A macrocyclic self-assembled molecular material based on carbazole and its preparation method, and a method for preparing perovskite photovoltaic modules.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-07
- Publication Date
- 2026-08-14
AI Technical Summary
主要原因为在紫外辐射下，单磷酸基SAM分子极易脱离金属氧化物基底，失去对功函数的调控作用，引发非辐射复合；同时，扩散到其他层的SAM分子可能会引发缺陷，加速器件的降解
[0038]与现有技术相比，本发明的基于咔唑的大环自组装分子材料及其制备方法、钙钛矿光伏组件的制备方法具有以下特点：
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Figure CN122562838A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of perovskite photovoltaic module technology, and specifically relates to a carbazole-based macrocyclic self-assembled molecular material and its preparation method, as well as a method for preparing perovskite photovoltaic modules. Background Technology
[0002] Carbazole phosphate self-assembled monolayers (SAMs) have been widely used in inverted perovskite photovoltaic modules in recent years. These small molecules consist of three parts: a functional host, a linking group, and an anchoring group. Through the acidic anchoring group, these small molecules can react with the hydroxyl groups on the surface of metal oxides (FTO, ITO, Al2O3, NiOx, etc.) to form an ordered monolayer through chemisorption. This aligns the functional host, composed of electron-rich aromatic rings such as carbazole, with the perovskite film layer, accelerating hole extraction. Compared to traditional organic hole transport materials such as P3HT, PTAA, and Spiro-OMeTAD, the energy levels of the metal oxides modified with self-assembled small molecules are more matched with the perovskite, resulting in faster hole extraction and stronger electron blocking. This effectively suppresses non-radiative recombination at the interface, thereby improving the efficiency of perovskite solar cells.
[0003] Current industry research focuses on structural fine-tuning of carbazole phosphate molecules containing a single phosphate group. This is achieved by fused other aromatic rings to the carbazole ring, adding substituents, altering the type of linking groups and carbon chain length, and changing the anchoring groups, all aimed at further improving the efficiency of perovskite photovoltaic modules. However, stability remains a major bottleneck for the commercialization of perovskite photovoltaic modules. Modules using existing single-phosphate SAM molecules exhibit very rapid degradation under ultraviolet radiation. This is primarily because under ultraviolet radiation, single-phosphate SAM molecules readily detach from the metal oxide substrate, losing their control over the work function and initiating non-radiative recombination. Simultaneously, SAM molecules diffusing to other layers may introduce defects, accelerating device degradation. Summary of the Invention
[0004] The technical problem to be solved by this invention is to provide a carbazole-based macrocyclic self-assembled molecular material and its preparation method, as well as a method for preparing perovskite photovoltaic modules. The carbazole-based macrocyclic self-assembled molecular material consists of four carbazole rings connected at positions 3 and 6 to form a macrocycle. Each nitrogen atom of the carbazole ring is connected to an acidic group by a carbon chain of different lengths, so that a molecule contains four acidic anchoring groups, which can bind more tightly to the metal oxide substrate. The four anchoring groups also determine the configuration of the molecule adsorbed on the metal oxide surface, so that the entire carbazole ring faces the perovskite thin film layer, which promotes hole extraction and ultimately improves the conversion efficiency and stability of the perovskite photovoltaic module.
[0005] This invention is achieved by providing a carbazole-based macrocyclic self-assembled molecular material, the general chemical formula of which is:
[0006]
[0007] Wherein, L represents a linker group, selected from straight-chain alkylene groups with a carbon chain length of 2 to 18;
[0008] Anc stands for anchoring group, which is selected from at least one of the following molecular groups:
[0009]
[0010] The R group can be any one of the following groups, either the same or different: hydrogen, halogen atom, methyl, ethyl, methoxy, mercapto, methylthio, hydroxyl, cyano, or aryl containing heteroatoms; or, either the same or different aromatic ring containing heteroatoms fused with a benzene ring.
[0011] This invention is implemented as follows, and also provides a method for preparing a macrocyclic self-assembled molecular material based on carbazole, comprising the following steps:
[0012] Step 1: Synthesis of intermediate IM01
[0013] Under a nitrogen atmosphere, 7.77 g and 23.9 mmol of 3,6-dibromo-9H-carbazole, 1.17 g and 3.52 mmol of tetrabutylammonium bromide, and 12.7 mL of 50% sodium hydroxide aqueous solution were added to 50 mL of 1,3-dibromopropane. The mixture was stirred and heated to 60 °C for 12 hours. After the reaction was completed and cooled to room temperature, the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The crude product was separated and purified by column chromatography with petroleum ether:dichloromethane = 30:1 as the eluent, yielding 9.81 g of a white solid intermediate IM01 with a yield of 92%.
[0014] Step 2: Synthesis of intermediate IM02
[0015] Under a nitrogen atmosphere, 5.36 g and 12.8 mmol of 3,6-diboronic acid pinacol ester-9H-carbazole, 0.62 g and 1.87 mmol of tetrabutylammonium bromide, and 6.8 mL of 50% potassium hydroxide aqueous solution were added to 25 mL of 1,3-dibromopropane. The mixture was stirred and heated to 60 °C for 12 hours. After the reaction was completed and cooled to room temperature, the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 6.01 g of a white solid intermediate IM02 with a yield of 87%.
[0016] Step 3: Synthesis of intermediate IM03
[0017] Under a nitrogen atmosphere, 0.85 g (1.91 mmol) of intermediate IM01, 1.54 g (2.86 mmol) of intermediate IM02, 40.4 mg (2.5 mol) of XPhos-Pd-G3, and 1.34 g (6.32 mmol) of potassium phosphate were added to 25 mL of tetrahydrofuran. The mixture was stirred and heated to 60 °C for 24 hours. After the reaction was completed and cooled to room temperature, water was added to quench the reaction. The mixture was filtered through diatomaceous earth coated with silica gel. The filtrate was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 0.29 g (53% yield) of white solid intermediate IM03.
[0018] Step 4: Synthesis of intermediate IM04
[0019] Under a nitrogen atmosphere, 0.14 g of intermediate IM03 was dissolved in 5 mL of triethanol phosphite, stirred and heated to 150 °C for 16 hours; after the reaction was completed and cooled to room temperature, the solvent was removed by rotary evaporation to obtain crude intermediate IM04.
[0020] Step 5: Synthesis of macrocyclic self-assembled molecular material MC-01
[0021] Under a nitrogen atmosphere, the crude intermediate IM04 was dissolved in 10 mL of dichloromethane, and 0.12 g of triethylbromosilane was added. The mixture was stirred at room temperature for 12 hours, followed by the addition of 10 mL of methanol and stirring at room temperature for another 12 hours. The solution was concentrated by rotary evaporation and slowly added dropwise to diethyl ether to precipitate the product. After filtration, the product was dissolved in dichloromethane and added dropwise back to diethyl ether to precipitate. This process was repeated three times to obtain 0.13 g of a light yellow solid macrocyclic self-assembled molecular material MC-01 with a two-step yield of 94%.
[0022] This invention is implemented as follows, and also provides a method for preparing a macrocyclic self-assembled molecular material based on carbazole, comprising the following steps:
[0023] Step 1: Synthesis of intermediate IM05
[0024] Under a nitrogen atmosphere, 1.65 g (3.70 mmol) of intermediate IM01, 1.85 g (5.62 mmol) of bis(pinacol) 1,4-phenylenediborate, 78.3 mg (2.5 mol) of XPhos-Pd-G3, and 2.64 g (12.43 mmol) of potassium phosphate were added to 40 mL of tetrahydrofuran. The mixture was stirred and heated to 60 °C for 24 hours. After the reaction was completed and cooled to room temperature, the reaction was quenched with water. The mixture was filtered through diatomaceous earth coated with silica gel. The filtrate was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 0.60 g (45% yield) of white solid intermediate IM05.
[0025] Step 2: Synthesis of intermediate IM06
[0026] Under a nitrogen atmosphere, 0.32 g of intermediate IM05 was dissolved in 10 mL of triethanol phosphite, stirred and heated to 150 °C for 16 hours; after the reaction was completed and cooled to room temperature, the solvent was removed by rotary evaporation to obtain crude intermediate IM06.
[0027] Step 3: Synthesis of macrocyclic self-assembled molecular material MC-03
[0028] Under a nitrogen atmosphere, the crude intermediate IM06 was dissolved in 18 mL of dichloromethane, and 0.20 g of triethylbromosilane was added. The mixture was stirred at room temperature for 12 hours, followed by the addition of 18 mL of methanol and stirring at room temperature for another 12 hours. The solution was concentrated by rotary evaporation and slowly added dropwise to diethyl ether to precipitate the product. After filtration, the product was dissolved in dichloromethane and added dropwise back to diethyl ether to precipitate. This process was repeated three times to obtain 0.30 g of a light yellow solid macrocyclic self-assembled molecular material MC-03 with a two-step yield of 93%.
[0029] The present invention is implemented as follows, and also provides a perovskite photovoltaic module, the perovskite photovoltaic module including a hole transport layer, the hole transport layer comprising a carbazole-based macrocyclic self-assembled molecular material as described in claim 1.
[0030] This invention is implemented as follows, and also provides a method for preparing a perovskite photovoltaic module, comprising the following steps:
[0031] (1) Clean the glass with FTO, ITO or other conductive metal oxide layers on the surface in sequence with surfactant, deionized water, acetone and isopropanol. After cleaning, dry it in an oven at 100°C and treat it with ultraviolet light or ozone for later use.
[0032] (2) A SAM solution with a concentration of 0.1-2 mg / mL was prepared from a carbazole-based macrocyclic self-assembled molecular material as described above. The solvent was at least one of anisole, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene, and an equal volume of at least one of 2-methoxyethanol, methanol, ethanol, n-propanol, and 2-hydroxytetrahydrofuran. Under nitrogen atmosphere, the SAM solution was coated or spin-coated onto the surface of a metal oxide substrate to prepare a hole transport layer film, and annealed on a heating stage at 90-120°C for 10 minutes. When using a doctor blade, the doctor blade was 15 μm away from the surface of the metal oxide substrate, and 30 μL of the above-prepared solution was injected into the gap between the doctor blades. The doctor blade travel speed was 800 mm / min, and the temperature of the coating stage was 80°C. When using the spin-coating method, 500 μL of the above-prepared solution was dropped onto the surface of the metal oxide substrate, and the spin-coating speed was 3000 rpm.
[0033] (3) Dissolve 17.7 mg of CsI, 21.8 mg of MABr, 180.3 mg of FAI, 24.6 mg of PbBr2, and 574.4 mg of PbI2 in 1 mL of DMF:DMSO at a volume ratio of 4:1 to prepare a 1.3 M perovskite precursor solution. The chemical formula of perovskite is CsI. 0.05 FA 0.8 MA 0.15 PbI 2.75 Br 0.25 The perovskite precursor solution was coated by blade coating or slit coating, followed by spin coating with an anti-solvent to crystallize the perovskite, and then annealed on a heating stage at 100°C for 30 minutes to obtain a perovskite thin film layer.
[0034] (4) A 25 nm thick C layer was deposited sequentially on the surface of the perovskite thin film using vacuum evaporation. 60 The process involved using 8nm BCP and 100nm silver to complete the fabrication of perovskite photovoltaic modules.
[0035] This invention is implemented as follows, and also provides a method for preparing a perovskite photovoltaic module, comprising the following steps:
[0036] The cleaned FTO glass substrate was treated with ultraviolet ozone for 15 min. The macrocyclic self-assembled molecular material MC-01, prepared by the method described above for preparing carbazole-based macrocyclic self-assembled molecular materials, or the macrocyclic self-assembled molecular material MC-03, prepared by the method described in claim 4, was dissolved in a mixed solvent of anisole and 2-methoxyethanol at a volume ratio of 1:1 to prepare a hole transport layer solution of 0.6 mg / mL. In air, a film was coated on the FTO surface using a doctor blade coating method, with the doctor blade 15 μm away from the glass, a liquid injection volume of 30 μL, a doctor blade travel speed of 800 mm / min, and a coating stage temperature of 80 °C. The hole transport layer was then annealed on a heating stage at 90 °C.
[0037] Subsequently, Cs was spin-coated onto the surface of the hole transport layer. 0.05 FA 0.8 MA 0.15 PbI 2.75 Br 0.25 Perovskite was crystallized by dynamic spin-coating with chlorobenzene, and then annealed on a heating stage at 120°C for 30 minutes to obtain a perovskite thin film layer; 25 nm C was then sequentially coated with... 60 8nm BCP and 100nm silver were deposited onto the surface of the perovskite thin film using vacuum evaporation until the perovskite photovoltaic module was fabricated.
[0038] Compared with existing technologies, the carbazole-based macrocyclic self-assembled molecular material and its preparation method, as well as the perovskite photovoltaic module preparation method of the present invention, have the following characteristics:
[0039] 1. The carbazole-based macrocyclic self-assembled molecular material of the present invention has excellent bonding force with metal oxide substrates, which solves the problems of uneven distribution of traditional small molecule carbazole phosphate on the substrate, large series resistance, easy diffusion during aging causing performance degradation of perovskite photovoltaic modules. Its application in large-area perovskite modules can achieve a dual improvement in efficiency and stability.
[0040] 2. In terms of molecular structure design, this invention links multiple carbazole molecules head-to-head to form a macrocycle. The final synthesized product remains a small molecule rather than a polymer, thus avoiding fluctuations in product structure across different synthesis batches and resulting in more stable thin film quality in perovskite photovoltaic modules. Furthermore, the cavity within the macrocycle can suppress iodine ion migration, giving it the ability to passivate interface defects.
[0041] 3. The synthetic route of the macrocyclic self-assembled molecular material based on carbazole in this invention is short, the raw materials are readily available, and the obtained macrocyclic carbazole SAM can be used to prepare thin films with various solvents and coating processes. The preparation process can be carried out in an air environment, thus making it easier to scale up for industrial production. Attached Figure Description
[0042] Figure 1 This is a schematic diagram of the synthesis route of MC-01, a macrocyclic self-assembled molecular material based on carbazole, in Example 2 of the present invention.
[0043] Figure 2 This is a schematic diagram of the synthetic route of MC-03, a macrocyclic self-assembled molecular material based on carbazole, in Example 3 of the present invention.
[0044] Figure 3 This is a comparison chart of the JV curves of the perovskite photovoltaic modules prepared in Examples 6, 7 and Comparative Example 1 of the present invention;
[0045] Figure 4 This is a comparison chart showing the stability test results of the perovskite photovoltaic modules prepared in Examples 6, 7, and Comparative Example 1 of the present invention.
[0046] Figure 5 The graph shows a comparison of the UV stability tests of the perovskite photovoltaic modules prepared in Examples 6, 7 and Comparative Example 1 of this invention. Detailed Implementation
[0047] To make the technical problems to be solved, the technical solutions, and the beneficial effects of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
[0048] Example 1
[0049] A preferred embodiment of the carbazole-based macrocyclic self-assembled molecular material of the present invention, wherein the general chemical structural formula of the carbazole-based macrocyclic self-assembled molecular material is as follows:
[0050]
[0051] Wherein, L represents a linker group, selected from straight-chain alkylene groups with a carbon chain length of 2 to 18;
[0052]
[0053] Anc stands for anchoring group, which is selected from at least one of the following molecular groups:
[0054]
[0055] The R group can be any one of the following groups, either the same or different: hydrogen, halogen atom, methyl, ethyl, methoxy, mercapto, methylthio, hydroxyl, cyano, or aryl containing heteroatoms; or, either the same or different aromatic ring containing heteroatoms fused with a benzene ring.
[0056] Specifically, the carbazole-based macrocyclic self-assembled molecular material is any one of the following general chemical structural formulas from MC-01 to MC-08:
[0057]
[0058]
[0059]
[0060] The carbazole-based macrocyclic self-assembled molecular material consists of four carbazole rings linked at positions 3 and 6 to form a macrocycle. Each nitrogen atom of the carbazole ring is connected to an acidic group via a carbon chain of varying lengths, resulting in four acidic anchoring groups within a single molecule. This allows for tighter bonding to the metal oxide substrate. The four anchoring groups also determine the adsorption configuration of the molecule on the metal oxide surface, aligning the entire carbazole ring with the perovskite thin film layer. This promotes hole extraction and ultimately enhances both the conversion efficiency and stability of the perovskite photovoltaic module.
[0061] By adding substituents to benzene rings or other aromatic rings, the overall energy levels of the molecule can be modulated to match perovskite systems with different energy level positions. The addition of aromatic rings increases the diameter of the cavity within the macroring, allowing the cavity to accommodate large-diameter lead and iodine ions. Some aromatic heterocycles can also coordinate with lead through heteroatoms, which not only enhances the bonding force between the hole extraction layer and the perovskite film layer and passivates defects at the perovskite film layer interface, but also effectively inhibits the migration and diffusion of lead and iodine at the interface.
[0062] Example 2
[0063] Please refer to Figure 1 As shown, this invention provides a first embodiment of a method for preparing macrocyclic self-assembled molecular materials based on carbazole. The preparation method is carried out according to... Figure 1 The preparation is carried out according to the synthetic route shown.
[0064] Specifically, the preparation method includes the following steps:
[0065] Step 1: Synthesis of intermediate IM01
[0066] Under a nitrogen atmosphere, 7.77 g of 3,6-dibromo-9H-carbazole (23.9 mmol), 1.17 g of tetrabutylammonium bromide (3.52 mmol), and 12.7 mL of 50% sodium hydroxide aqueous solution were added to 50 mL of 1,3-dibromopropane. The mixture was stirred and heated to 60 °C for 12 hours. After the reaction was completed and cooled to room temperature, the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was separated and purified by column chromatography using petroleum ether:dichloromethane (30:1) as the eluent, yielding 9.81 g of a white solid intermediate IM01 with a yield (the percentage obtained by dividing the actual product mass by the theoretical product mass calculated using stoichiometry) of 92%.
[0067] Step 2: Synthesis of intermediate IM02
[0068] Under a nitrogen atmosphere, 5.36 g (12.8 mmol) of 3,6-diboronic acid pinacol ester-9H-carbazole, 0.62 g (1.87 mmol) of tetrabutylammonium bromide, and 6.8 mL (50% potassium hydroxide aqueous solution) were added to 25 mL of 1,3-dibromopropane. The mixture was stirred and heated to 60 °C for 12 hours. After the reaction was completed and cooled to room temperature, the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to give 6.01 g (87% yield) of a white solid intermediate, IM02.
[0069] Step 3: Synthesis of intermediate IM03
[0070] Under a nitrogen atmosphere, 0.85 g (1.91 mmol) of intermediate IM01, 1.54 g (2.86 mmol) of intermediate IM02, 40.4 mg (2.5 mol) of XPhos-Pd-G3, and 1.34 g (6.32 mmol) of potassium phosphate were added to 25 mL of tetrahydrofuran. The mixture was stirred and heated to 60 °C for 24 hours. After the reaction was completed and cooled to room temperature, water was added to quench the reaction. The mixture was filtered through diatomaceous earth coated with silica gel. The filtrate was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to give 0.29 g (53% yield) of white solid intermediate IM03.
[0071] Step 4: Synthesis of intermediate IM04
[0072] Under a nitrogen atmosphere, 0.14 g of intermediate IM03 was dissolved in 5 mL of triethanol phosphite, stirred and heated to 150 °C for 16 hours; after the reaction was completed and cooled to room temperature, the solvent was removed by rotary evaporation to obtain crude intermediate IM04.
[0073] Step 5: Synthesis of macrocyclic self-assembled molecular material MC-01
[0074] Under a nitrogen atmosphere, the crude intermediate IM04 was dissolved in 10 mL of dichloromethane, and 0.12 g of triethylbromosilane was added. The mixture was stirred at room temperature for 12 hours, followed by the addition of 10 mL of methanol and stirring at room temperature for another 12 hours. The solution was concentrated by rotary evaporation, and the precipitate was slowly added dropwise to diethyl ether. After filtration, the precipitate was dissolved in dichloromethane and then added dropwise back to diethyl ether. This process was repeated three times to obtain 0.13 g of a pale yellow solid macrocyclic self-assembled molecular material MC-01 with a two-step yield of 94%.
[0075] Example 3
[0076] Please refer to Figure 2 As shown, this is a second embodiment of the method for preparing macrocyclic self-assembled molecular materials based on carbazole according to the present invention. The preparation method is carried out according to... Figure 2 The preparation is carried out according to the synthetic route shown.
[0077] Specifically, the preparation method includes the following steps:
[0078] Step 1: Synthesis of intermediate IM05
[0079] Under a nitrogen atmosphere, 1.65 g (3.70 mmol) of intermediate IM01, 1.85 g (5.62 mmol) of bis(pinacol) 1,4-phenylenediborate, 78.3 mg (2.5 mol) of XPhos-Pd-G3, and 2.64 g (12.43 mmol) of potassium phosphate were added to 40 mL of tetrahydrofuran. The mixture was stirred and heated to 60 °C for 24 hours. After the reaction was completed and cooled to room temperature, the reaction was quenched with water. The mixture was filtered through diatomaceous earth coated with silica gel, and the filtrate was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to give 0.60 g (45% yield) of white solid intermediate IM05.
[0080] Step 2: Synthesis of intermediate IM06
[0081] Under a nitrogen atmosphere, 0.32 g of intermediate IM05 was dissolved in 10 mL of triethanolamine phosphite, and the mixture was stirred and heated to 150 °C for 16 hours. After the reaction was completed and cooled to room temperature, the solvent was removed by rotary evaporation to obtain the crude intermediate IM06.
[0082] Step 3: Synthesis of macrocyclic self-assembled molecular material MC-03
[0083] Under a nitrogen atmosphere, the crude intermediate IM06 was dissolved in 18 mL of dichloromethane, and 0.20 g of triethylbromosilane was added. The mixture was stirred at room temperature for 12 hours, followed by the addition of 18 mL of methanol and stirring at room temperature for another 12 hours. The solution was concentrated by rotary evaporation, and the precipitate was slowly added dropwise to diethyl ether. After filtration, the precipitate was dissolved in dichloromethane and then added dropwise back to diethyl ether. This process was repeated three times to obtain 0.30 g of a pale yellow solid macrocyclic self-assembled molecular material MC-03 with a two-step yield of 93%.
[0084] Example 4
[0085] The present invention also discloses a perovskite photovoltaic module, the perovskite photovoltaic module including a hole transport layer, the hole transport layer comprising a carbazole-based macrocyclic self-assembled molecular material as described above.
[0086] Example 5
[0087] This invention also discloses a first embodiment of a method for preparing a perovskite photovoltaic module, comprising the following steps:
[0088] (1) Clean the glass with FTO, ITO or other conductive metal oxide layers on the surface in sequence with surfactant, deionized water, acetone and isopropanol. After cleaning, dry it in an oven at 100°C and treat it with ultraviolet light or ozone for later use.
[0089] (2) A SAM solution with a concentration of 0.1–2 mg / mL was prepared using a carbazole-based macrocyclic self-assembled molecular material as described above. The solvent was at least one of anisole, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene, mixed in equal volumes with at least one of 2-methoxyethanol, methanol, ethanol, n-propanol, and 2-hydroxytetrahydrofuran. Under nitrogen atmosphere, the SAM solution was applied to the surface of a metal oxide substrate by blade coating or spin coating to prepare a hole transport layer film, and then annealed on a heating stage at 90–120°C for 10 minutes. Specifically, when using blade coating, the blade was 15 μm away from the metal oxide substrate surface, and 30 μL of the prepared solution was injected into the blade gap. The blade travel speed was 800 mm / min, and the coating stage temperature was 80°C. When using spin coating, 500 μL of the prepared solution was dropped onto the metal oxide substrate surface at a spin coating speed of 3000 rpm.
[0090] (3) Dissolve 17.7 mg of CsI, 21.8 mg of MABr, 180.3 mg of FAI, 24.6 mg of PbBr2, and 574.4 mg of PbI2 in 1 mL of DMF:DMSO at a volume ratio of 4:1 to prepare a 1.3 M perovskite precursor solution. The chemical formula of perovskite is CsI. 0.05 FA 0.8 MA 0.15 PbI2.75 Br 0.25 The perovskite precursor solution is coated by blade coating or slit coating, followed by spin coating with an anti-solvent to crystallize the perovskite, and then annealed on a heating stage at 100°C for 30 minutes to obtain a perovskite thin film layer.
[0091] (4) A 25 nm thick C layer was deposited sequentially on the surface of the perovskite thin film using vacuum evaporation. 60 The process involved using 8nm BCP and 100nm silver to complete the fabrication of perovskite photovoltaic modules.
[0092] Example 6
[0093] The present invention also discloses a second embodiment of a method for preparing a perovskite photovoltaic module, comprising the following steps:
[0094] The cleaned FTO glass substrate was treated with UV ozone for 15 min. The macrocyclic self-assembled molecular material MC-01, prepared using the previously described method for preparing carbazole-based macrocyclic self-assembled molecular materials, was dissolved in a 1:1 (v / v) mixture of anisole and 2-methoxyethanol to prepare a hole transport layer solution of 0.6 mg / mL. The film was then coated onto the FTO surface in air using a doctor blade coating method. The doctor blade was 15 μm away from the glass, the injection volume was 30 μL, the doctor blade travel speed was 800 mm / min, and the coating stage temperature was 80 °C. Annealing was then performed on a heating stage at 90 °C to obtain the hole transport layer.
[0095] Subsequently, Cs was spin-coated onto the surface of the hole transport layer. 0.05 FA 0.8 MA 0.15 PbI 2.75 Br 0.25 Perovskite was crystallized by dynamic spin-coating with chlorobenzene, and then annealed on a heating stage at 120°C for 30 minutes to obtain a perovskite thin film. A 25nm C film was then sequentially coated with... 60 8nm BCP and 100nm silver were deposited onto the surface of the perovskite thin film using vacuum evaporation until the perovskite photovoltaic module was fabricated.
[0096] Example 7
[0097] This invention also discloses a third embodiment of a method for preparing perovskite photovoltaic modules. The only difference between this embodiment and Embodiment 6 is that MC-03, a macrocyclic self-assembled molecular material prepared by the method for preparing carbazole-based macrocyclic self-assembled molecular materials as described above, is used instead of MC-01. Other steps and conditions are the same as in Embodiment 6 and will not be repeated here.
[0098] Comparative Example 1
[0099] The only difference between Comparative Example 1 and Example 5 is that 0.3 mg / mL Me-4PACz dissolved in ethanol is used instead of MC-01 in Example 5. The other steps and conditions are the same as in Example 5 and will not be repeated here.
[0100] The general chemical structural formula of Me-4PACz is:
[0101]
[0102] The perovskite photovoltaic modules prepared in Example 6 (MC-01), Example 7 (MC-03), and Comparative Example 1 (Me-4PACz) were subjected to performance tests, and the results were as follows: Figure 3 The JV curves are shown, and the performance test data is presented in Table 1.
[0103] Table 1. Comparison of performance test data of perovskite photovoltaic modules prepared in Examples 6, 7 and Comparative Example 1
[0104]
[0105] The data in Table 1 are the average values after testing with 12 perovskite photovoltaic modules, which improves the representativeness of the test data.
[0106] from Figure 3 As can be seen from Table 1, compared with Comparative Example 1 (Me-4PACz), the perovskite photovoltaic module of Example 5 (MC-01) can achieve better parameters and overall device efficiency. Furthermore, based on the series resistance data of the device, it can be inferred that Me-4PACz has uneven distribution and local agglomeration on FTO, while MC-01 has good coverage of FTO.
[0107] The perovskite photovoltaic modules prepared in Example 6 (MC-01), Example 7 (MC-03), and Comparative Example 1 (Me-4PACz) were subjected to placement stability tests and ultraviolet stability tests, respectively, and the results were as follows: Figure 4 and Figure 5 The comparison chart.
[0108] The stability test was conducted in a nitrogen-atmosphere glove box. The fabricated perovskite photovoltaic modules were placed in sealed bags and stored in the nitrogen-atmosphere glove box, protected from light. Efficiency was tested approximately every 12 hours, and the average value of 12 perovskite photovoltaic modules was taken. The UV stability test required the fabricated perovskite photovoltaic modules to be encapsulated and placed in a UV aging chamber at 50mW / cm². 2 The cumulative radiation dose from the ultraviolet lamp irradiation reached 9 kWh / cm². 2 After that, every 3kWh / cm 2Take out the aging chamber and conduct a test. Take the average value of the test results for 12 perovskite photovoltaic modules. Record the average value in [the relevant file / system]. Figure 4 and Figure 5 middle.
[0109] from Figure 4 and Figure 5 The study found that perovskite photovoltaic modules based on Me-4PACz exhibited significantly poorer stability in both placement and ultraviolet radiation, while perovskite photovoltaic modules based on MC-01 and MC-03 demonstrated better stability in both placement and ultraviolet radiation.
[0110] In summary, the carbazole-based macrocyclic self-assembled molecular material of the present invention has the effect of improving efficiency and UV stability.
[0111] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A macrocyclic self-assembled molecular material based on carbazole, characterized in that, The general chemical structural formula of the carbazole-based macrocyclic self-assembled molecular material is: Wherein, L represents a linker group, selected from straight-chain alkylene groups with a carbon chain length of 2 to 18; Anc stands for anchoring group, which is selected from at least one of the following molecular groups: The R group can be any one of the following groups, either the same or different: hydrogen, halogen atom, methyl, ethyl, methoxy, mercapto, methylthio, hydroxyl, cyano, or aryl containing heteroatoms; or, either the same or different aromatic ring containing heteroatoms fused with a benzene ring.
2. The carbazole-based macrocyclic self-assembled molecular material as described in claim 1, characterized in that, The carbazole-based macrocyclic self-assembled molecular material is any one of the following general chemical structural formulas from MC-01 to MC-08:
3. A method for preparing a macrocyclic self-assembled molecular material based on carbazole, characterized in that, Includes the following steps: Step 1: Synthesis of intermediate IM01 Under a nitrogen atmosphere, 7.77 g and 23.9 mmol of 3,6-dibromo-9H-carbazole, 1.17 g and 3.52 mmol of tetrabutylammonium bromide, and 12.7 mL of 50% sodium hydroxide aqueous solution were added to 50 mL of 1,3-dibromopropane. The mixture was stirred and heated to 60 °C for 12 hours. After the reaction was completed and cooled to room temperature, the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was separated and purified by column chromatography with petroleum ether:dichloromethane = 30:1 as the eluent, yielding 9.81 g of a white solid intermediate IM01 with a yield of 92%. Step 2: Synthesis of intermediate IM02 Under a nitrogen atmosphere, 5.36 g and 12.8 mmol of 3,6-diboronic acid pinacol ester-9H-carbazole, 0.62 g and 1.87 mmol of tetrabutylammonium bromide, and 6.8 mL of 50% potassium hydroxide aqueous solution were added to 25 mL of 1,3-dibromopropane. The mixture was stirred and heated to 60 °C for 12 hours. After the reaction was completed and cooled to room temperature, the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to give 6.01 g of white solid intermediate IM02 in 87% yield. Step 3: Synthesis of intermediate IM03 Under a nitrogen atmosphere, 0.85 g (1.91 mmol) of intermediate IM01, 1.54 g (2.86 mmol) of intermediate IM02, 40.4 mg (2.5 mol) of XPhos-Pd-G3, and 1.34 g (6.32 mmol) of potassium phosphate were added to 25 mL of tetrahydrofuran. The mixture was stirred and heated to 60 °C for 24 hours. After the reaction was completed and cooled to room temperature, water was added to quench the reaction. The mixture was filtered through diatomaceous earth coated with silica gel. The filtrate was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 0.29 g (53% yield) of white solid intermediate IM03. Step 4: Synthesis of intermediate IM04 Under a nitrogen atmosphere, 0.14 g of intermediate IM03 was dissolved in 5 mL of triethanol phosphite, stirred and heated to 150 °C for 16 hours; after the reaction was completed and cooled to room temperature, the solvent was removed by rotary evaporation to obtain crude intermediate IM04. Step 5: Synthesis of macrocyclic self-assembled molecular material MC-01 Under a nitrogen atmosphere, the crude intermediate IM04 was dissolved in 10 mL of dichloromethane, and 0.12 g of triethylbromosilane was added. The mixture was stirred at room temperature for 12 hours, followed by the addition of 10 mL of methanol and stirring at room temperature for another 12 hours. The solution was concentrated by rotary evaporation and slowly added dropwise to diethyl ether to precipitate the product. After filtration, the product was dissolved in dichloromethane and added dropwise back to diethyl ether to precipitate. This process was repeated three times to obtain 0.13 g of a light yellow solid macrocyclic self-assembled molecular material MC-01 with a two-step yield of 94%.
4. The method for preparing a macrocyclic self-assembled molecular material based on carbazole as described in claim 3, characterized in that, Includes the following steps: Step 1: Synthesis of intermediate IM05 Under a nitrogen atmosphere, 1.65 g (3.70 mmol) of intermediate IM01, 1.85 g (5.62 mmol) of bis(pinacol) 1,4-phenylenediborate, 78.3 mg (2.5 mol) of XPhos-Pd-G3, and 2.64 g (12.43 mmol) of potassium phosphate were added to 40 mL of tetrahydrofuran. The mixture was stirred and heated to 60 °C for 24 hours. After the reaction was completed and cooled to room temperature, the reaction was quenched with water. The mixture was filtered through diatomaceous earth coated with silica gel. The filtrate was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography to obtain 0.60 g (45% yield) of white solid intermediate IM05. Step 2: Synthesis of intermediate IM06 Under a nitrogen atmosphere, 0.32 g of intermediate IM05 was dissolved in 10 mL of triethanol phosphite, stirred and heated to 150 °C for 16 hours; after the reaction was completed and cooled to room temperature, the solvent was removed by rotary evaporation to obtain crude intermediate IM06. Step 3: Synthesis of macrocyclic self-assembled molecular material MC-03 Under a nitrogen atmosphere, the crude intermediate IM06 was dissolved in 18 mL of dichloromethane, and 0.20 g of triethylbromosilane was added. The mixture was stirred at room temperature for 12 hours, followed by the addition of 18 mL of methanol and stirring at room temperature for another 12 hours. The solution was concentrated by rotary evaporation and slowly added dropwise to diethyl ether to precipitate the product. After filtration, the product was dissolved in dichloromethane and added dropwise back to diethyl ether to precipitate. This process was repeated three times to obtain 0.30 g of a light yellow solid macrocyclic self-assembled molecular material MC-03 with a two-step yield of 93%.
5. A perovskite photovoltaic module, the perovskite photovoltaic module comprising a hole transport layer, characterized in that, The hole transport layer comprises a carbazole-based macrocyclic self-assembled molecular material as described in claim 1.
6. A method for preparing a perovskite photovoltaic module, characterized in that, Includes the following steps: (1) Clean the glass with FTO, ITO or other conductive metal oxide layers on the surface in sequence with surfactant, deionized water, acetone and isopropanol. After cleaning, dry it in an oven at 100°C and treat it with ultraviolet light or ozone for later use. (2) A SAM solution with a concentration of 0.1-2 mg / mL is prepared from a carbazole-based macrocyclic self-assembled molecular material as described in claim 1 or 2. The solvent is at least one of anisole, toluene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene, and an equal volume of at least one of 2-methoxyethanol, methanol, ethanol, n-propanol, and 2-hydroxytetrahydrofuran. Under nitrogen atmosphere, the SAM solution is applied to the surface of a metal oxide substrate by doctor blade coating or spin coating to prepare a hole transport layer film, and then annealed on a heating stage at 90-120°C for 10 minutes. When using doctor blade coating, the doctor blade is 15 μm away from the surface of the metal oxide substrate, and 30 μL of the above-prepared solution is injected into the gap between the doctor blades. The doctor blade travel speed is 800 mm / min, and the temperature of the coating stage is 80°C. When using spin coating, 500 μL of the above-prepared solution is dropped onto the surface of the metal oxide substrate at a spin coating speed of 3000 rpm. (3) Dissolve 17.7 mg of CsI, 21.8 mg of MABr, 180.3 mg of FAI, 24.6 mg of PbBr2, and 574.4 mg of PbI2 in 1 mL of DMF:DMSO at a volume ratio of 4:1 to prepare a 1.3 M perovskite precursor solution. The chemical formula of perovskite is CsI. 0.05 FA 0.8 MA 0.15 PbI 2.75 Br 0.25 The perovskite precursor solution was coated by blade coating or slit coating, followed by spin coating of anti-solvent to crystallize the perovskite, and then annealed on a heating stage at 100°C for 30 minutes to obtain a perovskite thin film layer. (4) A 25 nm thick C layer was deposited sequentially on the surface of the perovskite thin film using vacuum evaporation. 60 The process involved using 8nm BCP and 100nm silver to complete the fabrication of perovskite photovoltaic modules.
7. A method for preparing a perovskite photovoltaic module, characterized in that, Includes the following steps: The cleaned FTO glass substrate was treated with ultraviolet ozone for 15 min. The macrocyclic self-assembled molecular material MC-01 prepared by the preparation method of carbazole-based macrocyclic self-assembled molecular material as described in claim 3 or the macrocyclic self-assembled molecular material MC-03 prepared by the preparation method of carbazole-based macrocyclic self-assembled molecular material as described in claim 4 was dissolved in a mixed solvent of anisole and 2-methoxyethanol with a volume ratio of 1:1 to prepare a hole transport layer solution of 0.6 mg / mL. In air, a film was coated on the FTO surface using a doctor blade coating method. The doctor blade was 15 μm away from the glass, the liquid injection volume was 30 μL, the doctor blade travel speed was 800 mm / min, and the coating stage temperature was 80 °C. The hole transport layer was obtained by annealing on a heating stage at 90 °C. Subsequently, Cs was spin-coated onto the surface of the hole transport layer. 0.05 FA 0.8 MA 0.15 PbI 2.75 Br 0.25 Perovskite was crystallized by dynamic spin-coating with chlorobenzene, and then annealed on a heating stage at 120°C for 30 minutes to obtain a perovskite thin film layer; 25 nm C was then sequentially coated with... 60 8nm BCP and 100nm silver were deposited onto the surface of the perovskite thin film using vacuum evaporation until the perovskite photovoltaic module was fabricated.