Triazole derivative-prothioconazole doped perovskite active layer and preparation method and application thereof
By introducing a triazole derivative, prothioconazole, into the perovskite precursor solution, the problem of grain boundary and interface defects in perovskite solar cells was solved, achieving a highly efficient and stable passivation effect, thus improving cell performance and commercial potential.
Patent Information
- Application Number
- CN202511400841.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-28
- Publication Date
- 2025-12-30
AI Technical Summary
In existing perovskite solar cells, high-density defects at grain boundaries and interfaces lead to severe nonradiative recombination losses, affecting carrier transport and ion migration. Existing modifier molecules suffer from insufficient passivation sites and inadequate chemical stability.
The triazole derivative, prothioconazole, was used as a modifier to dope the perovskite precursor solution. By forming Lewis acid-base pairs and passivating Pb2+ and halide defects, the crystal orientation of the perovskite film was regulated, thereby improving the passivation effect and chemical stability.
High-quality perovskite thin films with low defect density have been achieved, reducing non-radiative recombination losses and improving the conversion efficiency and stability of perovskite solar cells, making them suitable for large-area and flexible applications.
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Figure CN121240752A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of perovskite solar cells, in particular to a perovskite active layer containing triazole derivative-prothioconazole modification and a preparation method thereof and application thereof in trans perovskite solar cells. BACKGROUND
[0002] Organic-inorganic hybrid metal halide perovskite solar cells (PSCs) have attracted great attention due to their outstanding photovoltaic performance and huge potential for commercial deployment. Although the certified power conversion efficiency (PCE) of single-junction PSCs at the laboratory scale has soared from 3.8% to 27%, it is still far below the Shockley-Queisser (S-Q) limit, especially for large-area solar modules. Among them, the undesirable non-radiative recombination loss associated with defects at the interface and grain boundaries is urgently needed to be addressed. Therefore, developing effective passivation strategies is essential for pursuing high-quality perovskite films with low defect density, thus contributing to obtaining high-efficiency and stable PSCs and solar modules.
[0003] Previous studies have shown that high-density defects at the grain boundaries and interfaces can significantly affect non-radiative recombination, which in turn affects carrier transport and ion migration. In recent years, quite a few defect passivation methods have been developed to improve the performance of PSCs. These methods usually involve Pb 2+ Defects and halide defect passivation to reduce non-radiative recombination loss. Generally, passivation materials containing multifunctional groups, such as halides or pseudohalides (e.g., Cl, SCN, BF4, PF6, etc.) and small molecules (such as theophylline, 2-amino terephthalic acid, phenethylamine, t-butyl benzyl ammonium), are widely used because they can passivate both positively and negatively charged defects. In particular, functional groups with lone pairs of electrons, such as elements such as N, O, and S, can effectively passivate positively charged defects as Lewis bases. Therefore, the rational design of materials with effective passivation functional groups is crucial.
[0004] The efficiency and stability of PSCs mainly depend on the effectiveness of the defect passivation strategy and the selection of passivation materials, which play a crucial role in mitigating defects in perovskite thin films. From the literature, phenethylammonium iodide (PEAI) has become a universal passivation agent for bulk and surface perovskite films, taking advantage of its amino group (-NH3 + ) to form coordination bonds with under-coordinated lead ions and passivate cation vacancies. Recently, Tan et al. proposed a new passivation agent, 4-trifluoromethylphenylammonium (CF3-PA), which forms a coordination bond with the under-coordinated lead ions through its -NH3 +The side shows greater electropositivity and shows stronger interaction with perovskite than PEA, resulting in improved perovskite crystallinity and device performance. In addition, incorporating elements with lone pair electrons (such as S or N) into the passivation agent can form strong interactions with the perovskite lattice, thereby enhancing the passivation effect. For example, Yang et al. reported that due to the strong Pb-S interaction and the rich electron π functional group in the thienyl moiety, thienylmethylamine (TMA) is superior to PEA in photovoltaic performance, which effectively passivates Pb 2+ defects and improves charge mobility. Qin et al. introduced imidazole derivatives, especially 2- (aminomethyl) imidazole dihydrochloride (2-AD) into Sn-Pb mixed perovskite, proving that the lone pair electrons of N and the -NH2 group can coordinate with metal ions to regulate the crystallization process and improve the uniformity of the perovskite film.
[0005] Therefore, the modification agent molecules achieve effective multifunctional passivation and reduce non-radiative recombination at grain boundaries, interfaces, which is an effective way to obtain high-efficiency and stable transverse perovskite solar cells. However, most of the existing modification agent molecules have the problems of insufficient passivation sites and insufficient action strength, which is not conducive to the effective passivation of defects, and the intrinsic chemical stability of some modification agent molecules containing multi-functional groups has an important influence on the long-term effectiveness of defect passivation. Although some modification agent molecules containing multi-functional groups can achieve the simultaneous passivation of positively and negatively charged defects due to multi-passivation sites, the weak chemical stability leads to structural decomposition and failure during device operation. Therefore, a more excellent modification agent molecule should have multi-passivation sites, strong coordination ability, and high chemical stability, which is a necessary condition for long-term effective passivation. SUMMARY
[0006] The purpose of the present application is to provide a perovskite active layer doped with triazole derivative-propiconazole as a modification agent and a preparation method thereof. The triazole derivative-propiconazole is doped into the perovskite precursor solution to realize the coordination of Pb 2+ defects and halide defects, to reduce non-radiative recombination loss, thereby obtaining a high-quality perovskite thin film with low defect density. At the same time, the selected triazole derivative-propiconazole in the present application has a more complete conjugated system of the triazole ring than monoazole and diazole, higher bond energy, better acid, alkali and high temperature resistance, and is not prone to ring-opening degradation. At the same time, the benzene ring structure of propiconazole molecule can produce Π-cation interaction with Pb 2+ , further enhancing the coordination strength of propiconazole molecule with Pb 2+ .
[0007] Another object of the present application is to provide a trans-perovskite solar cell comprising the triazole derivative-propiconazole doped perovskite active layer and a preparation method thereof, and the triazole derivative-propiconazole can be introduced into the perovskite precursor solution by doping to effectively improve the distribution of components in the precursor solution, control the crystalline orientation of the perovskite thin film, achieve high-quality crystallization, and thus effectively improve the conversion efficiency of the trans-perovskite solar cell applied thereto.
[0008] To achieve the above-mentioned objects, the present application adopts the following technical solutions:
[0009] A triazole derivative-propiconazole doped perovskite active layer is prepared from a precursor solution comprising cesium iodide (CsI), formamidinium iodide (FAI), lead iodide (PbI2), methylammonium chloride (MACl), and propiconazole.
[0010] The triazole derivative-propiconazole has the structure of formula (I):
[0011] Formula (I).
[0012] In the present application, the components of the perovskite active layer are Cs 0.05 FA 0.95 PbI3, which can be prepared by referring to the prior art. The core of the present application lies in the use of the triazole derivative-propiconazole as a modifier for doping, and the doping method is not particularly limited and can be performed by using conventional methods in the art.
[0013] An exemplary method is a preparation method of a triazole derivative-propiconazole doped perovskite active layer, comprising the following steps:
[0014] (1) Dissolve cesium iodide (CsI), formamidinium iodide (FAI), lead iodide (PbI2), and methylammonium chloride (MACl) in a mixed organic solvent, and shake to dissolve to obtain a perovskite precursor solution;
[0015] (2) Dope the triazole derivative-propiconazole modifier into the perovskite precursor solution of step (1), and shake thoroughly to obtain a precursor solution containing the triazole derivative-propiconazole;
[0016] (3) Use the precursor solution containing the triazole derivative-propiconazole of step (2) to prepare a cesium-formamidinium lead iodide alloy perovskite thin film having an ABX3 crystal structure, which is a triazole derivative-propiconazole doped perovskite active layer; in the ABX3 crystal structure, A is a mixture of formamidinium ions and cesium ions, B is lead ions, and X is iodine ions.
[0017] In step (1), the perovskite precursor solution can be prepared by referring to existing technologies, such as dissolving cesium iodide (CsI), formamidinium hydroiodate (FAI), lead iodide (PbI2), and methylammonium chloride (MACl) in a mixed organic solvent at a molar ratio of 0.5:0.95:1.1:0.1 to finally form the perovskite precursor solution.
[0018] In a more specific embodiment, a method for preparing a perovskite active layer doped with a triazole derivative—prothioconazole—comprising the following steps:
[0019] (1) Cesium iodide (CsI), formamidine hydroiodate (FAI), lead iodide (PbI2), and methyl ammonium chloride (MACl) were dissolved in a mixed organic solvent at a molar ratio of 0.5:0.95:1.1:0.1 and the solution was shaken by a vortex mixer for more than four hours to ensure complete dissolution, thus obtaining a perovskite precursor solution.
[0020] (2) The triazole derivative-prothioconazole modifier is incorporated into the perovskite precursor solution in step (1), and the solution is shaken thoroughly to obtain a precursor solution containing the triazole derivative.
[0021] The triazole derivative, prothioconazole, has the structure of formula (I):
[0022] Formula (I)
[0023] The functional groups contained in the structure of formula (I) are: triazolylthione group, chlorine atom, hydroxyl group, cyclopropyl group, and benzene ring;
[0024] (3) The precursor solution containing triazole derivative-propiodine modified in step (2) is used to prepare a cesium-formamidine-based lead-iodine alloy perovskite film with ABX3 crystal structure by spin coating / coating process, which is the perovskite active layer modified by triazole derivative-propiodine. In the ABX3 structure, formamidine ions and cesium ions are mixed at the A site, lead ions are at the B site, and iodine ions are at the X site.
[0025] As a preferred embodiment of the present invention, the concentration of the triazole derivative-prothioconazole modifier in the perovskite precursor solution is 0.1~1.5 mg / mL, for example 0.2 mg / mL, 0.3 mg / mL, 0.4 mg / mL, 0.5 mg / mL, 0.6 mg / mL, 0.7 mg / mL, 0.8 mg / mL, 0.9 mg / mL, 1.0 mg / mL, 1.1 mg / mL, 1.2 mg / mL, 1.3 mg / mL, 1.4 mg / mL, etc., preferably 1.0 mg / mL.
[0026] As a preferred technical solution of the present invention, the mixed organic solvent is a mixed solvent of DMF and DMSO, preferably with a volume ratio of DMF:DMSO=4:1.
[0027] As a preferred technical solution of the present invention, the substrate used for coating the perovskite precursor solution modified with triazole derivative - prothioconazole is ITO conductive glass or FTO conductive glass.
[0028] As a preferred technical solution of the present invention, in step (3), the precursor solution containing triazole derivative-prothioconazole is coated by either spin coating or coating, and then annealed at 100~120℃, preferably at 110℃ for 20 minutes.
[0029] In another aspect, the present invention provides the application of a triazole derivative-prothioconazole-modified perovskite active layer as a perovskite active layer in an inverted perovskite solar cell.
[0030] An inverted perovskite solar cell includes, from bottom to top, a conductive glass substrate, a hole transport layer, a perovskite active layer doped with the aforementioned triazole derivative - prothioconazole, an electron transport layer, a hole blocking layer, and a metal electrode.
[0031] As a preferred embodiment of another aspect of the present invention, the hole transport layer used in the inverted perovskite solar cell is [4-(9H-9'-phenyl-3,3'-dicarbazo-9-yl)butyl]phosphoric acid (4PABCz) with a concentration of 0.5~2 mg / mL, such as 0.8 mg / mL, 1.0 mg / mL, 1.2 mg / mL, 1.5 mg / mL, 1.8 mg / mL, etc., soluble in ethanol solvent. Preferably, the concentration used is 1.5 mg / mL, soluble in ethanol solvent.
[0032] As a preferred embodiment of another aspect of the present invention, the electron transport layer used in the inverted perovskite solar cell is a fullerene derivative; the thickness of the electron transport layer is 15~30nm, such as 18nm, 20nm, 23nm, 25nm, 26nm, 28nm, etc., preferably 25nm.
[0033] As a preferred embodiment of another aspect of the present invention, the hole blocking layer used in the inverted perovskite solar cell is copper bath; the thickness of the hole blocking layer is 5~7nm, preferably 6nm.
[0034] As a preferred embodiment of another aspect of the present invention, the metal electrode used in the inverted perovskite solar cell is one of Au, Ag, and Cu; the thickness of the metal electrode is 90~110nm, for example 95nm, 100nm, 105nm, 110nm, etc., preferably 100nm.
[0035] Unless otherwise specified, the preparation method of the inverted perovskite solar cell in this invention can be referred to the prior art, and this invention is not particularly limited.
[0036] An exemplary preparation method is as follows: the preparation method of the inverted perovskite solar cell using the aforementioned triazole derivative-doped prothioconazole active layer includes the following steps:
[0037] (1) Perform UV ozone cleaning treatment on the conductive glass substrate, and then prepare a hole transport layer on the conductive glass substrate;
[0038] (2) Coating the hole transport layer with a precursor solution modified with a triazole derivative, prothioconazole;
[0039] (3) An electron transport layer, a hole blocking layer and a metal electrode are sequentially prepared on the perovskite active layer.
[0040] In a more specific embodiment, the method for fabricating the inverted perovskite solar cell includes the following steps:
[0041] (1) Perform UV ozone cleaning treatment on ITO conductive glass or FTO conductive glass substrate, and then prepare hole transport layer on the conductive glass substrate;
[0042] (2) A precursor solution modified with triazole derivative - prothioconazole is coated onto the hole transport layer by either spin coating or coating method;
[0043] (3) An electron transport layer, a hole blocking layer and a metal electrode are sequentially prepared on the perovskite active layer.
[0044] In some specific implementation schemes, steps (1) and (2) can be prepared and annealed in air or in an N2 glove box;
[0045] In some specific implementation schemes, step (3) uses vacuum evaporation to prepare the electron transport layer, hole transport layer and metal electrode sequentially.
[0046] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0047] Triazole derivatives - prothioconazole and Pb 2+The interaction between the FAI and the perovskite can passivate ionic and coordination defects in the perovskite through molecular interactions and hydrogen bonds. This not only improves the uniformity of colloidal size distribution in the perovskite precursor solution but also enhances wet film stability by inhibiting colloidal aggregation. The introduction of the triazole derivative, prothioconazole, as a modifier enables the achievement of high-quality perovskite films with low defect density, reduces non-radiative recombination losses at grain boundaries and interfaces, facilitates more ideal energy level alignment, promotes charge transfer, reduces open-circuit voltage loss, and thus improves the overall performance of the device.
[0048] The triazole derivative-modified prothioconazole perovskite active layer prepared by this invention is compatible with both large-area preparation and flexible application, providing an effective solution for balancing efficiency, stability and scalability in the commercialization process of perovskites. Attached Figure Description
[0049] Figure 1 This invention reflects the interaction between the triazole derivative-prothioconazole modifier and Pb. 2+ XPS Pb plots showing the interaction between them.
[0050] Figure 2 This is an XPS N plot reflecting the interaction between the triazole derivative-prothioconazole modifier and FAI in this invention.
[0051] Figure 3 The images show the XRD patterns of the triazole derivative-prothioconazole modifier before and after doping.
[0052] Figure 4 The images show SEM images of the triazole derivative-prothioconazole modifier before and after doping, as described in this invention.
[0053] Figure 5 This is a schematic diagram of the trans-perovskite solar cell structure using the triazole derivative-prothioconazole modifier of this invention.
[0054] Figure 6 The small area (0.06 cm) before and after doping with the triazole derivative-prothioconazole modifier of this invention is shown. 2 Current-voltage (JV) curve of an inverted perovskite solar cell. Detailed Implementation
[0055] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.
[0056] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional chemical reagents; and the experimental methods described are conventional methods.
[0057] Existing research indicates that high-density defects at grain boundaries and interfaces significantly affect nonradiative recombination, thereby impacting carrier transport and ion migration. To address this issue, this invention introduces a triazole derivative—prothioconazole—as a modifier into the precursor solution. Through hydrogen bonding and intermolecular interactions, this effectively passivates internal defects in the film, reducing nonradiative recombination at grain boundaries and interfaces. This facilitates more ideal energy level alignment, promotes charge transfer, and reduces open-circuit voltage loss. The multifunctional coordination enhances the uniformity of the colloidal size distribution in the precursor solution, and by suppressing internal colloidal aggregation, it enhances the uniformity and stability of the film, resulting in a high-quality perovskite film with low defect density. This further improves the photoelectric conversion efficiency of the applied inverted perovskite solar cell.
[0058] The precursor solution of this invention is prepared by dissolving formamidinium hydroiodate, cesium iodide, lead iodide, and methylammonium chloride in a mixed organic solvent (DMF:DMSO = 4:1), and introducing 0.1~1.5 mg / ml of the triazole derivative - prothioconazole as a modifier, followed by shaking to dissolve. Subsequently, the precursor solution is used to prepare a perovskite active layer modified with the triazole derivative - prothioconazole having an ABX3 crystal structure by either spin coating or coating method.
[0059] The perovskite active layer modified with the triazole derivative-prothioconazole prepared above was applied to an inverted perovskite solar cell. For example... Figure 5 As shown, the inverted perovskite solar cell includes a conductive glass FTO / ITO, a hole transport layer HTL, a perovskite active layer modified with a triazole derivative, prothioconazole, an electron transport layer ETL, a hole blocking layer (not shown), and a metal electrode Cu.
[0060] This invention effectively reduces nonradiative recombination losses at perovskite grain boundaries and interfaces by introducing a triazole derivative, prothioconazole, into the precursor solution, thereby optimizing the energy level arrangement between the perovskite active layer and the transport layer, promoting carrier transport, and further preparing a high photoelectric conversion efficiency inverted perovskite solar cell.
[0061] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described in detail below through specific embodiments.
[0062] Comparative Example 1:
[0063] The specific steps for fabricating an inverted perovskite solar cell based on an unmodified perovskite active layer are as follows:
[0064] (1) Cleaning of conductive glass: The transparent conductive glass ITO is cleaned with deionized water, anhydrous ethanol, acetone and isopropanol for 15 minutes each in sequence; before use, the ITO substrate is further cleaned by UV-ozone treatment for 15 minutes. The purpose is to remove surface organic matter and increase the hydroxyl concentration on the ITO surface.
[0065] (2) Hole transport layer preparation: After the ITO conductive glass is cooled to room temperature, it is transferred to a glove box for the spin coating process of hole transport layer. The glove box atmosphere is: Temp≤25℃, RH≤10%. 80μL of hole transport layer 4PABCz is dropped onto the rotating substrate and spin coated for 30s at a speed of 4000rpm and an acceleration of 2000rpm / s. The glass substrate after spin coating of hole transport layer is transferred to a hot stage at 100℃ for annealing for 10min.
[0066] (3) Preparation of the perovskite active layer: 97.4 mg cesium iodide (CsI), 1225 mg formamidine hydroiodate (FAI), 3562 mg lead iodide (PbI2), and 50.65 mg methylammonium chloride (MACl) were dissolved in a mixed organic solvent of 4 mL DMF and 1 mL DMSO. The solution was shaken and dissolved for at least 4 hours to obtain a perovskite precursor solution. 80 μL of the prepared precursor solution was dropped onto the hole transport layer, and a perovskite film was deposited using a spin-coating process. The spin-coating program was as follows: rotation speed 4000 rpm, acceleration 1000 rpm / s, spin-coating for 40 s, and 120 μL of anisole was added as an antisolvent at the 10th second from the end of the program. Then, the film was annealed at 110 °C for 20 minutes on a hot plate.
[0067] (4) Electron transport layer and metal electrode deposition: Place the glass with the perovskite thin film into the vapor deposition apparatus, start the automatic vacuum button, and wait until the vacuum reaches 1X10 -4 First, select the C60 evaporation program, set the evaporation temperature to 480 degrees Celsius, and wait until the evaporation rate reaches 0.07 Å / s. Then, open the substrate baffle to begin deposition, evaporating to 25 nm and ending the process. Next, begin BCP deposition, setting the evaporation temperature to 130 degrees Celsius. When the evaporation rate reaches 0.01 Å / s, open the substrate baffle to begin deposition, evaporating to 6 nm and ending the process. Break the vacuum, replace the silver evaporation template, and restart the automatic vacuuming process to 1 x 10⁻⁶. -4 Pa, select the Cu vapor deposition program. This program is in automatic operation mode. Just click to start the deposition. The program will automatically end and break the vacuum after vapor deposition up to 100nm.
[0068] Performance testing:
[0069] A circular hole with an area of 0.06 cm² is used.2 Using a 0.1mm thick alloy sheet as a light-shielding template, the current-voltage characteristic curves of the inverted perovskite solar cell were tested under AM 1.5 G illumination. The results are as follows: Figure 6 As shown.
[0070] Example 1
[0071] The inverted perovskite solar cell prepared based on the triazole derivative-prothioconazole modified perovskite active layer is the same as that in Comparative Example 1, except for step (3) as follows:
[0072] (3) Preparation of the perovskite active layer: 97.4 mg cesium iodide (CsI), 1225 mg formamidinium hydroiodate (FAI), 3562 mg lead iodide (PbI2), and 50.65 mg methylammonium chloride (MACl) were dissolved in a mixed organic solvent of 4 ml DMF and 1 ml DMSO, and the solution was shaken for at least 4 hours. Then, 0.1 mg / mL of the triazole derivative - prothioconazole was added to the above solution, and the solution was shaken for another hour to obtain the perovskite precursor solution. 80 μL of the prepared precursor solution was dropped onto the hole transport layer, and a perovskite film was deposited using a spin-coating process. The spin-coating program was as follows: rotation speed 4000 rpm, acceleration 1000 rpm / s, spin-coating for 40 s, and 120 μL of anisole was added as an antisolvent at the 10th second to last of the program. The film was then annealed at 110 °C for 20 minutes on a hot plate.
[0073] Performance testing:
[0074] Using the same test method as Comparative Example 1, the current-voltage characteristic test curve results are as follows: Figure 6 As shown, compared with the control example, the performance improvement of the embodiment is reflected in the increase of short-circuit current (Jsc) and fill factor (FF): Jsc increases from 24.77 mA / cm². 2 Increased to 24.81 mA / cm 2 The FF increased from 83.69% to 84.94%. Modifiers were introduced into the perovskite precursor solution via bulk doping, which modified the energy level matching between the perovskite and the transport layer, improving the perovskite's carrier advance capability. Specific interaction mechanisms are as follows: Figures 1-2 As shown. The perovskite films before and after doping with the triazole derivative—prothioconazole—were characterized using SEM and XRD, as shown. Figures 3-4 As shown, the perovskite film with molecular modification exhibits larger grain size and significantly reduced grain boundaries.
[0075] Example 2
[0076] The inverted perovskite solar cell based on the triazole derivative-propiozoazole modified perovskite active layer is prepared according to Example 1. The difference is that in this example, the doping concentration of the triazole derivative-propiozoazole is 0.5 mg / mL.
[0077] Using the same test method as Comparative Example 1, the current-voltage characteristic test curve results are as follows: Figure 6 As shown, the circuit current of the device during reverse scanning is 24.74 mA cm⁻¹. -2 The open-circuit voltage is 1.16 V, the fill factor is 85.48%, and the photoelectric conversion efficiency is 24.67%.
[0078] Example 3
[0079] The inverted perovskite solar cell prepared based on the triazole derivative-propiozoazole modified perovskite active layer is described in Example 1. The difference is that in this example, the doping concentration of the triazole derivative-propiozoazole is 1 mg / mL.
[0080] Using the same test method as Comparative Example 1, the current-voltage characteristic test curve results are as follows: Figure 6 As shown, the circuit current of the device during reverse scanning is 24.97 mA cm⁻¹. -2 The open-circuit voltage is 1.16 V, the fill factor is 85.92%, and the photoelectric conversion efficiency is 25.00%.
[0081] Example 4
[0082] The inverted perovskite solar cell prepared based on the triazole derivative-propiozoazole modified perovskite active layer is described in Example 1. The difference is that in this example, the doping concentration of the triazole derivative-propiozoazole is 1.5 mg / mL.
[0083] Using the same test method as Comparative Example 1, the current-voltage characteristic test curve results are as follows: Figure 6 As shown, the circuit current of the device during reverse scanning is 24.75 mA cm⁻¹. -2 The open-circuit voltage is 1.13 V, the fill factor is 84.28%, and the photoelectric conversion efficiency is 23.66%.
[0084] Comparative Example 2
[0085] The triazole derivative-prothioconazole modifier in Example 1 was replaced with a benzotriazole derivative, 2-(2'hydroxy-5'-methylphenyl)benzotriazole, while all other conditions remained the same.
[0086] Using the same test method as Comparative Example 1, the circuit current of the device during reverse scanning was 24.83 mA cm⁻¹.-2 The open-circuit voltage is 1.15 V, the fill factor is 84.42%, and the photoelectric conversion efficiency is 24.19%.
[0087] The specific parameters of open-circuit voltage (Voc), short-circuit current (Jsc), fill factor (FF), and power conversion efficiency (PCE) for the forward and reverse scans of Comparative Examples 1-2 and Examples 1-4 are shown in Table 1 below.
[0088] Table 1
[0089] As can be seen, in the preparation method of this invention, the introduction of the triazole derivative-prothioconazole modifier can achieve high-quality perovskite films with low defect density, reduce non-radiative recombination losses at grain boundaries and interfaces, help achieve more ideal energy level alignment, promote charge transfer, reduce open-circuit voltage loss, and thus improve the overall performance of the device. Although the 2-(2'hydroxy-5'-methylphenyl)benzotriazole molecule exhibits chemical stability comparable to that of the prothioconazole molecule, it cannot generate stronger coordination with positively and negatively charged defects due to insufficient effective passivation sites compared to the prothioconazole molecule, ultimately resulting in a relatively limited improvement in device efficiency.
[0090] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.
Claims
1. A triazole derivative - prothioconazole doped perovskite active layer characterized by, prepared from a precursor solution comprising cesium iodide (Csl), formamidinium iodide (FAI), lead iodide (PbI2), methylammonium chloride (MACl) and prothioconazole; The triazole derivative-prothioconazole has a structure of formula (I): Formula (I).
2. The method for preparing a triazole derivative - prothioconazole doped perovskite active layer according to claim 1, characterized in that, The method comprises the following steps: (1) Dissolve cesium iodide (Csl), formamidinium iodide (FAI), lead iodide (PbI2) and methylammonium chloride (MACl) in a mixed organic solvent, and shake to dissolve, to obtain a perovskite precursor solution; the molar ratio of Csl:FAI:PbI2:MACl is 1:1:1:1; (2) Dope the triazole derivative-prothioconazole modifier into the perovskite precursor solution of step (1), and shake thoroughly to obtain a precursor solution containing the triazole derivative-prothioconazole; (3) Use the precursor solution containing the triazole derivative-prothioconazole of step (2) to prepare a cesium-formamidinium lead iodide alloy perovskite thin film having an ABX3 crystal structure, i.e., a triazole derivative-prothioconazole-doped perovskite active layer; in the ABX3 crystal structure, A is a mixture of formamidinium ions and cesium ions, B is lead ions, and X is iodine ions.
3. The preparation method according to claim 2, characterized in that, The doping concentration of the triazole derivative-prothioconazole modifier in the perovskite active layer is 0.1-1.5 mg / mL, and is preferably 1.0 mg / mL.
4. The production method according to claim 2, characterized by, The mixed organic solvent is a mixed solvent of DMF and DMSO, and the volume ratio of DMF:DMSO is preferably 4:
1.
5. The preparation method according to claim 2, characterized in that, In step (3), the precursor solution containing the triazole derivative-prothioconazole of step (2) is coated by spin coating or coating, and then annealed at 100-120°C, preferably at 110°C for 20 minutes.
6. The production method according to claim 5, wherein In step (3), the precursor solution containing the triazole derivative-prothioconazole of step (2) is spin-coated or coated on a substrate, and the substrate is ITO conductive glass or FTO conductive glass.
7. A trans-fafium solar cell, characterized by, The trans perovskite solar cell comprises, from bottom to top, a conductive glass substrate, a hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and a metal electrode. The perovskite active layer is the triazole derivative-prothioconazole-doped perovskite active layer of claim 1 or the triazole derivative-prothioconazole-doped perovskite active layer prepared by the method of any one of claims 2-6.
8. The inverse perovskite solar cell according to claim 7, characterized in that, The hole transport layer is [4-(9H-9'-phenyl-3,3'-bicarbazole-9-yl)butyl]phosphonic acid (4PABCz), and the concentration is preferably 0.5-2 mg / mL, and the solvent is ethanol; and / or The electron transport layer is a fullerene derivative; preferably, the thickness of the electron transport layer is 15-30 nm; and / or The hole blocking layer is bathocuproin; preferably, the thickness of the hole blocking layer is 5-7 nm; and / or The metal electrode is any one of Au, Ag and Cu; preferably, the thickness of the metal electrode is 90-110 nm.
9. The method of producing a trans-faimiliar perovskite solar cell according to claim 7 or 8, characterized by, The method comprises the following steps: (1) Perform UV ozone cleaning treatment on the conductive glass substrate, and then prepare a hole transport layer on the conductive glass substrate; (2) coating a precursor solution containing a triazole derivative-propiconazole modified on the hole transport layer; (3) sequentially preparing an electron transport layer, a hole blocking layer and a metal electrode on the perovskite active layer.
10. The method for preparing an inverted perovskite solar cell according to claim 9, characterized in that, Step (1), step (2) is carried out in air or N2 glove box and annealing; Step (3) is prepared by vacuum evaporation method in sequence electron transport layer, hole transport layer and metal electrode.