Methods for perovskite crystallization, lead-based organic-inorganic hybrid perovskite solar cells and their fabrication methods

Abstract

This invention belongs to the fields of new materials technology and new energy technology. It discloses a method for perovskite crystallization, a lead-based organic-inorganic hybrid perovskite solar cell and its preparation method. The method involves spin-coating a lead iodide solution containing volatile DAP and rubidium, a mixed solution of formamidinium hydroiodate and methylamine hydrochloride containing a GABA hydrogen bond network, followed by spin-coating of a [6,6]-phenyl C61 butyrate solution and a 2,9-dimethyl-4,7-biphenyl-1,10-o-phenanthroline solution, and then depositing a silver electrode to assemble a lead-based organic-inorganic hybrid perovskite solar cell based on the synergistic effect of DAP and GABA dual intermediates. This invention proposes a staged control strategy to significantly improve the quality of the perovskite thin film. The perovskite solar cell prepared through the synergistic effect of the dual intermediates achieves a photoelectric conversion efficiency (PCE) exceeding 25.5%, and retains more than 95% of its initial efficiency after operating at maximum power for 1200 hours.

Description

Technical Field

[0001] This invention belongs to the fields of new materials technology and new energy technology, and particularly relates to a method for synergistic regulation of perovskite crystallization by volatile polyamines and zwitterionic compounds, a method for preparing lead-based organic-inorganic hybrid perovskite solar cells, and solar cells. Background Technology

[0002] Perovskite solar cells have become a research hotspot in the photovoltaic field due to their high photoelectric conversion efficiency and low fabrication cost. However, the crystallinity quality of perovskite thin films directly determines the device performance and stability. Their growth process involves complex precursor dissolution-coordination-crystallization kinetics. Especially in multi-step solution-based fabrication, coordinating the precursor dissociation and organic salt reaction rates remains a significant challenge. In existing technologies, researchers often introduce intermediates (such as methylamine chloride and dimethyl sulfoxide) or passivating agents (such as phenethylamine bromate and thiourea) to regulate crystallization, but problems such as the mismatch between precursor dissociation and solvent penetration, and the uncontrollable kinetics of organic salt reactions still exist.

[0003] First, while traditional volatile ligands (such as methylamine gas) can induce mesophase formation, it is difficult to precisely control the octahedral dissociation energy of PbI2, leading to uneven solvent penetration and a wide grain size distribution. Furthermore, a single ligand cannot simultaneously address both porous structure and reaction kinetics, resulting in low precursor conversion rates. Additionally, during perovskite conversion, excessively rapid deprotonation of organic salts (such as FAI) can easily induce disordered crystallization, forming pinholes and halogen vacancy defects. Although additives can slow the reaction, their static passivation mechanisms are insufficient to dynamically adapt to changes in the crystallization path, and large-molecule additives can easily block carrier transport channels, limiting the fill factor.

[0004] Based on the above analysis, the problems and shortcomings of the existing technology are as follows:

[0005] (1) In the prior art, the method of controlling crystallization by introducing intermediates or passivating agents has problems such as mismatch between precursor dissociation and solvent penetration and uncontrollable organic salt reaction kinetics.

[0006] (2) Traditional volatile ligands are difficult to precisely control the octahedral dissociation energy of PbI2, resulting in uneven solvent penetration and wide grain size distribution; and a single ligand cannot take into account both porous structure and reaction kinetics regulation, resulting in low precursor conversion rate.

[0007] (3) During the perovskite transformation process, the deprotonation rate of organic salts is too fast, which can easily lead to disordered crystallization, forming pinholes and halogen vacancy defects. Its static passivation mechanism is difficult to adapt to the changes in crystallization path, and macromolecular additives can easily block the carrier transport channels, resulting in limited filling factor. Summary of the Invention

[0008] To overcome the problems existing in related technologies, the present invention discloses a method for synergistic regulation of perovskite crystallization by volatile polyamines and zwitterionic compounds, particularly relating to a method for synergistic regulation of perovskite crystallization based on 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates and its application in high-efficiency solar cells. The technical solution is as follows:

[0009] This invention is achieved by using a method for synergistic regulation of perovskite crystallization by volatile polyamines and zwitterionic compounds, comprising the following steps:

[0010] S1, spin-coating a lead iodide solution containing volatile 1,3-propanediamine and rubidium;

[0011] S2, spin-coating a mixed solution of formamidin hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network;

[0012] S3, [6,6]-phenyl C61 butyrate methyl ester solution and 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline solution were spin-coated sequentially to achieve phased dynamic synergistic regulation of perovskite crystallization.

[0013] Another object of the present invention is to provide a method for preparing a lead-based organic-inorganic hybrid perovskite solar cell by implementing the method, the method comprising:

[0014] (1) Prepare an aqueous solution of nickel oxide with a concentration of 0.1-1.5 mg / mL, spin-coat the aqueous solution of nickel oxide onto a clean indium tin oxide conductive glass substrate, and anneal it to obtain a hole transport layer.

[0015] (2) Prepare an ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid with a concentration of 0.2-5 mg / mL. Spin-coat the ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid onto the surface of the hole transport layer prepared in step (1). After annealing, obtain a self-assembled molecular layer.

[0016] (3) Weigh PbI2 and RbI and dissolve them in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide to obtain a lead iodide solution containing rubidium; then dissolve 0.1-0.3 mg of 1,3-propanediamine in the lead iodide solution containing rubidium and heat to dissolve to obtain a lead iodide solution containing volatile 1,3-propanediamine and rubidium.

[0017] (4) Spin-coat the surface of the self-assembled molecular layer prepared in step (2) with a lead iodide solution containing volatile 1,3-propanediamine and rubidium, and anneal it to obtain a lead iodide thin film containing rubidium with vertically distributed cavities.

[0018] (5) Spin-coating a solution of a mixture of formamidine hydroiodate and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network onto the surface of the rubidium-containing lead iodide film prepared in step (4), and then annealing it at high temperature in air to obtain a lead-based organic-inorganic hybrid perovskite film.

[0019] (6) The lead-based organic-inorganic hybrid perovskite film prepared in step (5) is sequentially spin-coated with a solution of methyl [6,6]-phenyl C61 butyrate and a solution of 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline, and then annealed to obtain an electron transport layer.

[0020] (7) Silver electrodes are deposited on the surface of the electron transport layer in step (6) to assemble a lead-based organic-inorganic hybrid perovskite solar cell based on the synergistic effect of 1,3-propanediamine and γ-aminobutyric acid dual intermediates.

[0021] In step (3), the molar concentration of solute PbI2 is 1-1.8 mol / L, and the molar concentration of RbI is 0.01-0.018 mol / L; the volume ratio of N,N-dimethylformamide and dimethyl sulfoxide in the mixed solution is 9:1.

[0022] The concentration of 1,3-propanediamine in the rubidium-containing lead iodide solution is 0.1-0.3 mg / mL. The heating and dissolution temperature of the rubidium-containing lead iodide solution is 60-80℃, and the heating and dissolution time is 24-48 h.

[0023] In step (4), the spin coating speed of the rubidium-containing lead iodide film is 2300-2500 r / min, the annealing temperature is 60-80℃, and the annealing time is 60-90s.

[0024] In step (5), the concentration of γ-aminobutyric acid in the mixed isopropanol solution containing the γ-aminobutyric acid hydrogen bond network is 0.05-0.2 mg / mL, the concentration of formamidin hydroiodide is 70-110 mg / mL, and the concentration of methylamine hydrochloride is 7-11 mg / mL.

[0025] In step (5), the isopropanol solution containing a mixture of formamidinium hydroiodide and methylamine hydrochloride with a γ-aminobutyric acid hydrogen bond network is spin-coated at a speed of 2700-2900 r / min, annealed at a temperature of 150-170℃, and annealed for 10-15 min.

[0026] In step (6), the concentration of the [6,6]-phenyl C61 butyrate methyl ester solution is 20 mg / mL, and the concentration of the 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline solution is 2 mg / mL.

[0027] Another objective of this invention is to provide a lead-based organic-inorganic hybrid perovskite solar cell, which is prepared by the method described above. The cell has the following components arranged from bottom to top: (1) a conductive substrate, (2) a nickel oxide hole transport layer, (3) a self-assembled molecular layer, (4) a lead-based organic-inorganic hybrid perovskite thin film layer, (5) a [6,6]-phenyl C61 butyrate methyl ester electron transport layer, (6) a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline blocking layer, and (7) a silver electrode layer.

[0028] The conductive substrate is an indium tin oxide transparent conductive substrate; the hole transport layer is a nickel oxide and small molecule self-assembled layer with a thickness of 20 nm; the lead-based organic-inorganic hybrid perovskite layer is a lead-based organic-inorganic hybrid perovskite film treated with 1,3-propanediamine and γ-aminobutyric acid dual intermediates with a thickness of 680 nm; the electron transport layer is a [6,6]-phenyl C61 butyrate methyl ester film with a thickness of 20 nm; the electron transport layer is a 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline film with a thickness of 6 nm; and the counter electrode layer is a silver counter electrode layer with a thickness of 100 nm.

[0029] Furthermore, the battery has an open-circuit voltage of 1.00-1.16V and a short-circuit current of 23-25mA·cm. -2 The fill factor is 0.80-0.86, and the photoelectric conversion efficiency is 18.5-24.5%.

[0030] Another object of the present invention is to provide an application of the lead-based organic-inorganic hybrid perovskite solar cell photovoltaic cell module and photovoltaic curtain wall.

[0031] Combining all the above technical solutions, the beneficial effects of this invention are as follows:

[0032] First, addressing the problems of high precursor dissociation barriers, disordered crystallization, and high defect density in traditional perovskite thin film preparation processes, this invention innovatively proposes a staged control strategy. Firstly, volatile 1,3-propanediamine (DAP) is used to coordinate with PbI2 to form a porous intermediate layer PbI2(DAP)2, expanding the PbI2 lattice spacing by more than 20%, thus achieving vertical distribution of PbI2 film cavities and optimizing organic salt permeability. Subsequently, γ-aminobutyric acid (GABA) is introduced as a kinetic regulator for organic salt reactions, with its organic amine groups reacting with formamidinium ions (FA... +This method forms a hydrogen bond network, slows down the deprotonation rate, induces ordered molecular exchange, and inhibits halogen vacancy generation. It significantly improves the quality of perovskite thin films, achieving grain sizes of 800-1500 nm and reducing defect density by more than 33%. Perovskite solar cells prepared using this method achieve a power conversion efficiency (PCE) exceeding 25.5%, and retain over 95% of their initial efficiency after 1200 hours of operation at maximum power. This invention, through the synergistic effect of two intermediates, solves the industry challenge of coordinating the control of perovskite crystallization kinetics and thermodynamics, providing an innovative solution for the large-scale fabrication of high-performance, long-lifespan perovskite photovoltaic devices.

[0033] Secondly, this invention proposes for the first time a dual-intermediate synergistic mechanism of "gas-phase coordination-liquid-phase hydrogen bonding". Through a phased dynamic synergistic intervention mechanism, the perovskite crystal growth path is precisely optimized, fundamentally improving the crystal quality and carrier transport dynamics of lead-based organic-inorganic hybrid perovskite films. This results in high-performance lead-based organic-inorganic hybrid perovskite solar cells with low cost, high efficiency, and long lifetime, which has significant theoretical and practical value and promising market application prospects.

[0034] Compared to existing single-intermediate or static passivation technologies, this invention achieves precise optimization of the perovskite crystallization pathway through the staged synergistic effect of volatile 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates. Using the technical solution of this invention, the photoelectric conversion efficiency of lead-based organic-inorganic hybrid perovskite solar cells has been increased to over 25%, demonstrating significant technical effectiveness.

[0035] Traditional static passivation strategies are inadequate for addressing the dynamic defect formation in perovskites under stress conditions such as humidity, heat, and light. This invention, however, utilizes a synergistic passivation mechanism of DAP and GABA to achieve dynamic defect capture and repair. The GABA-embedded amine groups (-NH2) and ionized protons (H2O)... + This method forms a dual-site passivation network, providing technical support for extending the lifetime of organic-inorganic hybrid perovskite solar cells. Lead-based organic-inorganic hybrid perovskite solar cells prepared based on this method maintained over 95% of their initial efficiency after 1200 hours of continuous testing in a nitrogen atmosphere with a relative humidity of 40%, showing no significant efficiency degradation.

[0036] Third, the technical solution of this invention, once commercialized, is expected to significantly enhance the commercial competitiveness of perovskite photovoltaic modules and photovoltaic curtain walls. High-quality thin films (grain size 800-1500nm, defect density 3.83×10⁻⁶) are achieved through a phased control strategy. 15 / cm 3This technology can effectively reduce the manufacturing cost of optoelectronic devices. Its long-term stability meets international certification requirements, and it is expected to capture 20% of the mid-to-high-end perovskite photovoltaic market within five years, generating an annual output value exceeding 10 billion yuan. Furthermore, this technology can be extended to the field of perovskite-crystalline silicon tandem cells, helping to break through the 33% industry threshold for efficiency and seize the commanding heights of next-generation photovoltaic technology.

[0037] This invention innovatively solves the international technical bottleneck of kinetic and thermodynamic mismatch in the crystallization process of perovskite thin films through a staged dual-intermediate synergistic control strategy, filling the gap in the field of step-by-step controllable crystallization of lead-based organic-inorganic hybrid systems. Its pioneering synergistic mechanism of DAP-induced porous intermediate layer (lattice spacing expansion rate > 20%) and GABA hydrogen bond network slow-release effect overcomes the limitations of traditional single-phase control techniques in simultaneously addressing precursor dissociation, ordered molecular arrangement, and defect suppression. It achieves core industrialization indicators such as photoelectric conversion efficiency greater than 25.5% and long-term stability (T80 > 3000h), propelling perovskite photovoltaic technology from the laboratory to large-scale application and providing a highly efficient and stable original Chinese technical path for the global new energy industry.

[0038] This invention successfully overcomes the long-standing problem of crystallization kinetics and thermodynamic mismatch in the perovskite photovoltaic field: traditional processes result in a film defect density that is consistently higher than 10 due to the dense arrangement of precursors and disordered molecular exchange. 16 / cm 3 Furthermore, the grain size is limited to 200-500 nm. Through the synergistic mechanism of DAP-induced porous intermediate layer (lattice expansion rate 20%) and GABA hydrogen bond network regulation, ordered molecular exchange, efficient phase transformation, good crystal orientation, and simultaneous suppression of defects at grain boundaries (defect density 3.83 × 10⁻⁶) were achieved. 15 / cm 3 This breakthrough breaks the efficiency-stability inversion relationship (PCE>25.5% and T80>3000h).

[0039] This invention overcomes the long-standing technical bias in the perovskite photovoltaic field of the incompatibility between kinetic and thermodynamic control through a staged dual-intermediate synergistic strategy. Traditional processes typically employ single additives or annealing optimization, making it difficult to simultaneously achieve precursor lattice expansion and molecular order exchange, resulting in limitations on defect density and grain size. This technology constructs a porous intermediate layer (lattice expansion rate 20.8%) using DAP, synergistically combining it with a GABA hydrogen bond network to achieve high-quality thin films (grain size 800-1500 nm, defect density 3.83 × 10⁻⁶). 15 / cm 3 Breakthrough efficiency-stability inversion relationship (PCE>25.5% and T80>3000h). Attached Figure Description

[0040] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure;

[0041] Figure 1 This is a flowchart of a method for synergistic regulation of perovskite crystallization by volatile polyamines and zwitterionic compounds provided in an embodiment of the present invention;

[0042] Figure 2 This is a structural diagram of the lead-based organic-inorganic hybrid perovskite solar cell device prepared in Example 1 of the present invention;

[0043] Figure 3 These are scanning electron microscope images provided in the embodiments of the present invention; wherein (a) is a scanning electron microscope image of the lead-based organic-inorganic hybrid perovskite thin film prepared in Example 1, and (b) is a scanning electron microscope image of the thin film prepared in Comparative Example 1;

[0044] Figure 4 The JV curves are shown for the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of this invention and the solar cell prepared in Control Example 1.

[0045] Figure 5 This is a test diagram of the light stability of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of this invention;

[0046] Figure 6 These are the JV curves of the lead-based organic-inorganic hybrid perovskite solar cells prepared in Examples 2, 3, and 4 of this invention;

[0047] In the figure: 1. Conductive substrate; 2. Hole transport layer; 3. Self-assembled molecular layer; 4. Lead-based organic-inorganic hybrid perovskite thin film layer; 5. [6,6]-phenyl C61 butyrate methyl ester (PCBM) electron transport layer; 6. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) blocking layer; 7. Silver electrode layer. Detailed Implementation

[0048] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0049] The innovation of this invention lies in its innovative construction of a synergistic regulatory system between volatile polyamine (DAP) and zwitterionic compound (GABA), overcoming the challenge of thermodynamic-kinetic synergistic optimization in perovskite crystallization. DAP and PbI2 form a porous intermediate PbI2(DAP)2, constructing vertical channels to enhance organic salt permeation, achieving ordered molecular exchange, and completely volatilizing without residue after annealing; GABA reacts with FA through amino groups... + The formation of a hydrogen bond network delays deprotonation, and its carboxyl groups chelate Pb. 2+ Further suppression of halogen vacancy formation energy. After perovskite crystallization optimization, the grain size reaches 800-1500 nm, and the bulk defect density is 3.83 × 10⁻⁶. 15 / cm 3 The device achieves an efficiency of 25.52% and retains over 95% of its efficiency after operating at the maximum power point for 1200 hours, providing an innovative solution for the large-scale fabrication of high-performance, long-life perovskite photovoltaic devices.

[0050] Example 1, as Figure 1 As shown in the embodiments of the present invention, the method for synergistic regulation of perovskite crystallization by volatile polyamines and zwitterionic compounds includes the following steps:

[0051] S1, spin-coating a lead iodide solution containing volatile 1,3-propanediamine and rubidium;

[0052] S2, spin-coating a mixed solution of formamidin hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network;

[0053] S3, [6,6]-phenyl C61 butyrate methyl ester solution and 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline solution were spin-coated sequentially to achieve phased dynamic synergistic regulation of perovskite crystallization.

[0054] This invention, using 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) as dopants, describes a method for preparing a lead-based organic-inorganic hybrid perovskite solar cell based on the dual intermediates of 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA), specifically including the following steps:

[0055] (1) Prepare an aqueous solution of nickel oxide with a concentration of 1 mg / mL, wherein the nickel oxide is the solute and water is the solvent;

[0056] (2) Spin-coat 100 μL of nickel oxide aqueous solution onto a clean ITO conductive glass substrate. Spin-coat at 2000 r / min for 30 s and then anneal at 120 °C for 5 min to obtain a hole transport layer.

[0057] (3) Prepare an ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid with a concentration of 1 mg / mL, where [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid is the solute and ethanol is the solvent;

[0058] (4) Spin-coat 100 μL of ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid onto the hole transport layer. After spin-coating for 30 s at a speed of 3000 r / min, anneal at 100 °C for 10 min to obtain a self-assembled molecular layer.

[0059] (5) A certain amount of PbI2 and RbI were dissolved in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (the volume ratio of N,N-dimethylformamide and dimethyl sulfoxide was 9:1) to obtain a rubidium-containing lead iodide solution; wherein the molar concentration of solute PbI2 in the mixed solution was 1.8 mol / L and the molar concentration of solute CsI in the mixed solution was 0.018 mol / L; then 1,3-propanediamine (DAP) was added to make the concentration of 1,3-propanediamine in the rubidium-containing lead iodide solution 0.2 mg / mL; after stirring magnetically at 70 °C for 24 h, the solution was filtered using a polytetrafluoroethylene filter to obtain a DAP-coordinated rubidium-containing lead iodide solution;

[0060] (6) Spin-coat 75 μL of rubidium-containing lead iodide solution onto the self-assembled molecular layer at a spin-coating speed of 2500 r / min for 30 s; then anneal at 70 °C for 60 s using a constant temperature heating table to obtain a rubidium-containing lead iodide film.

[0061] (7) 110 μL of isopropanol solution containing 0.1 mg / mL of γ-aminobutyric acid (GABA) hydrogen bond network of formamidinium hydroiodate and methylamine hydrochloride was spin-coated onto a rubidium-containing lead iodide film. The concentration of GABA in the mixed isopropanol solution was 0.1 mg / mL, the concentration of formamidinium hydroiodate was 90 mg / mL, and the concentration of methylamine hydrochloride was 10 mg / mL. The film was magnetically stirred at room temperature for 30 min until completely dissolved. The spin-coating speed was 2900 r / min and the spin-coating time was 30 s. The film was annealed on a constant temperature heating stage at 150 °C in air for 10 min to obtain a lead-based organic-inorganic hybrid perovskite film containing a dual intermediate of 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA).

[0062] (8) The lead-based organic-inorganic hybrid perovskite film of the 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediate prepared in step (7) was sequentially spin-coated with 20 mg / mL [6,6]-phenyl C61 butyrate methyl ester solution and 2 mg / mL 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline solution. The spin-coating speed was 2000 r / min and the spin-coating time was 180 s.

[0063] (9) Silver electrodes were deposited by vapor deposition to prepare lead-based organic-inorganic hybrid perovskite solar cells containing 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates.

[0064] Figure 2 This is a device structure diagram of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of the present invention. The cell includes, from bottom to top, a conductive substrate 1, a nickel oxide hole transport layer 2, a self-assembled molecular layer 3, a lead-based organic-inorganic hybrid perovskite thin film layer 4, a [6,6]-phenyl C61 butyrate methyl ester (PCBM) electron transport layer 5, a 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) blocking layer 6, and a silver electrode layer 7. The conductive substrate 1 is an indium tin oxide (ITO) transparent conductive substrate; hole transport layers 2 and 3 are nickel oxide and small molecule self-assembled layers with a thickness of 20 nm; lead-based organic-inorganic hybrid perovskite layer 4 is a lead-based organic-inorganic hybrid perovskite film treated with 1,3-propanediamine and γ-aminobutyric acid dual intermediates with a thickness of 680 nm; PCBM electron transport layer 5 is a [6,6]-phenyl C61 butyrate methyl ester film with a thickness of 20 nm; BCP blocking layer 6 is a 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline film with a thickness of 6 nm; and counter electrode layer 7 is a silver counter electrode layer with a thickness of 100 nm.

[0065] Compared with Example 1, a lead-based organic-inorganic hybrid perovskite thin film without the addition of the dual intermediates of 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) was constructed. The steps of Comparative Example 1 and Example 1 are generally the same, except that in step (5), the molar concentration of solute PbI2 in the mixed solution is 1.2 mol / L and the molar concentration of solute CsI in the mixed solution is 0.012 mol / L; in step (7), the concentration of formamidin hydroiodate is 90 mg / mL and the concentration of methylamine hydrochloride is 10 mg / mL.

[0066] Scanning electron microscope images of the lead-based organic-inorganic hybrid perovskite thin film prepared in Example 1 of this invention and the thin film prepared in Control Example 1 are shown below. Figure 3 Figures (a) and (b) are shown in the table. The solar cells prepared in Example 1 and Comparative Example 1 were tested respectively, and the test results are shown below:

[0067] The test was conducted under standard test conditions (AM1.5 illumination). Figure 4 The JV curves are shown for the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of this invention and the solar cell prepared in Control Example 1. Figure 4 As shown, the reverse scanning photoelectric conversion efficiency of the solar cell device prepared in Example 1 of this invention is 25.52%, the open-circuit voltage is 1.166V, and the short-circuit current is 25.51mA / cm. 2 The fill factor is 85.80%. The solar cell device of Comparative Example 1 has a forward scanning photoelectric conversion efficiency of 21.87%, an open-circuit voltage of 1.066V, and a short-circuit current of 24.85mA / cm². 2 The fill factor was 82.60%. This demonstrates that the addition of the 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA) dual intermediates significantly improves the quality of perovskite films, increases the fill factor and open-circuit voltage, and enhances photoelectric conversion efficiency.

[0068] Figure 5 This is a test image showing the light stability of the lead-based organic-inorganic hybrid perovskite solar cell prepared in Example 1 of this invention. Figure 5 As shown, the solar cell prepared in Example 1 of this invention can maintain an initial efficiency of 95.2% after 1200 hours in a nitrogen atmosphere at 50°C. Therefore, the lead-based organic-inorganic hybrid perovskite solar cell prepared in this invention, with crystallization controlled by the dual intermediates of 1,3-propanediamine (DAP) and γ-aminobutyric acid (GABA), exhibits good photoelectric conversion efficiency and stability.

[0069] Example 2: The preparation process of this example is largely the same as that of Example 1. The similarities will not be repeated here. The difference is that γ-aminobutyric acid (GABA) was not added in step (7), and a lead-based organic-inorganic hybrid perovskite solar cell was constructed.

[0070] Example 3: The preparation process of this example is largely the same as that of Example 1. The similarities will not be repeated here. The difference is that 1,3-propanediamine (DAP) was not added in step (5), and a lead-based organic-inorganic hybrid perovskite solar cell was constructed.

[0071] Example 4: The preparation process of this example is generally the same as that of Example 1. The similarities will not be repeated here. The difference is that in step (5), 0.2 mg / mL of 1,3-propanediamine (DAP) is replaced with 0.3 mg / mL of 1,3-propanediamine (DAP), and in step (7), 0.1 mg / mL of γ-aminobutyric acid (GABA) is replaced with 0.2 mg / mL of γ-aminobutyric acid (GABA). A lead-based organic-inorganic hybrid perovskite solar cell is constructed.

[0072] The solar cells prepared in Examples 2-4 were tested respectively, and the test results are shown below:

[0073] The test was conducted under standard test conditions (AM1.5 illumination). Figure 6 The JV curves are shown for the lead-based organic-inorganic hybrid perovskite solar cells prepared in Examples 2-4 of this invention. Figure 6 As shown, in Example 2 of this invention, when 0.2 mg / mL of 1,3-propanediamine (DAP) was used, the photovoltaic conversion efficiency of the prepared solar energy device with reverse scanning was 24.44%, the open-circuit voltage was 1.149 V, and the short-circuit current was 25.36 mA / cm². 2 The fill factor was 83.87%. In Example 3 of this invention, when 0.1 mg / mL of γ-aminobutyric acid (GABA) was used, the photovoltaic conversion efficiency of the prepared solar energy device with reverse scanning was 24.51%, the open-circuit voltage was 1.138 V, and the short-circuit current was 25.42 mA / cm². 2 The fill factor was 84.72%. In Example 4 of this invention, when 0.3 mg / mL of 1,3-propanediamine (DAP) and 0.2 mg / mL of γ-aminobutyric acid (GABA) were used, the resulting solar cell device exhibited a reverse scanning photoelectric conversion efficiency of 24.87%, an open-circuit voltage of 1.163 V, and a short-circuit current of 25.12 mA / cm². 2 The fill factor is 85.10%.

[0074] Table 1 shows the relevant parameters of the lead-based organic-inorganic hybrid perovskite solar cells prepared in Examples 1-4 and Comparative Example 1 of the present invention. As shown in Table 1, Examples 1-4 of the present invention all show improved performance compared to Comparative Example 1. Further comparison of Examples 1-4 shows that the most significant improvement was achieved in Example 1 when the addition amount of 1,3-propanediamine (DAP) was 0.2 mg / mL and the addition amount of γ-aminobutyric acid (GABA) was 0.1 mg / mL, which is the preferred amount of additives.

[0075] Table 1. Process parameters of lead-based organic-inorganic hybrid perovskite solar cells compared with Example 1 and Examples 1-4.

[0076]

[0077]

[0078] Experimental design, experimental group and control group:

[0079] Experimental group: Employing the phased control strategy of this invention;

[0080] Step 1: Add 1,3-propanediamine (DAP) to the PbI2 precursor solution to form a porous intermediate layer PbI2(DAP)2, spin-coated and then annealed (100°C, 10 minutes).

[0081] Step 2: Add γ-aminobutyric acid (GABA) to formamidine lead iodide (FAI) solution, spin coat and anneal twice (150℃, 15 minutes).

[0082] Control group: Traditional one-step perovskite thin film preparation:

[0083] Direct spin-coating of a mixed solution of PbI2 and FAI was performed, and the annealing conditions were the same as those for the experimental group (150℃, 15 minutes).

[0084] Evaluation indicators:

[0085] Precursor lattice spacing: X-ray diffraction analysis of lattice spacing variations;

[0086] Perovskite crystal quality: grain size.

[0087] Perovskite defect density: Trap state density measured by space charge-limited current method.

[0088] The comparison results of key performance data between the experimental group and the control group are shown in Table 2.

[0089] Table 2 Comparison of key performance data between the experimental group and the control group

[0090]

[0091] This experiment demonstrates through quantitative data that a phased control strategy can significantly improve the quality of perovskite thin films and device performance, breaking through the bottleneck of efficiency-stability balance and providing a reliable technical path for industrial applications.

[0092] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by those skilled in the art within the scope of the technology disclosed in the present invention and within the spirit and principles of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for synergistic regulation of perovskite crystallization by volatile polyamines and zwitterionic compounds, characterized in that, The method includes the following steps: S1, spin-coating a lead iodide solution containing volatile 1,3-propanediamine and rubidium; S2, spin-coating a mixed solution of formamidin hydroiodide and methylamine hydrochloride containing a γ-aminobutyric acid hydrogen bond network; S3, [6,6]-phenyl C61 butyrate methyl ester solution and 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline solution were spin-coated sequentially to achieve phased dynamic synergistic regulation of perovskite crystallization.

2. A method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 1, characterized in that, The fabrication method of this lead-based organic-inorganic hybrid perovskite solar cell includes: (1) Prepare an aqueous solution of nickel oxide with a concentration of 0.1-1.5 mg / mL, spin-coat the aqueous solution of nickel oxide onto a clean indium tin oxide conductive glass substrate, and anneal to obtain a hole transport layer; (2) Prepare an ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid with a concentration of 0.2-5 mg / mL. Spin-coat the ethanol solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid onto the surface of the hole transport layer prepared in step (1). After annealing, obtain a self-assembled molecular layer. (3) Weigh PbI2 and RbI and dissolve them in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide to obtain a lead iodide solution containing rubidium; then add 1,3-propanediamine and dissolve it in the lead iodide solution containing rubidium to make the final concentration of 1,3-propanediamine 0.1-0.3 mg / mL, and heat to dissolve to obtain a lead iodide solution containing volatile 1,3-propanediamine and rubidium; (4) Spin-coat the surface of the self-assembled molecular layer prepared in step (2) with a solution of volatile 1,3-propanediamine and rubidium, and anneal to obtain a rubidium-containing lead iodide film with vertically distributed cavities. (5) Spin-coat the surface of the lead iodide-containing thin film containing γ-aminobutyric acid hydrogen bond network with a mixed isopropanol solution of formamidine hydroiodate and methylamine hydrochloride prepared in step (4) and then anneal it at high temperature in air to obtain a lead-based organic-inorganic hybrid perovskite thin film. (6) The lead-based organic-inorganic hybrid perovskite film prepared in step (5) is spin-coated sequentially with a solution of methyl [6,6]-phenyl C61 butyrate and a solution of 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline, and then annealed to obtain an electron transport layer. (7) Silver electrodes are deposited on the surface of the electron transport layer in step (6) to assemble a lead-based organic-inorganic hybrid perovskite solar cell based on the synergistic effect of 1,3-propanediamine and γ-aminobutyric acid dual intermediates.

3. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, characterized in that, In step (3), the molar concentration of solute PbI2 is 1-1.8 mol / L, and the molar concentration of RbI is 0.01-0.018 mol / L; the volume ratio of N,N-dimethylformamide to dimethyl sulfoxide in the mixed solution of N,N-dimethylformamide and dimethyl sulfoxide is 9:

1. The heating and dissolution temperature of rubidium-containing lead iodide solution is 60-80℃, and the heating and dissolution time is 24-48h.

4. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, characterized in that, In step (4), the spin coating speed of the rubidium lead iodide film is 2300-2500 r / min, the annealing temperature is 60-80℃, and the annealing time is 60-90s.

5. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, characterized in that, In step (5), the concentration of γ-aminobutyric acid in the mixed isopropanol solution containing the γ-aminobutyric acid hydrogen bond network is 0.05-0.2 mg / mL, the concentration of formamidin hydroiodide is 70-110 mg / mL, and the concentration of methylamine hydrochloride is 7-11 mg / mL.

6. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, characterized in that, In step (5), the isopropanol solution containing a mixture of formamidinium hydroiodide and methylamine hydrochloride with a γ-aminobutyric acid hydrogen bond network is spin-coated at a speed of 2700-2900 r / min, annealed at a temperature of 150-170℃, and annealed for 10-15 min.

7. The method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to claim 2, characterized in that, In step (6), the concentration of the [6,6]-phenyl C61 butyrate methyl ester solution is 20 mg / mL, and the concentration of the 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline solution is 2 mg / mL.

8. A lead-based organic-inorganic hybrid perovskite solar cell, characterized in that, This battery is prepared by the method for preparing a lead-based organic-inorganic hybrid perovskite solar cell according to any one of claims 2-7. The battery comprises, from bottom to top, the following components: (1) A conductive substrate, wherein the conductive substrate is an indium tin oxide transparent conductive substrate; (2) A hole transport layer disposed on the conductive substrate, the hole transport layer comprising a nickel oxide layer with a thickness of 20 nm and a self-assembled molecular layer thereon; (3) A lead-based organic-inorganic hybrid perovskite thin film layer disposed on the self-assembled molecular layer, wherein the lead-based organic-inorganic hybrid perovskite thin film layer is a lead-based organic-inorganic hybrid perovskite thin film with a thickness of 680 nm formed after treatment with 1,3-propanediamine and γ-aminobutyric acid dual intermediates. (4) An electron transport layer disposed on the lead-based organic-inorganic hybrid perovskite thin film layer, the electron transport layer comprising a [6,6]-phenyl C61 butyrate methyl ester thin film layer and a 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline blocking layer with a thickness of 6 nm. (5) A silver electrode layer with a thickness of 100 nm is disposed on the 2,9-dimethyl-4,7-biphenyl-1,10-o-diazaphenanthroline barrier layer.

9. The lead-based organic-inorganic hybrid perovskite solar cell according to claim 8, characterized in that, The battery has an open-circuit voltage of 1.00-1.16V and a short-circuit current of 23-25mA·cm. -2 The fill factor is 0.80-0.86, and the photoelectric conversion efficiency is 18.5-24.5%.

10. The application of the lead-based organic-inorganic hybrid perovskite solar cell as described in claim 9 in solar photovoltaic cell modules and photovoltaic curtain walls.

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