Perovskite solar cell and preparation method and application thereof, and perovskite solar cell module

Abstract

This invention discloses a perovskite solar cell, its fabrication method and application, and a perovskite solar cell module, relating to the field of perovskite solar cell technology. This invention proposes and applies an amphiphilic interface molecule that combines surface activity and hole transport functionality. Through a "one-step coating and in-situ construction of an integrated interface" process, a hole transport layer is formed in-situ on a transparent electrode substrate while simultaneously coating the perovskite layer, eliminating the need for a separate hole transport layer fabrication. This simplifies the device fabrication process, shortens the production cycle and reduces costs, and significantly reduces the difficulty of controlling film uniformity. Furthermore, it reduces defects, promotes charge extraction, and improves photoelectric conversion efficiency. Simultaneously, it solves the two major challenges of interface wettability and charge transport in the large-area fabrication of inverted perovskite solar cells, thereby achieving a revolutionary simplification of the process and a significant performance improvement. This further enables high-efficiency, high-uniformity large-area modules with broad engineering application prospects.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cell technology, and in particular to a perovskite solar cell, its preparation method and application, and a perovskite solar cell module. Background Technology

[0002] Perovskite solar cells, as a promising next-generation photovoltaic technology, have achieved certified efficiencies exceeding 27% for small-area laboratory devices, comparable to mature crystalline silicon technology, demonstrating enormous commercial potential. Currently, the core challenge in transitioning from high-efficiency laboratory processes to high-yield, low-cost industrial production lies in transforming laboratory spin-coating processes into industrial technologies suitable for large-scale, continuous production. Solution processing characteristics are the theoretical basis for achieving low-cost manufacturing of perovskite materials. To this end, researchers have explored various scalable coating technologies, such as spraying, screen printing, blade coating, and slot coating. Among these, blade coating is considered one of the most promising coating methods for industrialization due to its simple equipment, continuous process, and strong industrial compatibility. However, blade coating technology still faces significant challenges in preparing high-quality perovskite thin films over large areas, primarily due to its drastically different physical processes compared to spin-coating: 1) Film uniformity issues: During blade coating, solution flow dynamics (such as the "coffee ring effect") lead to uneven solute accumulation at the drying edge, resulting in macroscopically uneven film thickness, high roughness, and the presence of pinholes or cracks. This non-uniformity significantly amplifies the efficiency loss after battery series connection, and is a key bottleneck restricting the performance uniformity of large-area modules. 2) Interface wettability issues with the underlying transport layer: To achieve high efficiency, the perovskite layer usually needs to be deposited on top of an organic hole transport layer (such as PTAA, P3HT). However, the surfaces of these transport layers are often highly hydrophobic and have poor affinity with conventional perovskite precursor solutions. During the high-temperature, rapid drying process of blade coating, insufficient adhesion of the solution to the underlying layer can easily lead to film shrinkage, cracking, or incomplete coverage, seriously affecting the continuity of the film and the yield of the device.

[0003] To address these issues, engineers have attempted to improve the coating process through additive engineering. For example, introducing trace amounts of surfactants can modulate the rheological properties of the solution, enhancing wettability to the hydrophobic substrate and thus improving film quality. However, most related research focuses on physical modulation of a single function (such as improving leveling) without fundamentally innovating the device structure and production process. Furthermore, conventional processes still follow a complex, stacked process of "pre-preparing the transport layer independently - coating the perovskite layer - then independently preparing another transport layer," involving numerous steps, long production cycles, and the uniformity of each step constraining the performance of the final module. Therefore, current large-area coating processes still suffer from the following shortcomings: 1) High process complexity: Traditional processes require the independent preparation of hole transport layers and perovskite layers sequentially, involving numerous steps, and achieving uniformity over a large area is extremely difficult, resulting in long production cycles, low yields, and high costs. 2) Difficulty in controlling film uniformity: The coating process of the perovskite layer itself is already difficult to control. Subsequent uniform coating of another solution (such as a hole transport layer) on its surface without damaging the underlying layer increases the technical difficulty and equipment requirements exponentially, severely restricting module efficiency and consistency. There is an urgent need for a fabrication scheme that can greatly simplify the process, reduce production cycle time, and simultaneously ensure large-area uniformity.

[0004] Therefore, developing a novel fabrication process that can fundamentally solve the problems of thin film uniformity and interface compatibility, and greatly simplify the device manufacturing process, is of great practical significance for promoting the industrialization of perovskite solar cells. Summary of the Invention

[0005] This invention aims to address at least one of the technical problems existing in the prior art. To this end, this invention proposes a perovskite solar cell, its preparation method and application, and a perovskite solar cell module, aiming to solve the problems of current perovskite solar cells failing to fundamentally address thin film uniformity and interface compatibility issues, as well as the problems of the numerous production steps and inability to complete the coating in a single step in the existing coating process.

[0006] An embodiment of the first aspect of the present invention provides a method for fabricating a perovskite solar cell, comprising the steps of: S100, Preparation of perovskite precursor solution; S200. Add amphiphilic interface molecules to the perovskite precursor solution, mix evenly to obtain a modified precursor solution, wherein the amphiphilic interface molecules include at least one of 4PADCB, 6PADCB, or 8PADCB. S300. The modified precursor solution is coated onto a transparent electrode to prepare a perovskite functional layer. S400: An electron transport layer is prepared on the surface of the perovskite functional layer; S500: A barrier layer is prepared on the surface of the electron transport layer; S600, Prepare a top electrode on the surface of the barrier layer.

[0007] The method for fabricating a perovskite solar cell according to a first aspect of the present invention has at least the following beneficial effects: The fabrication method provided by the present invention introduces amphiphilic interface molecules (such as 4PADCB, 6PADCB, or 8PADCB) that have both surface activity and hole transport functions, thereby forming a hole transport layer in situ on a transparent electrode substrate while simultaneously coating the perovskite film. This simplifies the device fabrication process and simultaneously solves the core industrialization problems of poor uniformity of large-area film formation and low interface charge extraction efficiency. Contact angle tests show that after adding molecules such as 4PADCB, 6PADCB, or 8PADCB, the contact angle between the perovskite film and the substrate is significantly reduced; at the same time, the interface quality between the perovskite film and the substrate is optimized, the interface becomes continuous, dense, and more regularly arranged; the potential distribution at the interface is more uniform, and the average surface potential has shifted significantly, optimizing the interface energy level arrangement, reducing the charge extraction barrier, and improving the open-circuit voltage. Moreover, the process of the present invention is simple, using a one-step coating method to form a hole transport layer in situ while coating the perovskite film, eliminating the need to separately prepare the hole transport layer again. The aforementioned "one-step in-situ coating to construct an integrated interface" process is fundamentally different from the traditional "two-step coating on a pre-defined functional layer" process. It not only shortens the production cycle and reduces costs but also significantly reduces the difficulty of controlling film uniformity, ensuring the large-area uniformity and module efficiency of perovskite solar cell modules. Ultimately, this invention proposes and applies amphiphilic interface molecules that possess both surface activity and hole transport functions. Through a one-step coating process, defects are reduced, charge extraction is promoted, and photoelectric conversion efficiency is improved. This simultaneously solves the two major challenges of interface wettability and charge transport in the large-area fabrication of inverted perovskite solar cells, achieving a revolutionary simplification of the process and a significant performance improvement. This further enables high-efficiency, high-uniformity large-area modules with broad engineering application prospects.

[0008] In some embodiments of the present invention, the amphiphilic interface molecule includes at least one of 4PADCB, 6PADCB, or 8PADCB, but is not limited thereto.

[0009] The amphiphilic interface molecules of this invention include self-assembled monolayer (SAM) materials such as 4PADCB, 6PADCB, or 8PADCB, which have unique molecular structures and excellent photoelectric properties.

[0010] Specifically, the Chinese name of the 4PADCB is [4-(7H-dibenzocarbazole-7-yl)butyl]phosphoric acid, the CAS number is 2882156-63-8, and the structural formula is: .

[0011] Specifically, the Chinese name of the 6PADCB is [4-(7H-dibenzocarbazole-7-yl)hexyl]phosphoric acid, and its structural formula is as follows: .

[0012] In some embodiments of the present invention, the synthesis steps of the 6PADCB include: Step 1: Synthesis of 7-(6-bromohexyl)-7H-dibenzo[a,c]carbazole (N-alkylation reaction) Reactants: 7H-dibenzo[a,c]carbazole, 1,6-dibromohexane Reagents and conditions: Add 7H-dibenzo[a,c]carbazole (1 equivalent), 1,6-dibromohexane (2-3 equivalents, avoid disubstitution), and the phase transfer catalyst tetrabutylammonium bromide (TBAB, 0.05-0.1 equivalents) to the reaction vessel, and add an organic solvent (such as toluene, DMF, or dichloromethane) and stir to dissolve.

[0013] Add potassium hydroxide (KOH, 2-3 equivalents, in solid or aqueous solution) in batches, stir and react at room temperature or heated to 50-80°C for 6-12 hours, and monitor the reaction of the raw materials by TLC until complete.

[0014] Reaction principle: Under alkaline conditions, carbazole NH is deprotonated to form a nitrogen anion, which undergoes SN2 nucleophilic substitution with 1,6-dibromohexane under the action of a phase transfer catalyst, introducing a 6-bromohexyl side chain onto the nitrogen atom to obtain a monobromoalkyl carbazole intermediate.

[0015] Post-processing: The reaction solution was cooled and quenched with water, extracted with dichloromethane / ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography to obtain a pale yellow solid / oil intermediate. Yield: 89%.

[0016] Step 2: Synthesis of diethyl(6-(7H-dibenzo[a,c]carbazole-7-yl)hexyl)phosphonate (Michaelis-Arbuzov reaction) Reactants: 7-(6-bromohexyl)-7H-dibenzo[a,c]carbazole, triethyl phosphite (P(OEt)3) Reagents and conditions: The above-mentioned brominated intermediate (1 equivalent) and excess triethyl phosphite (3-5 equivalent, also used as a reaction solvent) were added to a reaction flask and heated to 140-160°C under nitrogen protection and refluxed for 8-16 hours. The starting material was observed to disappear by TLC.

[0017] Reaction principle: Triethyl phosphite acts as a nucleophile to attack the bromine-linked methylene group. After the bromide ion leaves, the Arbuzov rearrangement occurs, resulting in the removal of one molecule of bromoethane to give the diethyl phosphonate product.

[0018] Post-processing: After the reaction is cooled, excess triethyl phosphite and the byproduct bromoethane are removed by vacuum distillation. The remaining oily substance can be directly added to the next step, or purified by column chromatography to obtain phosphonate intermediates.

[0019] Step 3: Synthesis of (6-(7H-dibenzo[a,c]carbazole-7-yl)hexyl)phosphonic acid (phosphonate deprotection reaction) Reactant: Diethyl(6-(7H-dibenzo[a,c]carbazole-7-yl)hexyl)phosphonate Reagents and conditions: The phosphonate intermediate (1 equivalent) was dissolved in anhydrous dichloromethane, and trimethylbromosilane (TMSBr, 4-6 equivalents) was slowly added dropwise under ice-water bath cooling. After the addition was complete, the mixture was brought to room temperature and stirred for 12-24 hours.

[0020] After the reaction was monitored by TLC until it was complete, the solvent was removed by concentration under reduced pressure. Methanol (CH3OH) was added to the residue and the mixture was stirred at room temperature for 2-4 hours to quench the hydrolysis.

[0021] Reaction principle: TMSBr breaks the P-OEt bond of the phosphonate to generate a trimethylsilyl-protected phosphonic acid intermediate. After the addition of methanol, the silyl group is alcoholyzed, releasing free phosphonic acid groups (-PO(OH)2).

[0022] Post-processing: The methanol solution was concentrated, and the resulting solid was recrystallized from ethyl acetate / n-hexane, or the final phosphonic acid product was obtained by precipitation and washing, followed by vacuum drying to obtain the target product as a white or pale yellow solid. The overall yield of the three steps was 71%.

[0023] The chemical formula for the synthesis steps of 6PADCB is shown below:

[0024] Specifically, the Chinese name of the 8PADCB is [4-(7H-dibenzocarbazole-7-yl)octyl]phosphoric acid, and its structural formula is as follows: .

[0025] In some embodiments of the present invention, the synthesis steps of the 8PADCB include: Step 1: Synthesis of 7-(8-bromooctyl)-7H-dibenzo[a,c]carbazole (N-alkylation reaction) Reactants: 7H-dibenzo[a,c]carbazole, 1,8-dibromooctane Reagents and conditions: Tetrabutylammonium bromide (TBAB, phase transfer catalyst), potassium hydroxide (KOH, base), usually in an organic solvent (such as toluene, dichloromethane or DMF), reacted at room temperature or with heating and stirring.

[0026] Reaction mechanism: Under alkaline conditions, the NH of carbazole is deprotonated by KOH to form a nitrogen anion. Under the action of the phase transfer catalyst TBAB, it undergoes a nucleophilic substitution reaction (SN2) with 1,8-dibromooctane, introducing an 8-bromooctyl chain onto the nitrogen atom to obtain a monosubstituted bromoalkyl carbazole intermediate.

[0027] Post-processing: After the reaction was complete, water was added to quench the reaction, followed by extraction with an organic solvent. The organic phase was dried and concentrated, and then purified by column chromatography to obtain the target intermediate. Yield: 82%.

[0028] Step 2: Synthesis of diethyl(8-(7H-dibenzo[a,c]carbazole-7-yl)octyl)phosphonate (Michaelis-Arbuzov reaction) Reactants: 7-(8-bromooctyl)-7H-dibenzo[a,c]carbazole, triethyl phosphite (P(OEt)3) Reagents and conditions: The brominated product is usually mixed with an excess of triethyl phosphite and heated under reflux (usually 120-160°C) for several hours.

[0029] Reaction mechanism: It belongs to the classic Arbuzov rearrangement reaction. Triethyl phosphite acts as a nucleophile to attack the carbon atom attached to the bromine atom of the bromine alkane, and leaves the bromide ion. Then the bromide ion attacks the ethyl group to undergo a deethylation reaction, and rearranges to give the diethyl phosphonate product.

[0030] Post-processing: After the reaction is complete, excess triethyl phosphite and the generated bromoethane are removed by vacuum distillation. The residue can be used directly in the next step or purified by column chromatography to obtain phosphonate intermediates.

[0031] Step 3: Synthesis of (8-(7H-dibenzo[a,c]carbazole-7-yl)octyl)phosphonic acid (phosphonate deprotection reaction) Reactant: Diethyl(8-(7H-dibenzo[a,c]carbazole-7-yl)octyl)phosphonate Reagents and conditions: Trimethylbromosilane (TMSBr, deprotecting agent) is usually reacted in an inert solvent such as dichloromethane at room temperature or by heating; then methanol (CH3OH) is added to quench and hydrolyze the reaction.

[0032] Reaction mechanism: TMSBr breaks the ethyl-oxygen bond of the phosphonate to generate a trimethylsilyl-protected phosphonic acid intermediate. After the addition of methanol, the silyl group is alcoholyzed by methanol to obtain a free phosphonic acid group (-PO(OH)2).

[0033] Post-processing: The reaction solution was concentrated, and the final phosphonic acid product was obtained by recrystallization or precipitation. The overall yield of the three steps was 63%, and it can be further purified by recrystallization and other methods.

[0034] The chemical formula for the synthesis steps of 8PADCB is shown below:

[0035] In some embodiments of the present invention, the amphiphilic interface molecule is preferably 6PADCB. Compared to 4PADCB, 6PADCB has a longer carbon chain variation, which leads to superior performance: stronger hydrophobicity and intermolecular forces: the C6 chain has stronger hydrophobic interactions and van der Waals forces than the C4 chain; higher conformational freedom and better spatial adaptability: the longer flexible chain allows the molecule more room for conformational adjustment at the interface to match the micro-undulations of the substrate surface and the initial template for perovskite crystallization. Moreover, the present invention, through a systematic comparison of molecules with different carbon chain lengths (such as 4PADCB and 6PADCB), found that a moderate increase in carbon chain length brings unexpected comprehensive performance optimization: 1) Optimized energy level arrangement and charge extraction: experimental data (such as KPFM plots) show that the device using 6PADCB has a more uniform interface potential distribution. This may be due to its superior molecular arrangement, achieving more ideal interface dipole and energy level alignment, thereby more effectively reducing the hole extraction barrier. 2) Significantly improved device fill factor (FF): JV test results show that the FF of the device using 6PADCB is increased to 78.60%, significantly higher than the 65.41% of the device using 4PADCB. This leap in key performance demonstrates that longer carbon chains can greatly improve the internal charge transport performance of the device by optimizing interfacial contact and reducing nonradiative recombination.

[0036] In some embodiments of the present invention, the concentration of the amphiphilic interface molecules in the modified precursor solution is 0.3~0.8 mg / ml, preferably about 0.5 mg / ml. Exemplarily, it can be 0.3 mg / ml, 0.4 mg / ml, 0.5 mg / ml, 0.6 mg / ml, 0.7 mg / ml, 0.8 mg / ml, or within any two of the above values.

[0037] In some embodiments of the present invention, the scraping speed is 10-20 mm / s. Exemplarily, it can be 10 mm / s, 11 mm / s, 12 mm / s, 13 mm / s, 14 mm / s, 15 mm / s, 16 mm / s, 17 mm / s, 18 mm / s, 19 mm / s, 20 mm / s, or within any two of the above values.

[0038] In some embodiments of the present invention, the gap between the scraper blades used for coating is 100~300μm. Exemplarily, it can be 100μm, 150μm, 200μm, 250μm, 300μm, or within any two of the above values.

[0039] In some embodiments of the present invention, the pressure of the air knife used for coating is 0.3~0.8 MPa. Exemplarily, it can be 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, or within any two of the above values.

[0040] In some embodiments of the present invention, after the coating is applied, the step further includes annealing on a hot plate at 100-150°C for 10-20 minutes. Exemplarily, the temperature can be 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or within any two of the above values.

[0041] This invention employs a "one-step in-situ coating process to construct an integrated interface" and defines the aforementioned coating parameters. This is fundamentally different from the traditional "two-step coating on a pre-defined functional layer" process. The one-step coating process of this invention not only shortens the production cycle and reduces costs but also significantly reduces the difficulty of controlling film uniformity, decreases defects, promotes charge extraction, and improves photoelectric conversion efficiency. Simultaneously, it solves the two major challenges of interface wettability and charge transport in the large-area fabrication of inverted perovskite solar cells, thereby achieving a revolutionary simplification of the process and a significant improvement in performance. This further enables the creation of high-efficiency, high-uniformity large-area modules with broad engineering application prospects.

[0042] In some embodiments of the present invention, the method for preparing the perovskite solar cell includes at least one of (a1) to (a6): (a1) The perovskite precursor solution comprises a binary cationic perovskite component, the chemical formula of which is FA. x Cs y PbI3, 0.88≤x≤0.95, 0.05≤y≤0.12, and x+y=1; (a2) The perovskite precursor solution includes a solvent, which includes at least one of DMF or NMP; (a3) The transparent electrode includes at least one of ITO electrode, FTO electrode, or AZO electrode; (a4) The electron transport layer includes a C60 thin film or a PCBM thin film; (a5) The barrier layer includes a BCP film; (a6) The top electrode includes a Cu electrode or an Ag electrode.

[0043] In some embodiments of the present invention, the method for preparing the perovskite solar cell includes at least one of (b1) to (b5): (b1) The thickness of the transparent electrode is 100~200nm; (b2) The thickness of the perovskite functional layer is 600~800 nm; (b3) The thickness of the electron transport layer is 30~50nm; (b4) The thickness of the barrier layer is 6~10nm; (b5) The thickness of the top electrode is 100~200nm.

[0044] In some embodiments of the present invention, the perovskite precursor solution comprises a binary cationic perovskite component, the chemical formula of which is FA. x Cs y PbI3, 0.88≤x≤0.95, 0.05≤y≤0.12, and x+y=1.

[0045] Specifically, the binary cationic perovskite component includes FA. 0.88 Cs 0.12 PbI3, FA 0.9 Cs 0.1 PbI3, or FA 0.95 Cs 0.05 PbI3, but not limited to this.

[0046] In some embodiments of the present invention, the perovskite precursor solution includes a solvent, which includes, but is not limited to, at least one of DMF (N,N-dimethylformamide) or NMP (N-methylpyrrolidone). Preferably, a mixed solvent of DMF and NMP is used.

[0047] In some specific embodiments of the present invention, the perovskite precursor solution is composed of 151.4 mg FAI, 31.2 mg CsI2, 461 mg PbI2, and 20.3 mg MACl. 0.88 Cs 0.12 PbI3 was mixed in a mixed solvent of DMF:NMP at a ratio of 500:96.

[0048] In some specific embodiments of the present invention, the perovskite precursor solution is composed of 154.7 mg FAI, 25.99 mg CsI2, 461 mg PbI2, and 27.8 mg PbCl2. 0.9 Cs 0.1 PbI3 was mixed in a mixed solvent of DMF:NMP at a ratio of 500:96.

[0049] In some specific embodiments of the present invention, the perovskite precursor solution is composed of 163.31 mg FAI, 13 mg CsI2, 484 mg PbI2, and 20.3 mg MACl. 0.95 Cs 0.05 PbI3 was mixed in a mixed solvent of DMF:NMP at a ratio of 500:96.

[0050] In some embodiments of the present invention, the transparent electrode includes at least one of ITO (indium tin oxide) electrode, FTO (fluorine-doped tin oxide) electrode, or AZO (aluminum-doped zinc oxide) electrode, but is not limited thereto. These materials have large band gaps and absorb only ultraviolet light, not visible light, hence the term "transparent electrode." Commonly used transparent electrodes in the art can be reasonably applied.

[0051] In some embodiments of the present invention, the thickness of the transparent electrode is 100-200 nm; preferably about 150 nm. Exemplarily, it can be 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, or within any two of the above values.

[0052] In some embodiments of the present invention, the thickness of the perovskite functional layer is 600-800 nm; preferably about 700 nm. Exemplarily, it can be 600 nm, 620 nm, 640 nm, 660 nm, 680 nm, 700 nm, 720 nm, 740 nm, 760 nm, 780 nm, 800 nm, or within any range of two of the above values.

[0053] In some embodiments of the present invention, the electron transport layer includes a C60 thin film or a PCBM thin film, but is not limited thereto. Thin films with electron transport functions commonly used in the art can be reasonably applied.

[0054] C60 is a member of the fullerene family, composed of 60 carbon atoms. Its shape resembles a soccer ball, hence it is also known as "soccerolene". The unique structure of fullerenes endows them with excellent electron transport properties.

[0055] In some embodiments of the present invention, the thickness of the electron transport layer is 30-50 nm; preferably about 40 nm. Exemplarily, it can be 30 nm, 32 nm, 34 nm, 36 nm, 38 nm, 40 nm, 42 nm, 44 nm, 46 nm, 48 nm, 50 nm, or within any two of the above values.

[0056] In some embodiments of the present invention, the barrier layer includes, but is not limited to, a BCP thin film. Commonly used barrier films in the art can be reasonably applied. The barrier layer can prevent the metal electrode from reacting with the perovskite functional layer.

[0057] In some embodiments of the present invention, the thickness of the barrier layer is 6-10 nm; preferably about 8 nm. Exemplarily, it can be 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, or within any two of the above values.

[0058] In some embodiments of the present invention, the top electrode includes a Cu electrode or an Ag electrode, but is not limited thereto. Commonly used top electrodes in the art can be reasonably applied.

[0059] In some embodiments of the present invention, the thickness of the top electrode is 100-200 nm; preferably about 100 nm. Exemplarily, it can be 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, or within any two of the above values.

[0060] According to a second aspect of the present invention, a perovskite solar cell is provided, which is prepared by the above-described preparation method.

[0061] According to a third aspect of the present invention, a perovskite solar cell module is provided, comprising a plurality of perovskite solar cells connected in series, wherein the perovskite solar cells are prepared by the above-described preparation method.

[0062] In some embodiments of the present invention, the method for preparing the perovskite solar cell module further includes the step of pre-treating the transparent electrode, wherein the pre-treating includes: using laser scribing to perform P1 etching on the transparent electrode, followed by ultrasonic cleaning and ultraviolet-ozone cleaning.

[0063] In some embodiments of the present invention, the laser scribing step uses a pulsed laser with a wavelength of 1064 nm and an average laser power of 30 W to scribble through the transparent electrode.

[0064] In some embodiments of the present invention, in the ultrasonic cleaning step, conductive glass that has undergone laser scribing is cleaned sequentially with conductive glass cleaner, deionized water, and ethanol, and ultrasonic cleaning is performed for 30 minutes at 99% power.

[0065] In some embodiments of the present invention, in the ultraviolet-ozone cleaning step, the ultrasonically cleaned conductive glass is irradiated in an ultraviolet-ozone cleaning machine for 30 minutes.

[0066] Figure 1 The diagram shown is a schematic diagram of the perovskite solar cell module of the present invention. The perovskite solar cell module shown in the figure includes, in sequence, an ITO electrode, a perovskite functional layer, an electron transport layer / barrier layer, and a copper electrode. P1 is a line drawing of the ITO electrode, P2 is a line drawing of the barrier layer, electron transport layer, and perovskite functional layer, and P3 is a line drawing of the copper electrode.

[0067] In some embodiments of the present invention, the method for preparing the perovskite solar cell module includes the following steps: S1000. Pre-treatment of the transparent electrode, the pre-treatment includes: using laser scribing to etch the transparent electrode with P1, followed by ultrasonic cleaning and ultraviolet-ozone cleaning. S2000, Preparation of perovskite precursor solution; S3000: Add amphiphilic interface molecules to the perovskite precursor solution, mix evenly to obtain a modified precursor solution, wherein the amphiphilic interface molecules include at least one of 4PADCB, 6PADCB, or 8PADCB. S4000: The modified precursor solution is coated onto the pretreated transparent electrode to prepare a perovskite functional layer. S5000: An electron transport layer is prepared on the surface of the perovskite functional layer; S6000: A barrier layer is prepared on the surface of the electron transport layer; S7000, A top electrode is prepared on the surface of the barrier layer.

[0068] The method for fabricating a perovskite solar cell module provided by this invention has at least the following beneficial effects: By introducing amphiphilic interface molecules (such as 4PADCB, 6PADCB, or 8PADCB) that possess both surface activity and hole transport functions, a hole transport layer is formed in situ on the transparent electrode substrate simultaneously with the coating of perovskite. This simplifies the device fabrication process and simultaneously solves the core industrialization challenges of poor uniformity in large-area film formation and low interface charge extraction efficiency. Contact angle tests show that the addition of molecules such as 4PADCB, 6PADCB, or 8PADCB significantly reduces the contact angle between the perovskite film and the substrate. Simultaneously, it optimizes the interface quality between the perovskite film and the substrate, making the interface more continuous, dense, and more regularly arranged. The potential distribution at the interface is more uniform, and the average surface potential shows a significant shift, optimizing the interface energy level arrangement, reducing the charge extraction barrier, and increasing the open-circuit voltage. Furthermore, this invention employs a one-step coating method, forming the hole transport layer in situ simultaneously with the coating of perovskite, eliminating the need for separate fabrication of the hole transport layer. The aforementioned "one-step in-situ coating to construct an integrated interface" process is fundamentally different from the traditional "two-step coating on a pre-defined functional layer" process. It not only shortens the production cycle and reduces costs but also significantly reduces the difficulty of controlling film uniformity, ensuring the large-area uniformity and module efficiency of perovskite solar cell modules. Ultimately, this invention proposes and applies amphiphilic interface molecules that possess both surface activity and hole transport functions. Through a one-step coating process, defects are reduced, charge extraction is promoted, and photoelectric conversion efficiency is improved. This simultaneously solves the two major challenges of interface wettability and charge transport in the large-area fabrication of inverted perovskite solar cells, achieving a revolutionary simplification of the process and a significant performance improvement. This further enables high-efficiency, high-uniformity large-area modules with broad engineering application prospects.

[0069] In the fabrication method of the perovskite solar cell module, the perovskite precursor solution, amphiphilic interface molecules, transparent electrode, perovskite functional layer, electron transport layer, barrier layer, top electrode, etc., are as described above and will not be repeated here.

[0070] In some embodiments of the present invention, a one-step coating method for preparing large-area perovskite solar cell modules is provided, comprising the following steps: 1) P1 etching is performed on ITO (indium tin oxide) or FTO (fluorine-doped tin dioxide) conductive glass using laser scribing. In the laser scribing step, a pulsed laser with a wavelength of 1064nm and an average laser power of 30W is used to scribble through the conductive glass. 2) Clean the laser-scribing conductive glass sequentially with conductive glass cleaner, deionized water, and ethanol, and then sonicate it at 99% power for 30 minutes to obtain a clean ITO / FTO conductive glass substrate. 3) Take a clean conductive glass substrate and irradiate it in an ultraviolet ozone cleaner for 30 minutes; 4) Take 15 mg of amphiphilic interface molecules and stir them in 1 ml of N,N-dimethylformamide solution. Stir for 30 min and let stand to obtain a homogeneous SAM molecular solution. The amphiphilic interface molecules include at least one of 4PADCB, 6PADCB, or 8PADCB. 5) Take 461 mg PbI2, 142.8 mg FAI, 27.8 mg PbCl2 and 44.2 mg CsI2 and stir them in a mixed solution of DMF:NMP=500:96. Stir for 2 hours and let stand to obtain a homogeneous perovskite precursor solution. 6) Take 20 μl of uniform SAM molecular solution and add it to the perovskite precursor solution. Continue stirring for 30 min and let it stand to obtain a uniform modified precursor solution. 7) Take a well-stirred modified precursor solution and prepare a hole transport layer / perovskite light-absorbing layer on conductive glass using a blade coating method. The preparation parameters for the blade coating method are: blade coating speed 10~20mm / s, blade gap 100~300 μm, air knife pressure 0.3~0.8MPa. Then, anneal on a hot stage at 100~150℃ for 10~20min. 8) Sequentially deposit C60 thin film or PCBM thin film (thickness 30~50nm), BCP barrier layer (thickness 6~10nm), Cu electrode or Ag electrode (thickness 100~200nm).

[0071] An embodiment of the fourth aspect of the present invention provides an application of the above-described perovskite solar cell or the above-described perovskite solar cell module in the photovoltaic field, electronic devices, new energy vehicles, space field, or building field.

[0072] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures particularly pointed out in the description, claims, and drawings. Attached Figure Description

[0073] Figure 1 A schematic diagram of the perovskite solar cell module provided by the present invention; Figure 2 This is a schematic diagram of the contact angle test results of Embodiments 1-2 and Comparative Example 1 of the present invention; Figure 3 These are SEM images of the perovskite buried interface in Examples 1-2 and Comparative Example 1 of the present invention. Figure 4 These are KPFM test images of the perovskite buried interface in Examples 1-2 and Comparative Example 1 of the present invention; Figure 5 This is a schematic diagram of the JV test results of the module devices in Embodiments 1-2 and Comparative Examples 1-2 of the present invention. Detailed Implementation

[0074] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0075] In the description of this invention, the terms "one embodiment," "some embodiments," "illustrative embodiment," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0076] In the description of this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are both real numbers. Unless otherwise stated, the various reaction or operation steps may be performed sequentially or not. Preferably, the reaction methods in this invention are performed sequentially.

[0077] Experimental methods in the following examples, unless otherwise specified, are generally performed under standard conditions or as recommended by the manufacturer. Unless otherwise specified, the materials and reagents used in these examples are commercially available.

[0078] Example 1 1) P1 etching of ITO conductive glass is performed using laser scribing. In the laser scribing step, a pulsed laser with a wavelength of 1064nm and an average laser power of 30W is used to scribble through the ITO conductive glass. 2) Clean the etched ITO conductive glass sequentially with conductive glass cleaner, deionized water, and ethanol, and then perform ultrasonication at 99% power for 30 minutes to obtain a clean ITO conductive glass substrate. 3) Take a clean ITO conductive glass substrate and irradiate it in a UV-ozone cleaner for 30 minutes; 4) Take 15 mg of 4PADCB (commercially available), shake and stir it in 1 ml of N,N-dimethylformamide solution, stir for 30 min, and let it stand to obtain a homogeneous SAM molecular solution; 5) Take 461 mg PbI2, 142.8 mg FAI, 27.8 mg PbCl2 and 44.2 mg CsI2 and stir them in a mixed solution of DMF:NMP = 500 (μl): 96 (μl) for 2 hours. Let it stand to obtain a homogeneous perovskite precursor solution. 6) Take 20 μl of uniform SAM molecular solution and add it to the perovskite precursor solution in step 5). Continue stirring for 30 min and let it stand to obtain a uniform modified precursor solution. 7) Take the well-stirred modified precursor solution and use the blade coating method to prepare a perovskite functional layer (integrated hole transport layer / perovskite light-absorbing layer) on the ITO conductive glass substrate obtained in step 3). The blade coating preparation parameters are: blade coating speed 10 mm / s, blade gap 50 μm, air knife pressure 0.3 MPa. Then, anneal on a hot stage at 150℃ for 10 min to form the perovskite functional layer. 8) Place the perovskite functional layer obtained in step 7) in a vacuum evaporation chamber, and sequentially deposit a C60 thin film (40 nm thick), a BCP thin film (8 nm thick), and a Cu electrode (100 nm thick) to obtain a perovskite solar cell module.

[0079] Example 2 The only difference between this embodiment and Embodiment 1 is that in step 4), 15 mg of 6 PADCB is used instead of 4 PADCB.

[0080] The synthesis steps of 6PADCB include: Step 1: Synthesis of 7-(6-bromohexyl)-7H-dibenzo[a,c]carbazole (N-alkylation reaction) Reactants: 7H-dibenzo[a,c]carbazole, 1,6-dibromohexane Reagents and conditions: Add 7H-dibenzo[a,c]carbazole (1 equivalent), 1,6-dibromohexane (3 equivalents), and the phase transfer catalyst tetrabutylammonium bromide (TBAB, 0.1 equivalents) to the reaction vessel, and add the organic solvent DMF and stir to dissolve.

[0081] Potassium hydroxide (KOH, 3 equivalents, in aqueous solution) was added in batches, and the mixture was heated to 70°C and stirred for 12 hours. The reaction of the raw materials was monitored by TLC until it was complete.

[0082] Post-processing: The reaction solution was cooled and quenched with water, extracted with dichloromethane / ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography to obtain a pale yellow solid / oil intermediate. Yield: 89%.

[0083] Step 2: Synthesis of diethyl(6-(7H-dibenzo[a,c]carbazole-7-yl)hexyl)phosphonate (Michaelis-Arbuzov reaction) Reactants: 7-(6-bromohexyl)-7H-dibenzo[a,c]carbazole, triethyl phosphite (P(OEt)3) Reagents and conditions: The above-mentioned brominated intermediate (1 equivalent) and excess triethyl phosphite (5 equivalent, also used as a reaction solvent) were added to a reaction flask and heated to 150°C under nitrogen protection and refluxed for 16 hours. The starting material was observed to disappear by TLC.

[0084] Post-processing: After the reaction is cooled, excess triethyl phosphite and the byproduct bromoethane are removed by vacuum distillation. The remaining oily substance can be directly added to the next step, or purified by column chromatography to obtain phosphonate intermediates.

[0085] Step 3: Synthesis of (6-(7H-dibenzo[a,c]carbazole-7-yl)hexyl)phosphonic acid (phosphonate deprotection reaction) Reactant: Diethyl(6-(7H-dibenzo[a,c]carbazole-7-yl)hexyl)phosphonate Reagents and conditions: The phosphonate intermediate (1 equivalent) was dissolved in anhydrous dichloromethane, and trimethylbromosilane (TMSBr, 6 equivalent) was slowly added dropwise under ice-water bath cooling. After the addition was complete, the mixture was brought to room temperature and stirred for 24 hours.

[0086] After the reaction was monitored by TLC until it was complete, the solvent was removed by concentration under reduced pressure. Methanol (CH3OH) was added to the residue and the mixture was stirred at room temperature for 2-4 hours to quench the hydrolysis.

[0087] Post-processing: The methanol solution was concentrated, and the resulting solid was recrystallized from ethyl acetate / n-hexane, or the final phosphonic acid product was obtained by precipitation and washing, followed by vacuum drying to obtain the target product as a white or pale yellow solid. The overall yield of the three steps was 71%.

[0088] The chemical formulas for the synthetic steps of 6PADCB are shown below:

[0089] The rest is the same as in Example 1, and will not be repeated here.

[0090] Comparative Example 1 1) P1 etching of ITO conductive glass is performed using laser scribing. In the laser scribing step, a pulsed laser with a wavelength of 1064nm and an average laser power of 30W is used to scribble through the ITO conductive glass. 2) Clean the etched ITO conductive glass sequentially with conductive glass cleaner, deionized water, and ethanol, and then perform ultrasonication at 99% power for 30 minutes to obtain a clean ITO conductive glass substrate. 3) Take a clean ITO conductive glass substrate and irradiate it in a UV-ozone cleaner for 30 minutes; 4) Take 461 mg PbI2, 142.8 mg FAI, 27.8 mg PbCl2 and 44.2 mg CsI2 and stir them in a mixed solution of DMF:NMP = 500 (μl): 96 (μl) for 2 hours. Let it stand to obtain a homogeneous perovskite precursor solution. 5) Take the well-stirred perovskite precursor solution and use the blade coating method to prepare a perovskite thin film on the ITO conductive glass substrate obtained in step 3). The blade coating method preparation parameters are: blade coating speed 10 mm / s, blade gap 50 μm, air knife pressure 0.3 MPa. Then, anneal on a hot stage at 150℃ for 10 min to form a perovskite thin film. 6) Place the perovskite thin film obtained in step 5) in a vacuum evaporation chamber, and sequentially deposit a C60 thin film (thickness of 40 nm), a BCP thin film (thickness of 8 nm), and a Cu electrode (thickness of 100 nm) to obtain a perovskite solar cell module.

[0091] Comparative Example 2 1) P1 etching of ITO conductive glass is performed using laser scribing. In the laser scribing step, a pulsed laser with a wavelength of 1064nm and an average laser power of 30W is used to scribble through the ITO conductive glass. 2) Clean the etched ITO conductive glass sequentially with conductive glass cleaner, deionized water, and ethanol, and then perform ultrasonication at 99% power for 30 minutes to obtain a clean ITO conductive glass substrate. 3) Take a clean ITO conductive glass substrate and irradiate it in a UV-ozone cleaner for 30 minutes; 4) Dissolve 0.5 mg of 4PADCB molecules in 1 ml of IPA solution and stir with shaking for 30 min; 5) Take the 4 PADCB molecules that are stirred evenly and use the blade coating method to prepare a hole transport layer on the ITO conductive glass substrate obtained in step 3). The blade coating parameters are: blade coating speed 20 mm / s, blade gap 50 μm, air knife pressure 0.2 MPa. Then, anneal on a hot stage at 100℃ for 10 min. 6) Take 461 mg PbI2, 142.8 mg FAI, 27.8 mg PbCl2 and 44.2 mg CsI2 and stir them in a mixed solution of DMF:NMP = 500 (μl): 96 (μl) for 2 hours. Let it stand to obtain a homogeneous perovskite precursor solution. 7) Take the well-stirred perovskite precursor solution and use the blade coating method to prepare a perovskite thin film on the ITO conductive glass substrate obtained in step 3). The blade coating method preparation parameters are: blade coating speed 10 mm / s, blade gap 50 μm, air knife pressure 0.3 MPa. Then, anneal on a hot stage at 150℃ for 10 min to form a perovskite thin film. 8) Place the perovskite thin film obtained in step 5) in a vacuum evaporation chamber, and sequentially deposit a C60 thin film (thickness of 40 nm), a BCP thin film (thickness of 8 nm), and a Cu electrode (thickness of 100 nm) to obtain a perovskite solar cell module.

[0092] Test case 1. Contact Angle Test The contact angle of the perovskite precursor solutions in Examples 1-2 and Comparative Example 1 was tested using a contact angle meter, with a solution volume of 1 μl.

[0093] The results are as follows Figure 2 As shown. Data shows that without the addition of SAM molecules (Comparative Example 1, Figure 2 The precursor solution (left image) exhibits a large contact angle on the substrate, indicating poor wettability. However, the addition of 4PADCB (Example 1) results in... Figure 2 (intermediate image in the image) or 6PADCB molecule (Example 2, Figure 2 (See the right image in the middle). After this, the contact angle decreased significantly. This indicates that adding SAM molecules such as 4PADCB or 6PADCB can optimize the perovskite subsurface interface quality, reduce defects, and promote charge extraction.

[0094] 2. SEM testing The buried interface of the perovskite solar cell modules obtained in Examples 1-2 and Comparative Example 1 was observed using scanning electron microscopy (SEM). The results are as follows: Figure 3 As shown in the comparison, it is clear from the SEM images that without SAM (Comparative Example 1), Figure 3 When adding 4PADCB (Example 1), voids, poor contact, or disordered grains may exist at the interface between the perovskite and the underlying substrate. Figure 3 (intermediate image in the image) or 6PADCB (Example 2, Figure 3 (See the right image in the middle). After that, the interface becomes continuous, dense, and more regularly arranged.

[0095] 3. KPFM test The perovskite solar cell modules obtained in Examples 1-2 and Comparative Example 1 were subjected to KPFM testing. Specifically, conductive silver paste was used to fix the buried interface sample on the test stage, and the equipment used was an atomic force microscope.

[0096] The results are as follows Figure 4 As shown, where, Figure 4 The left-middle figure is Comparative Example 1. Figure 4 The middle diagram is from Example 1. Figure 4 The right-hand figure shows Example 2. The surface potential map measured by KPFM shows that after adding SAM molecules, the potential distribution at the interface is more uniform, and the average surface potential shifts significantly. This indicates that adding SAM molecules can optimize the interface energy level arrangement, reduce the charge extraction barrier, and improve the open-circuit voltage buried interface. Furthermore, the KPFM diagram shows that the device using 6PADCB has a more uniform interface potential distribution, which may be due to its superior molecular arrangement, achieving more ideal interface dipole and energy level alignment, thereby more effectively reducing the hole extraction barrier.

[0097] 4. Module component JV testing JV testing was performed on the perovskite solar cell modules obtained in Examples 1-2 and Comparative Examples 1-2. Specifically, the four-wire method was used, with the starting voltage set to 7.5V, the ending voltage set to -0.1V, the scan step size set to 0.1V, and the effective cell area set to 12.5cm². 2 The light intensity is 100 Mw / cm 2 .

[0098] The results are as follows Figure 5 As shown in Table 1, the data demonstrates that the module prepared using a SAM (4PADCB / 6PADCB) precursor solution exhibits significantly higher power conversion efficiency (PCE) and fill factor (FF) than Comparative Examples 1-2. This ultimately achieves a large-area module with high efficiency and high uniformity. Meanwhile, the efficiency of Comparative Example 2 is lower than that of Examples 1 and 2, indicating that incorporating SAM (4PADCB / 6PADCB) molecules into the perovskite precursor for one-step coating is better than simply using it as a hole transport layer. Furthermore, JV testing results show that the FF of the device using 6PADCB is increased to 78.60%, significantly higher than the 76.08% using 4PADCB. This improvement in key performance demonstrates that longer carbon chains can greatly improve the internal charge transport performance of the device by optimizing interfacial contact and reducing non-radiative recombination.

[0099] Table 1 Efficiency Comparison Table Open circuit voltage (V) Photoelectric conversion efficiency (%) Fill factor (%) Current density (mA / cm2) Comparative Example 1 5.48 8.54 39.18 3.97 Comparative Example 2 7.07 18.86 65.41 4.07 Example 1 7.10 21.16 76.08 3.92 Example 2 7.12 23.41 78.60 4.17 The above is a detailed description of the preferred embodiments of this application. However, this application is not limited to the above embodiments. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of this application. All such equivalent modifications or substitutions are included within the scope defined by the claims of this application.

Claims

1. A method for preparing a perovskite solar cell, characterized in that, Including the following steps: Preparation of perovskite precursor solution; An amphiphilic interface molecule is added to the perovskite precursor solution and mixed evenly to obtain a modified precursor solution. The amphiphilic interface molecule includes at least one of 4PADCB, 6PADCB, or 8PADCB. The modified precursor solution was coated onto a transparent electrode to prepare a perovskite functional layer. An electron transport layer is prepared on the surface of the perovskite functional layer; A barrier layer is prepared on the surface of the electron transport layer; A top electrode is fabricated on the surface of the barrier layer.

2. The method for preparing a perovskite solar cell according to claim 1, characterized in that, In the modified precursor solution, the concentration of the amphiphilic interface molecules is 0.3~0.8 mg / ml.

3. The method for preparing a perovskite solar cell according to claim 1, characterized in that, The scraping speed is 10~20mm / s; And / or, the gap between the scraper blades used for coating is 100~300μm; And / or, the air knife pressure for the coating is 0.3~0.8MPa; And / or, after scraping, the process also includes the step of annealing on a hot plate at 100~150℃ for 10~20 minutes.

4. The method for preparing a perovskite solar cell according to claim 1, 2, or 3, characterized in that, Including at least one of (a1) to (a6): (a1) The perovskite precursor solution comprises a binary cationic perovskite component, the chemical formula of which is FA. x Cs y PbI3, 0.88≤x≤0.95, 0.05≤y≤0.12, and x+y=1; (a2) The perovskite precursor solution includes a solvent, which includes at least one of DMF or NMP; (a3) The transparent electrode includes at least one of ITO electrode, FTO electrode, or AZO electrode; (a4) The electron transport layer includes a C60 thin film or a PCBM thin film; (a5) The barrier layer includes a BCP film; (a6) The top electrode includes a Cu electrode or an Ag electrode.

5. The method for preparing a perovskite solar cell according to claim 4, characterized in that, Including at least one of (b1) to (b5): (b1) The thickness of the transparent electrode is 100~200nm; (b2) The thickness of the perovskite functional layer is 600~800 nm; (b3) The thickness of the electron transport layer is 30~50nm; (b4) The thickness of the barrier layer is 6~10nm; (b5) The thickness of the top electrode is 100~200nm.

6. A perovskite solar cell, characterized in that, The perovskite solar cell is prepared using the preparation method described in any one of claims 1-5.

7. A perovskite solar cell module, characterized in that, The invention comprises a plurality of perovskite solar cells connected in series, wherein the perovskite solar cells are prepared by the preparation method described in any one of claims 1-5.

8. The perovskite solar cell module according to claim 7, characterized in that, The method for preparing the perovskite solar cell module further includes the step of pre-treating the transparent electrode, wherein the pre-treating includes: using laser scribing to perform P1 etching on the transparent electrode, followed by ultrasonic cleaning and ultraviolet-ozone cleaning.

9. The perovskite solar cell module according to claim 8, characterized in that, In the laser scribing step, a pulsed laser with a wavelength of 1064nm and an average laser power of 30W is used to scribble through the transparent electrode.

10. An application of a perovskite solar cell as described in claim 6 or a perovskite solar cell module as described in any one of claims 7-9 in the photovoltaic field, electronic devices, new energy vehicles, aerospace field, or building field.

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