Perovskite photovoltaic device regulated by benzotriazine derivative and preparation method thereof
By passivating the molecules of benzotriazine derivatives and modifying the interface, the problems of nonradiative recombination of charge carriers and uneven nucleation in wide-bandgap perovskite photovoltaic devices were solved, thereby improving the photoelectric conversion efficiency and stability.
Patent Information
- Application Number
- CN202611231169.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-08-14
- Publication Date
- 2026-11-03
AI Technical Summary
Existing wide-bandgap perovskite photovoltaic devices suffer from nonradiative recombination of charge carriers and uneven nucleation, which leads to reduced photoelectric conversion efficiency and stability.
Benzotriazine derivative molecules are used to passivate bulk and interface defects in perovskite. By coordinating Pb2+ with nitrogen heteroatoms, nonradiative recombination of charge carriers is reduced, and the thin film crystallization process is dynamically controlled. Molecular modifiers or organic salt modifiers are used to modify the interface of the perovskite light-absorbing layer.
It improves photoelectric conversion efficiency and stability, and enhances the overall performance of the device.
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Figure CN123035807A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of solar cell technology, specifically relating to a perovskite photovoltaic device regulated by a benzotriazine derivative and its preparation method. Background Technology
[0002] In recent years, perovskite photovoltaic devices have been recognized as a new technology for next-generation space photovoltaics due to their excellent photoelectric conversion efficiency and low-cost fabrication process. Currently, the internationally certified efficiency of crystalline silicon-perovskite tandem devices has reached 35.2%, comparable to gallium arsenide cells, which are the mainstream technology in space photovoltaics. In crystalline silicon-perovskite tandem devices, wide-bandgap perovskite photovoltaic devices are chosen as the top cell in the overall device structure. This requires them to meet the condition of bandgap matching with the underlying silicon cell. Therefore, wide-bandgap perovskite photovoltaic devices are a key factor driving the large-scale application of crystalline silicon-perovskite tandem cells in the future.
[0003] However, perovskite photovoltaic devices prepared by low-temperature spin coating still have many internal problems. For example, excessive defects at the hole transport layer / perovskite interface can lead to nonradiative recombination of charge carriers, reducing the photoelectric conversion efficiency of the device. Moreover, the Pb-Br binding energy is greater than that of Pb-I, so the Br-containing component usually crystallizes first, resulting in uneven nucleation and significantly reducing the performance of the device. These are all major challenges that wide-bandgap perovskite photovoltaic devices currently face in realizing space photovoltaic applications.
[0004] Currently, to address these issues, multifunctional molecular strategies can be employed to modulate perovskite thin films, passivate the perovskite interface, and simultaneously improve the quality of the perovskite film, thereby enhancing the photoelectric conversion efficiency and stability of wide-bandgap perovskite solar cells. However, determining the appropriate multifunctional molecular strategy to comprehensively improve the photoelectric conversion efficiency and stability of wide-bandgap perovskite photovoltaic devices remains a pressing issue. Summary of the Invention
[0005] To address the shortcomings of the prior art, this invention utilizes benzotriazine derivatives (1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, 1,2,4-benzotriazine-3-amine) molecules to passivate perovskite bulk defects and their lower interface defects. The abundant nitrogen heteroatoms in the benzotriazine derivative molecules act as Lewis bases, coordinating unsaturated Pb at the perovskite lower interface. 2+This reduces nonradiative recombination of charge carriers at the perovskite light-absorbing layer and its lower interface; at the same time, the weak basicity of the benzotriazine molecule itself allows it to exchange with formamidinium and methylamine ions in the perovskite solution, thereby dynamically controlling the crystallization process of the thin film, suppressing phase separation of the thin film, and improving the overall photoelectric conversion efficiency of the device.
[0006] To address the problems existing in the prior art, this invention proposes a perovskite photovoltaic device regulated by a benzotriazine derivative, the structure of which includes: a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a charge blocking layer, a back electrode layer, and molecular modifiers and organic salt modifiers for modifying perovskite solar cells. The upper or lower interface of the perovskite light-absorbing layer is coated with a molecular modifier or an organic salt modifier, or a molecular passivator is added to the perovskite light-absorbing layer. The molecular modifier comprises one or more benzotriazine derivative molecules, and the organic salt modifier comprises phenethylamine hydroiodate.
[0007] Furthermore, the molecular modifier or organic salt modifier also contains a first organic solvent, which is one or more of methanol, isopropanol, 2-methoxypropanol and chlorobenzene.
[0008] Furthermore, the molecular passivating agent also contains a second organic solvent, which is at least one selected from acetonitrile, isopropanol, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.
[0009] Furthermore, the benzotriazine derivative is one or more of the following five molecules: 1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, and 1,2,4-benzotriazine-3-amine.
[0010] This invention also provides a method for preparing the perovskite photovoltaic device regulated by the above-mentioned benzotriazine derivative, the method comprising the following steps: S1. Preparation of perovskite precursor solution: Dissolve the perovskite precursor in a third organic solvent in an anhydrous and oxygen-free nitrogen glove box to prepare a perovskite precursor solution with a concentration of 1.0-2.0M, and heat and stir at 20-40℃ for 2-12h; the third organic solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and when multiple solvents are selected, the volume ratio of the mixed solvents is 6:1-2:1; S2. Pre-treat the conductive substrate; the pre-treatment is ultraviolet ozone surface pre-treatment or plasma surface pre-treatment of the conductive substrate. S3. Spin-coat a hole transport layer solution onto a pretreated conductive substrate and anneal it to obtain a hole transport layer; the spin-coating time of the hole transport layer solution is 30s and the annealing temperature is 105℃. S4. Prepare a perovskite light-absorbing layer with molecular or organic salt modification on the hole transport layer to obtain a perovskite light-absorbing layer-upper interface modification layer or a perovskite light-absorbing layer-lower interface modification layer. S5. An electron transport layer and an electron blocking layer are sequentially spin-coated onto a perovskite light-absorbing layer modified with molecules or organic salts. A metal electrode layer is then thermally vapor-deposited above the electron blocking layer to obtain a perovskite photovoltaic device regulated by benzotriazine derivatives.
[0011] Furthermore, when step S4 is to prepare the perovskite light-absorbing layer-lower interface modification layer, the molecular modifier is first spin-coated onto the hole transport layer obtained in step S3, and after annealing, the perovskite precursor solution of step S1 is spin-coated onto the conductive substrate with the hole transport layer modified by the lower interface to obtain the perovskite light-absorbing layer-lower interface modification layer. The spin coating speed for spin coating the molecular modifier onto the hole transport layer is 2000-6000 rpm / min, and the spin coating time is 10-40 s; the annealing temperature is 100-120℃, and the annealing time is 5-20 min.
[0012] Furthermore, when step S4 is to prepare the perovskite light-absorbing layer-upper interface modification layer, the perovskite precursor solution of step S1 is first spin-coated onto the hole transport layer obtained in step S3, and after annealing heat treatment, the perovskite light-absorbing layer is obtained. Then, the organic salt modifier is spin-coated or scraped onto the perovskite light-absorbing layer, and after annealing heat treatment, the perovskite light-absorbing layer-upper interface modification layer is obtained. The spin coating speed of the perovskite precursor solution on the hole transport layer is 3000-6000 rpm / min, the spin coating time is 10-60 s, and the amount of perovskite precursor solution added is 30-100 μL; the annealing heat treatment temperature is 100-150℃, and the treatment time is 10-30 min.
[0013] Furthermore, when step S4 involves adding a molecular passivator to the perovskite light-absorbing layer, the molecular passivator and the perovskite precursor solution from step S1 are mixed and spin-coated onto a conductive substrate with a hole transport layer. After annealing and heat treatment, a perovskite light-absorbing layer with added molecular passivator is obtained. When the molecular passivator and the perovskite precursor solution are mixed, the amount of molecular passivator added is 1μL-20μL.
[0014] Furthermore, the concentration of the molecular modifier used in spin coating is 0.1-2.0 mg / mL.
[0015] Furthermore, the concentration of the organic salt modifier used in spin coating is 0.1-2.0 mg / mL.
[0016] Furthermore, the concentration of the added molecular modifier is 0.1-2.0 mg / mL.
[0017] Compared with the prior art, the present invention has the following beneficial technical effects: 1. This invention utilizes benzotriazine derivatives (1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, 1,2,4-benzotriazine-3-amine) molecules to passivate defects at the perovskite under-interface. The abundant nitrogen heteroatoms in the benzotriazine derivative molecules act as Lewis bases, coordinating unsaturated Pb at the perovskite under-interface. 2+ This reduces nonradiative recombination of charge carriers at the interface beneath the perovskite light-absorbing layer, further improving photoelectric conversion efficiency.
[0018] 2. This invention utilizes benzotriazine derivatives (1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, 1,2,4-benzotriazine-3-amine) molecules mixed into the perovskite precursor solution. Due to their weak alkalinity, they can exchange with formamidinium and methylamine ions in the perovskite solution, thereby dynamically controlling the crystallization process of the thin film, inhibiting perovskite phase separation, and improving the overall photoelectric conversion efficiency of the device.
[0019] 3. The benzotriazine derivative of the present invention has a molecular protective effect that is not limited by position. It can be used as a modifier to modify the lower surface of the perovskite light-absorbing layer, or as a molecular passivator added into the perovskite light-absorbing layer, thereby achieving multi-position optimization effect. It is also compatible with other perovskite surface passivation technologies and has repeatability. Attached Figure Description
[0020] To more clearly illustrate the technical solutions of the embodiments of this disclosure, the accompanying drawings of the embodiments will be briefly described below. It should be understood that the drawings described below only relate to some embodiments of this disclosure and are not intended to limit this disclosure, wherein: Figure 1 This is a structural diagram of a perovskite solar cell covering the positions of molecular bulk passivation, upper interface modification, and lower interface modification provided by the present invention; Figure 2The present invention provides the molecular structural formulas of benzotriazine derivatives, wherein (a) is the structural formula of 1,2,4-benzotriazine-3-amine, (b) is the structural formula of 1,2,3-benzotriazine-4(3H)-one, (c) is the structural formula of 1,2,3-benzotriazine-4(3H)-thiol, (d) is the structural formula of 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, and (e) is the structural formula of 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol; Figure 3 The images show the current-voltage curves (a), SEM images (b), and SEM images (c) of the perovskite solar cells prepared in Comparative Example 1, which are the control group perovskite solar cells prepared in Comparative Example 1. Figure 4 The images show the current-voltage curve (a) of the perovskite solar cell with lower interface modification of 1,2,4-benzotriazine-3-amine molecule prepared in Example 1 of this invention and the SEM image (b) of the lower interface of the perovskite layer in Example 1. Figure 5 The current-voltage curve (a) of the perovskite solar cell with lower interface modification of 1,2,3-benzotriazine-4(3H)-one molecule prepared in Example 2 of the present invention and the SEM image of the lower interface of the perovskite layer in Example 2 (b) are shown. Figure 6 The current-voltage curve (a) of the perovskite solar cell with lower interface modification of 1,2,3-benzotriazine-4(3H)-thiol molecule prepared in Example 3 of the present invention and the SEM image of the lower interface of the perovskite layer in Example 3 (b) are shown. Figure 7 The current-voltage curve (a) of the perovskite solar cell with lower interface modification of 3-hydroxy-1,2,3-benzotriazine-4(3H)-one molecule prepared in Example 4 of the present invention and the SEM image of the lower interface of the perovskite layer in Example 4 (b) are shown. Figure 8 The current-voltage curve (a) of the perovskite solar cell with interface modification of 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol molecule prepared in Example 5 of the present invention and the SEM image of the perovskite layer surface in Example 5 (b). Figure 9 The images show the current-voltage curve (a) of the perovskite solar cell with 1,2,4-benzotriazine-3-amine molecular bulk phase doped prepared in Example 6 of this invention and the SEM image (b) of the perovskite layer surface in Example 6. Figure 10 The current-voltage curve (a) of the perovskite solar cell doped with 1,2,3-benzotriazine-4(3H)-one molecules prepared in Example 7 of the present invention and the SEM image of the perovskite layer surface in Example 7 (b). Figure 11 The current-voltage curve (a) of the perovskite solar cell doped with 1,2,3-benzotriazine-4(3H)-thiol molecular bulk phase prepared in Example 8 of the present invention and the SEM image of the perovskite layer surface in Example 8 (b). Figure 12 The current-voltage curve (a) of the perovskite solar cell doped with 3-hydroxy-1,2,3-benzotriazine-4(3H)-one molecules prepared in Example 9 of the present invention and the SEM image of the perovskite surface in Example 9 (b). Figure 13 The current-voltage curve (a) of the perovskite solar cell with 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol molecular bulk phase doped in Example 10 of the present invention and the SEM image of the perovskite layer surface of Example 10 (b). Detailed Implementation
[0021] To make the objectives, technical solutions, and advantages of the embodiments of this disclosure clearer, the technical solutions of the embodiments of this disclosure will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this disclosure. All other embodiments obtained by those skilled in the art based on the described embodiments of this disclosure without creative effort are also within the scope of protection of this disclosure.
[0022] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter pertains. It will be further understood that terms such as those defined in commonly used dictionaries shall be interpreted as having meanings consistent with their meanings in the context of the specification and in the relevant art, and shall not be interpreted in an idealized or overly formal form unless otherwise explicitly defined herein.
[0023] This invention provides a broadband perovskite solar cell based on benzotriazine derivatives and its preparation method. The perovskite solar cell structure is configured by sequentially stacking a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a charge buffer layer, and a back electrode layer. It also includes molecular modifiers prepared from benzotriazine derivatives (mainly 1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, and 1,2,4-benzotriazine-3-amine). For the above molecules, the substituent functional groups at different positions include one or more of halogens (Cl, Br, I, etc.), methoxy, hydroxyl, carboxyl, methyl, and nitro groups.
[0024] The following is a detailed description through examples.
[0025] Comparative Example 1: Without introducing lower interface molecular modifiers, a control group perovskite solar cell was prepared.
[0026] S1: Preparation of perovskite precursor solution: In a nitrogen-filled environment, N,N-dimethylformamide and dimethyl sulfoxide were first mixed in a 4:1 volume ratio. Then, FAI, MABr, PbI2, PbBr2 and CsI were dissolved in the mixture in a molar ratio of 0.73:0.22:0.77:0.23:0.05. The mixture was stirred at 30°C for 10 h. Finally, after filtration, a 1.6 M perovskite precursor solution (CsI) was obtained. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 3; S2: Preparation of hole transport layer: FTO conductive glass was placed in a UV cleaner for 25 min and then transferred to a dry nitrogen glove box; [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was dissolved in anhydrous ethanol to prepare hole transport layer solution. 50 μL of hole transport layer solution was taken and dropped onto the center of FTO glass. After spin coating for 40 s, the substrate of hole transport layer was obtained after heat treatment at 110℃. S3: Preparation of perovskite light-absorbing layer: 50 μL of perovskite precursor solution was dropped onto the center of the hole transport layer substrate and rotated at 4000 rpm / min for 40 s. After annealing at 120℃ for 20 min, a perovskite film was formed and placed in a dry place for cooling. S4: Preparation of electron transport layer: Isomethyl [6,6]-phenyl-C61-butyrate (PCBM) was dissolved in chlorobenzene to prepare an electron transport layer solution. 40 μL of the electron transport layer solution was spin-coated onto the perovskite interface modification layer and then heat-treated to obtain the electron transport layer. S5: Preparation of electron blocking layer: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was dissolved in isopropanol to prepare an electron blocking layer solution, and 100 μL of the solution was spin-coated onto the electron transport layer. After heat treatment, the electron blocking layer was obtained. S6: Preparation of metal electrode layer: Using thermal evaporation, 120 nm of silver is deposited on top of the electron blocking layer.
[0027] like Figure 3As shown, the final fabricated perovskite solar cell achieved a maximum photoelectric conversion efficiency of 18.48% and an effective area of 0.05 cm². 2 .
[0028] Example 1: 1,2,4-benzotriazine-3-amine was used as a molecular modifier at the perovskite interface for the fabrication of perovskite solar cells. Isopropanol was used as the solvent for dissolution, and the concentration of the prepared molecular modifiers was 1.0 mg / mL. S1: Preparation of molecular modifier: In a nitrogen glove box, 1,2,4-benzotriazine-3-amine molecules were dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 1.0 mg / mL. S2: Preparation of perovskite precursor solution: In a nitrogen-filled environment, N,N-dimethylformamide and dimethyl sulfoxide were first mixed in a 4:1 volume ratio. Then, FAI, MABr, PbI2, PbBr2, and CsI were dissolved in the mixture in a molar ratio of 0.73: 0.22: 0.77: 0.23: 0.05. The mixture was stirred at 30°C for 10 h. Finally, after filtration, a 1.6 M perovskite precursor solution (CsI) was obtained. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 3; S3: Preparation of hole transport layer: FTO conductive glass was placed in a UV cleaner for 25 min and then transferred to a dry nitrogen glove box; [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was dissolved in anhydrous ethanol to prepare hole transport layer solution. 50 μL of hole transport layer solution was taken and dropped onto the center of FTO glass. After spin coating for 40 s, the substrate of hole transport layer was obtained after heat treatment at 110℃. S4: Preparation of the lower interface modification layer: Take 50 μL of the molecular modifier solution prepared in S1 and drop it onto the hole transport layer-lower interface modification layer. Rotate at 2000-4000 rpm / min for 30 s, and then heat treat at 100℃ for 10 min to obtain the lower interface modification layer. S5: Preparation of perovskite light-absorbing layer: 50 μL of perovskite precursor solution was dropped onto the center of the hole transport layer-lower interface modification layer substrate, rotated at 4000 rpm / min for 40 s, and then annealed at 120 ℃ for 20 min to form a perovskite film, and placed in a dry place for cooling. S6: Preparation of electron transport layer: Isomethyl [6,6]-phenyl-C61-butyrate (PCBM) was dissolved in chlorobenzene to prepare an electron transport layer solution. 40 μL of the electron transport layer solution was spin-coated onto the perovskite interface modification layer and then heat-treated to obtain the electron transport layer. S7: Preparation of electron blocking layer: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was dissolved in isopropanol to prepare an electron blocking layer solution, and 100 μL of the solution was spin-coated onto the electron transport layer. After heat treatment, the electron blocking layer was obtained. S8: Preparation of metal electrode layer: 120 nm of silver was deposited on top of the electron blocking layer using thermal evaporation.
[0029] like Figure 4 As shown, the final perovskite solar cell achieved a maximum photoelectric conversion efficiency of 23.80% and an effective area of 0.05 cm². 2 .
[0030] Example 2: 1,2,3-benzotriazine-4(3H)-one molecules were used as molecular modifiers at the lower interface of perovskite for the preparation of perovskite solar cells. Isopropanol was used as the solvent for dissolution, and the concentration of the prepared molecular modifiers was 0.5 mg / mL. S1: Preparation of molecular modifier: In a nitrogen glove box, the 1,2,3-benzotriazine-4(3H)-one molecule was dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL; Steps S2-S8 are the same as in Example 1.
[0031] like Figure 5 As shown, the final fabricated perovskite solar cell achieved a maximum photoelectric conversion efficiency of 21.72% and an effective area of 0.05 cm². 2 .
[0032] Example 3: 1,2,3-benzotriazine-4(3H)-thiol was used as a molecular modifier at the perovskite interface for the fabrication of perovskite solar cells. Isopropanol was used as the solvent for dissolution, and the concentration of the prepared molecular modifiers was 0.5 mg / mL. S1: Preparation of molecular modifier: In a nitrogen glove box, 1,2,3-benzotriazine-4(3H)-thiol molecules were dissolved in isopropanol as a solvent to obtain a molecular modifier solution with a concentration of 0.5 mg / mL. Steps S2-S8 are the same as in Example 1.
[0033] like Figure 6As shown, the final fabricated perovskite solar cell achieved a maximum photoelectric conversion efficiency of 22.16% and an effective area of 0.05 cm². 2 .
[0034] Example 4: 3-Hydroxy-1,2,3-benzotriazine-4(3H)-one was used as a molecular modifier at the perovskite interface for the fabrication of perovskite solar cells. Isopropanol was used as the solvent for dissolution, and the concentration of the prepared molecular modifiers was 0.5 mg / mL. S1: Preparation of molecular modifier: In a nitrogen glove box, the 3-hydroxy-1,2,3-benzotriazine-4(3H)-one molecule was dissolved in isopropanol as a solvent to obtain a molecular additive solution with a concentration of 0.5 mg / mL. Steps S2-S8 are the same as in Example 1.
[0035] like Figure 7 As shown, the final fabricated perovskite solar cell achieved a maximum photoelectric conversion efficiency of 21.61% and an effective area of 0.05 cm². 2 .
[0036] Example 5: 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol was used as a molecular modifier at the perovskite interface for the preparation of perovskite solar cells. Isopropanol was used as the solvent for dissolution, and the concentration of the prepared molecular modifiers was 0.5 mg / mL. S1: Preparation of molecular additive solution: In an anhydrous and oxygen-free environment, an appropriate amount of 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol molecules are dissolved in isopropanol to obtain a molecular modifier solution with a concentration of 0.5 mg / mL. Steps S2-S8 are the same as in Example 1.
[0037] like Figure 8 As shown, the measured photoelectric conversion efficiency of the perovskite solar cell is 21.73%, and the effective area is 0.05 cm². 2 .
[0038] Example 6: 1,2,4-benzotriazine-3-amine molecules were doped into a perovskite precursor solution to prepare perovskite solar cells. The solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and the solution concentration was 0.05 mg / mL.
[0039] S1: Preparation of molecular passivating agent solution: In a nitrogen glove box environment, N,N-dimethylformamide and dimethyl sulfoxide are mixed at a volume ratio of 4:1, and an appropriate amount of 1,2,4-benzotriazine-3-amine molecules are dissolved to obtain a molecular passivating agent solution with a concentration of 10 mg / mL. S2: Preparation of perovskite precursor solution: In a nitrogen-filled environment, N,N-dimethylformamide and dimethyl sulfoxide were first mixed in a 4:1 volume ratio. Then, FAI, MABr, PbI2, PbBr2, and CsI were dissolved in the mixture in a molar ratio of 0.73:0.22:0.77:0.23:0.05. Subsequently, 10 μL of the molecular passivating agent solution prepared in S1 was added dropwise to the perovskite precursor solution. The mixture was stirred at 30°C for 10 h. Finally, the solution was filtered through a filter to obtain a 1.6 M perovskite precursor solution CsI. 0.05 (FA 0.77 MA 0.23 ) 0.95 Pb(I 0.77 Br 0.23 3; S3: Preparation of hole transport layer: FTO conductive glass was placed in a UV cleaner for 25 min and then transferred to a dry nitrogen glove box; [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was dissolved in dimethoxyethanol solution to prepare hole transport layer solution; 50 μL of hole transport layer solution was taken and dropped onto the center of FTO glass; after spin coating for 30 s, the substrate of hole transport layer was obtained after heat treatment at 100℃; S4: Preparation of molecular passivation-perovskite light-absorbing layer: 50 μL of molecular passivation-perovskite precursor solution was dropped onto the center of the hole transport layer substrate and rotated at 5000 pm / min for 40 s. After annealing at 120℃ for 20 min, a perovskite film was formed and placed in a dry place for cooling. Step S5: Prepare the electron transport layer; Step S6: Prepare the electron blocking layer; and Step S7: Prepare the metal electrode layer, as in Example 1.
[0040] like Figure 9 As shown, the measured photoelectric conversion efficiency of the perovskite solar cell is 21.30%, and the effective area is 0.05 cm². 2 .
[0041] Example 7: 1,2,3-benzotriazine-4(3H)-one molecules were doped into the perovskite precursor solution to prepare perovskite solar cells. The solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and the solution concentration was 10.0 mg / mL.
[0042] S1: Preparation of molecular passivating agent solution: In a nitrogen glove box environment, N,N-dimethylformamide and dimethyl sulfoxide are mixed at a volume ratio of 4:1, and an appropriate amount of 1,2,3-benzotriazine-4(3H)-one molecules are dissolved to obtain a molecular passivating agent solution with a concentration of 10.0 mg / mL. Steps S2-S7 are the same as in Example 6.
[0043] like Figure 10 As shown, the measured photoelectric conversion efficiency of the perovskite solar cell is 22.23%, and the effective area is 0.05 cm². 2 .
[0044] Example 8: 1,2,3-benzotriazine-4(3H)-thiol molecules were doped into the perovskite precursor solution to prepare perovskite solar cells. The solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and the solution concentration was 10.0 mg / mL.
[0045] S1: Preparation of molecular passivating agent solution: In a nitrogen glove box environment, N,N-dimethylformamide and dimethyl sulfoxide are mixed at a volume ratio of 4:1, and an appropriate amount of 1,2,3-benzotriazine-4(3H)-thiol molecules are dissolved to obtain a molecular passivating agent solution with a concentration of 10.0 mg / mL. Steps S2-S7 are the same as in Example 6.
[0046] like Figure 11 As shown, the measured photoelectric conversion efficiency of the perovskite solar cell is 21.66%, and the effective area is 0.05 cm². 2 .
[0047] Example 9: 3-hydroxy-1,2,3-benzotriazine-4(3H)-one molecules were doped into the perovskite precursor solution to prepare perovskite solar cells. The solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and the solution concentration was 10.0 mg / mL.
[0048] S1: Preparation of molecular passivating agent solution: In a nitrogen glove box environment, N,N-dimethylformamide and dimethyl sulfoxide are mixed at a volume ratio of 4:1, and an appropriate amount of 3-hydroxy-1,2,3-benzotriazine-4(3H)-one molecules are dissolved to obtain a molecular passivating agent solution with a concentration of 10.0 mg / mL. Steps S2-S7 are the same as in Example 6.
[0049] like Figure 12 As shown, the measured photoelectric conversion efficiency of the perovskite solar cell is 22.37%, and the effective area is 0.05 cm². 2 .
[0050] Example 10: 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol molecules were doped into the perovskite precursor solution to prepare perovskite solar cells. The solvent of the molecular passivator solution was one or more of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and the solution concentration was 10.0 mg / mL.
[0051] S1: Preparation of molecular passivating agent solution: In a nitrogen glove box environment, N,N-dimethylformamide and dimethyl sulfoxide are mixed at a volume ratio of 4:1, and an appropriate amount of 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol molecules are dissolved to obtain a molecular passivating agent solution with a concentration of 10.0 mg / mL. Steps S2-S7 are the same as in Example 6.
[0052] like Figure 13 As shown, the measured photoelectric conversion efficiency of the perovskite solar cell is 22.26%, and the effective area is 0.05 cm². 2 .
[0053] Comparative Example 1 ( Figure 3 ) and Examples 1-10 ( Figure 4-13 Comparing the data from the previous section, it can be found that the open-circuit voltage and short-circuit current of the device are improved after molecular modification and passivation. This indicates that after introducing benzotriazine derivative molecules (1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, 1,2,4-benzotriazine-3-amine), the abundant nitrogen heteroatoms in the benzotriazine derivative molecules can act as Lewis bases, coordinating the unsaturated Pb at the perovskite interface. 2+This reduces nonradiative recombination of charge carriers at the interface below the perovskite light-absorbing layer. Simultaneously, after the benzotriazine derivative molecules mix into the perovskite precursor solution, their weak alkalinity allows them to exchange with formamidinium and methylamine ions in the perovskite solution, thereby dynamically controlling the crystallization process of the thin film, suppressing perovskite phase separation, and effectively improving the overall photoelectric conversion efficiency of the device.
[0054] The above results demonstrate that the benzotriazine derivative molecules of the present invention (1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, 1,2,4-benzotriazine-3-amine) can effectively improve the photoelectric conversion efficiency and stability of perovskite photovoltaic devices, and have high commercial application potential.
[0055] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A perovskite photovoltaic device regulated by a benzotriazine derivative, characterized in that, The perovskite solar cell structure includes: a conductive substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a charge-blocking layer, and a back electrode layer; as well as molecular modifiers, organic salt modifiers, and molecular passivators for modifying the perovskite solar cell. The perovskite light-absorbing layer has its upper and / or lower interfaces coated with a molecular modifier or an organic salt modifier, and / or a molecular passivator added to the perovskite light-absorbing layer. Both the molecular modifier and the molecular passivator contain one or more benzotriazine derivatives, and the organic salt modifier contains phenethylamine hydroiodate.
2. The perovskite photovoltaic device regulated by benzotriazine derivatives according to claim 1, characterized in that, The molecular modifier or organic salt modifier further comprises a first organic solvent, wherein the first organic solvent is one or more of methanol, isopropanol, 2-methoxypropanol and chlorobenzene.
3. The perovskite photovoltaic device regulated by benzotriazine derivatives according to claim 1, characterized in that, The molecular passivating agent further comprises a second organic solvent, which is at least one of acetonitrile, isopropanol, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.
4. The perovskite photovoltaic device regulated by benzotriazine derivatives according to claim 1, characterized in that, The benzotriazine derivative molecule is one or more of 1,2,3-benzotriazine-4(3H)-one, 1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-thiol, 3-hydroxy-1,2,3-benzotriazine-4(3H)-one, and 1,2,4-benzotriazine-3-amine.
5. A method for preparing a perovskite photovoltaic device regulated by a benzotriazine derivative as described in any one of claims 1-4, characterized in that, The preparation method includes the following steps: S1. Prepare perovskite precursor solution; S2. Pre-treat the conductive substrate; S3. Spin-coat the hole transport layer solution onto the pretreated conductive substrate and anneal it to obtain the hole transport layer. S4. Prepare a perovskite light-absorbing layer with molecular or organic salt modification on the hole transport layer to obtain a perovskite light-absorbing layer-upper interface modification layer or a perovskite light-absorbing layer-lower interface modification layer. S5. An electron transport layer and an electron blocking layer are sequentially spin-coated onto a perovskite light-absorbing layer modified with molecules or organic salts. A metal electrode layer is then thermally vapor-deposited above the electron blocking layer to obtain a perovskite photovoltaic device regulated by benzotriazine derivatives.
6. The method for fabricating a perovskite photovoltaic device regulated by a benzotriazine derivative according to claim 5, characterized in that, When step S4 is to prepare the perovskite light-absorbing layer-lower interface modification layer, the molecular modifier is first spin-coated onto the hole transport layer obtained in step S3. After annealing, the perovskite precursor solution from step S1 is then spin-coated onto the conductive substrate with the hole transport layer modified at the lower interface to obtain the perovskite light-absorbing layer-lower interface modification layer.
7. The method for fabricating a perovskite photovoltaic device regulated by a benzotriazine derivative according to claim 5, characterized in that, When step S4 is to prepare the perovskite light-absorbing layer-upper interface modification layer, the perovskite precursor solution from step S1 is first spin-coated onto the hole transport layer obtained in step S3, and after annealing heat treatment, the perovskite light-absorbing layer is obtained. Then, the organic salt modifier is spin-coated or scraped onto the perovskite light-absorbing layer, and after annealing heat treatment, the perovskite light-absorbing layer-upper interface modification layer is obtained.
8. The method for fabricating a perovskite photovoltaic device regulated by a benzotriazine derivative according to claim 5, characterized in that, When step S4 involves adding a molecular passivator to the perovskite light-absorbing layer, the molecular passivator and the perovskite precursor solution from step S1 are mixed and spin-coated onto a conductive substrate with a hole transport layer. After annealing and heat treatment, a perovskite light-absorbing layer with added molecular passivator is obtained.
9. A method for fabricating a perovskite photovoltaic device regulated by a benzotriazine derivative according to any one of claims 5, characterized in that, The concentration of the molecular modifier used in spin coating is 0.1-2.0 mg / mL.
10. The method for fabricating a perovskite photovoltaic device regulated by a benzotriazine derivative according to claim 5, characterized in that, The concentration of the added organic salt modifier is 0.1-2.0 mg / mL and / or the concentration of the spin-coated molecular passivator is 0.1-2.0 mg / mL.