, indicating that the amine groups in the mixed SAM promote the crystallization of the buried interface of the perovskite film. The in-situ PL intensity change during annealing also confirms the accelerated crystallization kinetics of the perovskite on the mixed substrate.

[0075] Further characterization of light absorption and carrier lifetime was performed on perovskite thin films prepared on different substrates.

[0076] Figure 14 The images show the UV-Vis absorption spectra, steady-state photoluminescence spectra, and time-resolved photoluminescence decay curves of the perovskite films prepared in Example 1 and Comparative Example 1. Figure 14(a) shows the UV-Vis absorption spectra of perovskite films prepared on different SAMs. Figure 14 (b) shows the corresponding Tauc bandgap plot. Figure 14 (c) shows the steady-state photoluminescence spectrum. Figure 14 (d) shows the time-resolved photoluminescence decay curve. It can be seen that the perovskite film prepared on the substrate of Example 1 exhibits stronger light absorption, meaning that more photogenerated carriers can be generated. The Tauc bandgap diagram shows that the optical bandgap of the perovskite film prepared on the hybrid SAM substrate has changed accordingly. The perovskite layer prepared in Example 1 has a higher PL intensity, indicating better carrier transport and reduced non-radiative recombination in the perovskite. The TRPL decay curve shows that the rapid decay component (τ1) of the perovskite film prepared on the substrate of Example 1 is significantly shortened from 5.62 ns to 2.03 ns, proving that carrier transport is faster and interfacial recombination is effectively suppressed.

[0077] The uniformity of perovskite films deposited on different SAM substrates was further characterized using laser confocal fluorescence lifetime imaging microscopy (FLIM).

[0078] Figure 15 The images show laser confocal fluorescence lifetime images of the perovskite thin films prepared in Example 1 and Comparative Example 1. Figure 15 Image (a) shows the PL lifetime image of the perovskite top of the perovskite film prepared in Comparative Example 1. Figure 15 Image (b) shows a PL lifetime image of the perovskite top of the perovskite film prepared in Example 1. Figure 15 Image (c) shows the PL lifetime image of the perovskite bottom of the perovskite film prepared in Comparative Example 1. Figure 15 Image (d) shows the PL lifetime image of the perovskite bottom of the perovskite film prepared in Example 1. Figure 15 Image (e) shows the TRPL lifetime image of the perovskite thin film prepared in Comparative Example 1. Figure 15 Image (f) shows the TRPL lifetime imaging of the perovskite film prepared in Example 1. It can be seen that the perovskite film of Comparative Example 1 exhibits low and uneven PL lifetime imaging at both the buried and top surfaces, indicating a significant nonradiative recombination loss between the buried interface and the perovskite bulk phase. In contrast, the perovskite film prepared on the substrate of Example 1 exhibits enhanced PL lifetime and uniformity, and the TRPL lifetime imaging shows the same trend. This indicates that Me-4PACz+SPANI can significantly suppress charge defects at the buried interface and within the perovskite bulk phase, reduce nonradiative recombination loss, and improve the electrical quality of the perovskite film.

[0079] To further verify the effect of the co-mixing strategy of SPANI and Me-4PACz in this invention on improving the uniformity of SAM layer and the crystal quality of perovskite film over a large area, SAM layer and perovskite film were prepared by blade coating on a large area substrate of 14 cm × 14 cm, and PL mapping was performed for characterization.

[0080] Figure 16 Photoluminescence mapping images of perovskite thin films prepared on a 14 cm × 14 cm large-area substrate for Example 1 and Comparative Example 1, and statistical plots of PLQY and TRPL for 25 slices are shown. Figure 16 (a) shows the PL mapping diagram of Comparative Example 1 on a large-area substrate. Figure 16 (b) is a PL mapping diagram of the composite interface layer described in Example 1 on a large-area substrate. Figure 16 (c) is a PLQY statistical chart showing the interface layer described in Comparative Example 1 divided into 25 parts. Figure 16 (d) is a PLQY statistical chart showing the composite interface layer described in Example 1 cut into 25 parts. Figure 16 In Figure (e), the TRPL statistical chart is shown when the interface layer described in Comparative Example 1 is divided into 25 parts. Figure 16 (f) is a TRPL statistical chart showing the composite interface layer described in Example 1 cut into 25 parts. Figure 16 In the middle (g), the TRPL fitting plot is obtained by cutting the control sample into 25 parts. Figure 16 Figure (h) shows the TRPL fitting lifetime diagrams of the composite interface layer described in Example 1, cut into 25 portions. It can be seen that most areas of the sample obtained based on Comparative Example 1 failed to emit light, which may be due to local SAM aggregation; while the sample obtained based on Example 1 exhibits enhanced and uniform luminescence. This indicates that the present invention, by co-mixing SPANI with Me-4PACz, effectively avoids local aggregation of the SAM layer during large-area coating, achieving the preparation of a large-area uniform SAM layer. Further statistical analysis of the perovskite film prepared on a 14×14 cm large-area substrate, shows that the PLQY intensity and TRPL of the large-area perovskite film prepared on Me-4PACz alone exhibit large fluctuations, and the overall intensity level decreases significantly; while the PLQY intensity and TRPL of the large-area perovskite film prepared on the Me-4PACz+SPANI substrate show high consistency. This indicates that the present invention has good uniformity and repeatability over large areas, low internal defect density of the film, and effective suppression of non-radiative recombination effects.

[0081] Figure 17 The figures show the photovoltaic performance and carrier dynamics test results of the perovskite solar modules in Example 1 and Comparative Example 1. Figure 17In figure (a), the current density-voltage (JV) curve is shown. Figure 17 (b) is the electroluminescence (EL) mapping diagram. Figure 17 Image (c) shows the transient photocurrent (TPC) curve. Figure 17 In the middle (d), the transient photovoltage (TPV) curve is shown. Figure 17 In Figure (e), the transient absorption (TA) spectrum of the module prepared by the interface layer described in Comparative Example 1 is shown. Figure 17 In Figure (f), the transient absorption (TA) spectrum of the module prepared by the composite interface layer described in Example 1 is shown. Figure 17 The graph in (h) shows the long-term stability of the normalized power conversion efficiency (PCE) over time. Figure 17 As shown in Figure (a), under reverse scanning conditions, the perovskite solar module prepared based on the interface layer described in Comparative Example 1 has a PCE of 18.72% and a VOC of 14.67 V. SC Reached 175.32 mA cm -2 The FF was 72.78%. In comparison, the perovskite solar module prepared with the composite interface layer described in Example 1 achieved a significant performance improvement: the PCE under reverse scanning jumped to 22.52%, VOC increased to 15.80 V, and I SC Increased to 184.28 mA cm -2 The FF was also optimized to 77.36%. These results demonstrate that the combination of SPANI and Me-4PACZ in this invention effectively promotes a comprehensive improvement in various key performance indicators of the inverse perovskite solar module. Figure 17 As shown in (b), under the same voltage bias, compared to the interface layer described in Comparative Example 1, the composite interface layer described in Example 1 exhibits significantly improved luminescence uniformity and intensity in EL mapping. This indicates that the co-mixing of SPANI and Me-4PACz in this invention effectively improves the uniformity of large-area SAM coating, while promoting efficient transport and recombination of photogenerated carriers, thereby improving the luminescence efficiency of the module. Figure 17 As shown in (c), compared to the interface layer described in Comparative Example 1, the composite interface layer described in Example 1 exhibits a shorter carrier extraction lifetime in TPC testing. This indicates that the strongly bonded hole transport layer prepared in this invention effectively improves the charge extraction efficiency, enabling photogenerated carriers to be collected by the electrodes more rapidly. Figure 17 As shown in (d), the photovoltage decay lifetime of the composite interface layer described in Example 1 is significantly longer in the TPV test compared to the interface layer described in Comparative Example 1. This indicates that the introduction of SPANI in this invention effectively suppresses the charge recombination process at the interface, reduces charge loss, and thus improves the performance of the perovskite module. Figure 17 (e) and Figure 17 As shown in (f), a ground-state bleaching (GSB) characteristic peak was observed near the 800 nm wavelength in the transient absorption spectrum. Compared to Comparative Example 1, the GSB peak of the composite interface layer described in Example 1 exhibits a faster decay trend, indicating that the mixed SAM effectively accelerates carrier extraction in the perovskite film. This invention hypothesizes that the polyaniline modification in the mixed SAM optimizes NiO. x The interface with perovskite lowers the hole transport barrier, increasing the injection of holes from the perovskite valence band into NiO. x The rate. For example... Figure 17 As shown in Figure (h), during a continuous 1000-hour test, the module efficiency of the composite interface layer described in Example 1 showed almost no degradation, and the curve remained stable. In contrast, the module efficiency of the interface layer described in Comparative Example 1 showed a significant decreasing trend, with its normalized PCE decreasing to only 56.37% after approximately 680 hours. This indicates that the introduction of SPANI in this invention effectively suppresses the desorption of Me-4PACz under high-temperature light conditions, enabling the composite interface layer to maintain excellent charge extraction capabilities under long-term operating conditions, thereby endowing the perovskite solar module with extremely excellent long-term operational stability.

[0082] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A large-area uniform strongly bonded hole transport layer, characterized in that, The strongly bonded hole transport layer includes a nickel oxide layer and a composite interface layer disposed on the nickel oxide layer; wherein, the composite interface layer includes Me-4PACz and doped polyaniline with dodecylbenzenesulfonate.

2. In the large-area uniform strongly bonded hole transport layer according to claim 1, the mass ratio of Me-4PACz to the dodecylbenzenesulfonate-doped polyaniline is 1:1 to 1:

10.

3. A large-area uniform strongly bonded hole transport layer according to claim 1 or 2, characterized in that, The surface molecular coverage of the composite interface layer is ≥6×10 13 Number of molecules / cm 2 .

4. A perovskite solar cell, characterized in that, It includes the strongly bonded hole transport layer as described in any one of claims 1-3.

5. The perovskite solar cell according to claim 4, characterized in that, The perovskite solar cell comprises, from bottom to top, the following layers stacked sequentially: a transparent conductive substrate, a strongly bonded hole transport layer, a perovskite light absorption layer, an electron transport layer, and a back electrode.

6. The perovskite solar cell according to claim 5, characterized in that, Multiple perovskite solar cells are connected in series to form a perovskite solar module, the module having an effective illumination area of ​​100 cm². 2 above.

7. A method for preparing a large-area uniform strongly bonded hole transport layer according to any one of claims 1-3, characterized in that, Includes the following steps: Me-4PACz and dodecylbenzenesulfonate-doped polyaniline were dissolved together in an organic solvent of dimethyl sulfoxide and isopropanol and stirred to obtain a homogeneous mixed solution. The mixed solution is deposited on a nickel oxide substrate by a blade coating method, followed by annealing to form a composite interface layer on the nickel oxide substrate. The composite interface layer and the nickel oxide substrate together form a strongly bonded hole transport layer.

8. The method for preparing a large-area uniform strongly bonded hole transport layer according to claim 7, characterized in that, The volume ratio of isopropanol to dimethyl sulfoxide is 0:1 to 2:5, and the total concentration of Me-4PACz and doped polyaniline in the mixed solution is 0.6 mg / mL to 3.5 mg / mL; the stirring time is 8 hours to 10 hours.

9. The preparation method according to claim 8, characterized in that, The coating speed of the blade coating method is 5 mm / s to 25 mm / s.

10. The preparation method according to claim 9, characterized in that, The annealing treatment is performed at a temperature of 80 ℃ to 150 ℃ for a time of 3 minutes to 20 minutes, and the thickness of the composite interface layer is 3 nm to 20 nm.

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