A self-assembled monolayer hole transport material functionalized with ion salt, its preparation method and application
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-29
- Publication Date
- 2026-08-14
AI Technical Summary
[0004]常用的自组装单分子层材料，如(4-(3,6-二甲基-9H-咔唑-9-基)丁基)膦酸（4PACz），其传输电荷效率低，浸润性差，效率低，同时不能有效的钝化钙钛矿表面的缺陷等一系列缺点限制了钙钛矿太阳能电池效率的进一步提升（Angew. Chem. Int. Ed. 2025,64, e202416188）
[0051]1、本发明提供的一种离子盐功能化的自组装单分子层材料，膦酸为锚定基团能够实现材料与ITO基底牢固的相互作用，此外，引入的铵盐钝化剂有助于钝化钙钛矿表面缺陷，促进高质量钙钛矿薄膜的产生。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of perovskite solar cell technology, and relates to the synthesis of hole transport materials, particularly to an ion salt functionalized self-assembled monolayer hole transport material and its preparation method, as well as its application in perovskite solar cells. Background Technology
[0002] Developing new photovoltaic technologies is considered an effective solution to address severe environmental pollution and ever-increasing energy demands. Perovskite solar cells, due to their low-temperature manufacturing process, solution processability, excellent photoelectric performance, and outstanding compatibility, are considered one of the most promising photovoltaic technologies. Since their initial report in 2009, the photoelectric conversion efficiency of perovskite solar cells has rapidly increased from an initial 3.8% to 28%, approaching the level of traditional silicon-based solar cells. However, improving the interface quality between the hole transport layer and the perovskite, and enhancing charge extraction and transport at the interface, is crucial for further improving device efficiency and stability.
[0003] Generally, self-assembled monolayers (SAMs) consist of three parts: anchoring groups, or linking chains, and terminal functional groups. The anchoring groups and terminal functional groups play the most crucial roles, with phosphate groups often used as anchoring groups to achieve tight bonding with the conductive substrate. The anchoring group, as the core element of SAM design, determines the bonding strength between the substrate and the SAM. The linking chain in SAMs, serving as the key framework connecting the anchoring groups and terminal functional groups, is mainly composed of non-conjugated alkyl chains or conjugated aromatic rings. Terminal functional groups typically constitute the functional ends of the molecule, and their properties are inherently determined. By changing the type of terminal group, their hydrophilicity or hydrophobicity and energy levels can be altered, thereby controlling the device's performance. SAM molecules possess a series of advantages, including precise molecular-level control, excellent film uniformity, flexible functionalization design, and substrate universality, making them the primary choice for fabricating high-efficiency and highly stable large-scale components.
[0004] Commonly used self-assembled monolayer materials, such as (4-(3,6-dimethyl-9H-carbazole-9-yl)butyl)phosphonic acid (4PACz), suffer from low charge transfer efficiency, poor wettability, and low overall efficiency. Furthermore, they cannot effectively passivate defects on the perovskite surface, limiting further improvements in the efficiency of perovskite solar cells (Angew. Chem. Int. Ed. 2025, 64, e202416188). In addition, 4PACz exhibits low efficiency and poor stability in large-area devices. Therefore, there is an urgent need for a novel SAM material that can effectively transfer charge, passivate perovskite surface defects, and improve cell stability. This is of great significance for promoting the industrialization of perovskite solar cells. Summary of the Invention
[0005] In view of the shortcomings of the prior art, the present invention aims to provide a self-assembled monolayer material that is simple in structure, cost-effective, and efficient.
[0006] This invention constructs an ion salt functionalized self-assembled monolayer material, introducing common ammonium salt passivators to effectively passivate defects on the perovskite surface, thereby improving its battery efficiency and stability.
[0007] This invention is achieved through the following techniques:
[0008] An ion salt-functionalized self-assembled monolayer hole transport material has the following general structural formula:
[0009]
[0010] The head group of general formula I is one of the following structural formulas.
[0011] The "Ar1" group in general structural formula I is one of the following structural formulas:
[0012]
[0013] The "Ar2" group in general formula II is one of the following structural formulas:
[0014]
[0015] The bridging groups of general formulas I and II are one of the following structural formulas:
[0016]
[0017] In general structural formulas I and II, R is one of the following structural formulas:
[0018]
[0019] Where n is 1 or 2.
[0020] Furthermore, the ion salt-functionalized self-assembled monolayer hole transport material is one of the following compounds:
[0021]
[0022]
[0023] Where n is 0, 1, or 2.
[0024] This invention provides a method for preparing an ion salt-functionalized self-assembled monolayer hole transport material with structural formula (I), the synthetic route being as follows:
[0025]
[0026] Where n is 0, 1, or 2;
[0027] Includes the following steps:
[0028] (a) Compound 1aa undergoes a Suzuki substitution reaction to generate intermediate 1cc;
[0029] (b) The compound 1cc undergoes a Ullmann coupling reaction to generate intermediate 1dd;
[0030] (c) Compound 1dd undergoes a substitution reaction with triethyl phosphite to generate intermediate 1ee;
[0031] (d) Cause the compound 1ee to undergo a hydrolysis reaction to generate the target product (I), namely the ion salt-functionalized self-assembled monolayer hole transport material.
[0032] This invention provides a method for preparing an ion salt-functionalized self-assembled monolayer hole transport material with structural formula (Ⅱ), the synthetic route being as follows:
[0033]
[0034] Where n is 0, 1, or 2;
[0035] (e) To induce boron esterification of compound 2aa to generate intermediate 2cc;
[0036] (f) The compound 2cc undergoes a Suzuki coupling reaction to generate intermediate 2ee;
[0037] (g) Causes compound 2ee to undergo a Ullmann coupling reaction to generate intermediate 2ff;
[0038] (h) Compound 2ff undergoes a substitution reaction with triethyl phosphite to generate intermediate 2gg;
[0039] (i) Cause the compound 2gg to undergo a hydrolysis reaction to generate the target product II, i.e., a self-assembled monolayer material.
[0040] Further, in step (a), under nitrogen atmosphere, compounds 1aa and 1bb, palladium catalyst, base and solvent are added and reacted at 100 °C for 8-12 h; after the reaction is completed, compound 1cc is obtained by separation and purification; the molar ratio of compound 1aa to 1bb, palladium catalyst and base is 1:1.1-1.5:0.01-0.1:2-5.
[0041] Further, in step (b), under nitrogen atmosphere, compound 1cc is reacted with the dibromo compound of the bridging group at 60 °C for 4-10 h under the catalysis of sodium hydroxide and tetrabutylammonium bromide; after the reaction, compound 1dd is obtained by separation and purification; the molar ratio of the reactant compound 1cc to the dibromo compound of the two bridging groups, sodium hydroxide, and tetrabutylammonium bromide is 1:2~10:5-15:0.01-0.1.
[0042] Further, in step (c), in a nitrogen atmosphere, compound 1dd reacts with triethyl phosphite at 160 °C for 12-24 h; after the reaction is completed, compound 1ee is obtained by separation and purification; the molar ratio of the reactant compound 1dd to triethyl phosphite is 1:10-15.
[0043] Further, the specific process of step (d) is as follows: compound 1ee is dissolved in dichloromethane, trimethylbromosilane is added under nitrogen atmosphere, the reaction is carried out at room temperature for 5-24 h, the solvent is evaporated after the reaction is completed, the product is dissolved in methanol, distilled water is added and slurry is stirred, and the mixture is filtered to obtain compound I; the molar ratio of compound 1ee to trimethylbromosilane is 1:8~25.
[0044] Further, in step (e), under nitrogen atmosphere, compounds 2aa, 2bb, palladium catalyst, base and solvent are added, and the reaction is carried out at 100 °C for 8-12 h; after the reaction is completed, compound 2cc is obtained by separation and purification; the molar ratio of compound 2aa to 2bb, palladium catalyst and base is 1:1.1-1.5:0.01-0.1:2-5.
[0045] Furthermore, in step (f), under nitrogen atmosphere, compounds 2cc and 2dd are dissolved in 1,4-dioxane, alkali is added, and the reaction is carried out at 100 °C for 10-14 h. After the reaction is completed, compound 2ee is obtained by separation and purification. The molar ratio of compounds 2cc and 2dd, palladium catalyst, and alkali is 1:1.1-1.5:0.01-0.1:2-5.
[0046] Furthermore, in step (g), under nitrogen atmosphere, compound 2ee is reacted with the dibromo-based bridging compound at 60 °C for 4-10 h under the catalysis of sodium hydroxide and tetrabutylammonium bromide; after the reaction, compound 2ff is obtained by separation and purification; the molar ratio of the reactant compound 2ee to the dibromo-based bridging compound, sodium hydroxide, and tetrabutylammonium bromide is 1:2~10:5-15:0.01-0.1.
[0047] Furthermore, in step (h), in a nitrogen atmosphere, compound 2ff reacts with triethyl phosphite at 160 °C for 12-24 h; after the reaction is completed, compound 2gg is obtained by separation and purification; the molar ratio of the reactant compound 2ff to triethyl phosphite is 1:10-15.
[0048] Further, in step (i), compound 2gg is dissolved in dichloromethane, trimethylbromosilane is added under nitrogen atmosphere, and the reaction is carried out at room temperature for 5-24 h. After the reaction is completed, the solvent is evaporated, the product is dissolved in methanol, distilled water is added and the mixture is filtered to obtain compound II; the molar ratio of compound 2gg to trimethylbromosilane is 1:8-25.
[0049] The present invention further provides the application of the above-mentioned ion salt functionalized self-assembled monolayer material in perovskite solar cells.
[0050] The beneficial effects of this invention are as follows:
[0051] 1. The present invention provides an ion salt functionalized self-assembled monolayer material, in which phosphonic acid is used as an anchoring group to achieve a strong interaction between the material and the ITO substrate. In addition, the introduced ammonium salt passivator helps to passivate perovskite surface defects and promotes the generation of high-quality perovskite films.
[0052] 2. The π-extended functional framework is beneficial for enhancing intermolecular interactions and promoting hole transport.
[0053] 3. The application of the self-assembled monolayer material provided by this invention in perovskite solar cells can achieve a photoelectric conversion efficiency of over 27%, further promoting the industrialization process of perovskite solar cells. Attached Figure Description
[0054] Figure 1 This is a schematic diagram of the molecular structure of the ion salt-functionalized self-assembled monolayer hole transport material prepared in this invention.
[0055] Figure 2 The NMR spectrum of formula I-1-C4 prepared according to the present invention;
[0056] Figure 3 The nuclear magnetic resonance spectrum of formula II-1-C4 prepared according to the present invention;
[0057] Figure 4 The NMR spectrum of formula II-7-C4 prepared according to this invention;
[0058] Figure 5 Differential thermal scanning spectroscopy (DSC) images of the compounds of formulas I-1-C3, II-1-C4, I-1-C4, and II-7-C4 prepared in this invention as self-assembled monolayer materials are shown.
[0059] Figure 6 JV curves of perovskite solar cells prepared using formula II-7-C4 as a self-assembled monolayer material according to the present invention. Detailed Implementation
[0060] The invention will now be described in detail with specific examples.
[0061] The following will take formulas I-1-C4 and II-7-C4 as examples for detailed explanation.
[0062] Example 1: Synthesis of compound I-1-C4, a self-assembled monolayer hole transport material.
[0063]
[0064] Synthesis of compound 1c:
[0065] In a 100 mL double-necked flask, compounds 1a (2.00 g, 6.21 mmol), 1b (3.89 g, 15.52 mmol), Pb(dba)3 (0.31 mmol, 0.28 g), and K2CO3 (2.57 g, 18.63 mmol) were dissolved in a mixed solvent of toluene (30 mL) and deionized water (10 mL). The mixture was refluxed at 110 °C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 8:1, v / v) to give compound 1c as a white solid, approximately 3.22 g, in 90% yield.
[0066] Synthesis of compound 1d:
[0067] In a 100 mL double-necked flask, compound 1c (3.00 g, 5.19 mmol), TBAB (164.22 g, 0.51 mmol), and 50% potassium hydroxide aqueous solution (2.90 g, 51.90 mmol) were placed in 30 mL of 1,4-dibromobutane and refluxed at 60 °C for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, volatile components were removed by concentration under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give 3.25 g of compound 1d as a white solid, with a yield of 90%.
[0068] Synthesis of compound 1e:
[0069] Compound 1d (3.00 g, 4.20 mmol) was reacted with triethyl phosphite (20 mL) in a 50 mL double-necked flask and refluxed at 170 °C for 24 hours under a nitrogen atmosphere. After the reaction was complete, the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give 3.07 g of compound 1e as a white solid, with a yield of 95%.
[0070] Synthesis of compound I-1-C4:
[0071] In a 100 mL three-necked flask, compound 1e (2.00 g, 3.90 mmol) was dissolved in anhydrous dichloromethane (30 mL) under a nitrogen atmosphere, and trimethylsilane iodide (0.59 mL, 4.50 mmol) was added dropwise. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After the reaction was complete, the solvent was partially evaporated under reduced pressure. The residual liquid was dissolved in methanol (10 mL), and then distilled water (50 mL) was added dropwise until the solution became cloudy. The solid product was collected by suction filtration, washed with water, and dried to give 2.74 g of compound I-1-C4 as a reddish-brown solid, with a yield of 90%. 1 H NMR (400 MHz, DMSO-d6) δ 8.69 (d, J = 1.9 Hz, 1H),8.18 (s, 3H), 7.88 (dd, J = 22.0, 8.5 Hz, 3H), 7.75 (d, J = 8.7 Hz, 1H), 7.58(d, J = 7.9 Hz, 2H), 4.48 (s, 1H), 4.12 (s, 2H), 1.90 (s, 1H), 1.54 (s, 2H).
[0072] Example 2: Synthesis of self-assembled monolayer hole transport material compound I-1-C3.
[0073]
[0074] Synthesis of compound 2c:
[0075] In a 100 mL double-necked flask, compounds 3a (2.00 g, 6.21 mmol), 1b (3.89 g, 15.52 mmol), Pb(dba)3 (0.31 mmol, 0.28 g), and K2CO3 (2.57 g, 18.63 mmol) were dissolved in a mixed solvent of toluene (30 mL) and deionized water (10 mL). The mixture was refluxed at 110 °C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 8:1, v / v) to give compound 2c as a white solid, approximately 3.22 g, in 90% yield.
[0076] Synthesis of compounds of formula 2d:
[0077] In a 100 mL double-necked flask, compound 2c (3.00 g, 5.19 mmol), TBAB (164.22 g, 0.51 mmol), and 50% potassium hydroxide aqueous solution (2.90 g, 51.90 mmol) were placed in 15 mL of 1,4-dibromobutane and refluxed at 60 °C for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, volatile components were removed by concentration under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give 3.25 g of compound 2d as a white solid, with a yield of 90%.
[0078] Synthesis of compound 2e:
[0079] Compound 2d (3.00 g, 4.30 mmol) was reacted with triethyl phosphite (20 mL) in a 50 mL double-necked flask and refluxed at 170 °C for 24 hours under a nitrogen atmosphere. After the reaction was completed, the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give 2.17 g of compound 2e as a white solid.
[0080] Synthesis of compound I-1-C3:
[0081] In a 100 mL three-necked flask, compound 2e (2.00 g, 2.65 mmol) was dissolved in anhydrous dichloromethane (30 mL) under a nitrogen atmosphere, and trimethylsilane iodide (0.59 mL, 4.50 mmol) was added dropwise. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After the reaction was complete, the solvent was partially evaporated under reduced pressure. The residual liquid was dissolved in methanol (10 mL), and then distilled water (50 mL) was added dropwise until the solution became cloudy. The solid product was collected by suction filtration, washed with water, and dried to give 2.65 g of compound I-1-C3 as a reddish-brown solid, with a yield of 89%. 1 H NMR (400 MHz, DMSO-d6) δ 8.71 (d, J = 1.7 Hz, 4H), 8.54 (d, J = 1.9 Hz, 1H), 8.18 (s, 12H), 7.95 – 7.83 (m, 13H), 7.78 (d, J =8.8 Hz, 5H), 1.56 (dd,J = 17.5, 8.7 Hz, 5H), 1.09 (t, J = 7.0 Hz, 4H).
[0082] Example 3: Synthesis of compound II-1-C3, a self-assembled monolayer hole transport material.
[0083]
[0084] Synthesis of compound 3c:
[0085] In a 100 mL double-necked flask, compounds 3a (2.00 g, 6.21 mmol), 1b (1.95 g, 7.76 mmol), Pb(dba)3 (0.16 mmol, 0.14 g), and K2CO3 (1.88 g, 9.32 mmol) were dissolved in a mixed solvent of toluene (30 mL) and deionized water (10 mL). The mixture was refluxed at 110 °C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 8:1, v / v) to give compound 3c as a white solid in 83% yield.
[0086] Synthesis of 3d compounds:
[0087] In a 100 mL double-necked flask, compound 3c (3.00 g, 6.67 mmol), TBAB (164.22 g, 0.51 mmol), and 50% potassium hydroxide aqueous solution (2.90 g, 51.90 mmol) were placed in 15 mL of 1,4-dibromobutane and refluxed at 60 °C for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, volatile components were removed by concentration under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give compound 3d as a white solid in 88% yield.
[0088] Synthesis of compound of formula 3e:
[0089] Compound 3d (3.00 g, 5.12 mmol) was reacted with triethyl phosphite (20 mL) in a 50 mL double-necked flask and refluxed at 170 °C for 24 hours under a nitrogen atmosphere. After the reaction was complete, the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give 1.98 g of compound 3e as a white solid.
[0090] Synthesis of compound I-1-C3:
[0091] In a 100 mL three-necked flask, compound 3e (2.00 g, 3.11 mmol) was dissolved in anhydrous dichloromethane (30 mL) under a nitrogen atmosphere, and trimethylsilane iodide (0.59 mL, 4.50 mmol) was added dropwise. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After the reaction was complete, the solvent was partially evaporated under reduced pressure. The residual liquid was dissolved in methanol (10 mL), and then distilled water (50 mL) was added dropwise until the solution became cloudy. The solid product was collected by suction filtration, washed with water, and dried to give compound I-1-C3 as a reddish-brown solid, with a yield of 84%. 11 H NMR (400 MHz, DMSO-d6) δ 8.67 (s, 1H), 8.16 (s, 3H), 7.87(dd, J = 23.0, 8.5 Hz, 4H), 7.73 (d, J = 8.6 Hz, 2H), 7.58 (d, J = 8.0 Hz, 3H), 4.47 (t, J = 8.4 Hz, 2H), 4.12 (s, 3H), 1.90 (s, 2H), 1.56 (s, 2H).
[0092] Example 4: Synthesis of self-assembled monolayer hole transport material compound I-8-C4.
[0093]
[0094] Synthesis of compound 1c:
[0095] In a 100 mL double-necked flask, compounds 1a (2.00 g, 6.21 mmol), 1b (3.89 g, 15.52 mmol), Pb(dba)3 (0.31 mmol, 0.28 g), and K2CO3 (2.57 g, 18.63 mmol) were dissolved in a mixed solvent of toluene (30 mL) and deionized water (10 mL). The mixture was refluxed at 110 °C for 12 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 8:1, v / v) to give compound 1c as a white solid, approximately 3.22 g, in 90% yield.
[0096] Synthesis of 4d compounds:
[0097] In a 100 mL double-necked flask, compound 1c (3.00 g, 5.19 mmol), compound 4a (2.11 g, 6.00 mmol), TBAB (164.22 g, 0.51 mmol), and 50% potassium hydroxide aqueous solution (2.90 g, 51.90 mmol) were placed in 30 mL of 1,4-dibromobutane and refluxed at 60 °C for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, volatile components were removed by concentration under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give compound 4d as a white solid in 82% yield.
[0098] Synthesis of compound 4e:
[0099] Compound 4d (3.00 g, 3.54 mmol) was reacted with triethyl phosphite (20 mL) in a 50 mL double-necked flask and refluxed at 170 °C for 24 hours under a nitrogen atmosphere. After the reaction was complete, the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give compound 4e as a white solid in 88% yield.
[0100] Synthesis of compound I-8-C4:
[0101] In a 100 mL three-necked flask, compound 4e (2.00 g, 2.21 mmol) was dissolved in anhydrous dichloromethane (30 mL) under a nitrogen atmosphere, and trimethylsilane iodide (0.59 mL, 4.50 mmol) was added dropwise. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After the reaction was complete, the solvent was partially evaporated under reduced pressure. The residual liquid was dissolved in methanol (10 mL), and then distilled water (50 mL) was added dropwise until the solution became cloudy. The solid product was collected by suction filtration, washed with water, and dried to give compound I-8-C4 as a reddish-brown solid, with a yield of 81%. 1 H NMR (400 MHz, DMSO-d6) δ 8.38 (s, 6H), 8.08 (d, J = 8.0Hz, 1H), 7.99 (m, 3H), 7.88 (s, 2H), 7.77 (d, J = 8.3 Hz, 2H), 7.75 (d, J =7.9 Hz, 4H), 7.49 (t, J = 7.9 Hz, J = 7.9 Hz, 4H), 7.45 (s, 1H), 7.33 (s,1H), 7.28 (d, J = 8.0 Hz, 1H), 7.16 (d, J = 7.8 Hz, 1H), 4.12 (s, 4H), 1.69 (s, 6H).
[0102] Example 5: Synthesis of compound II-7-C4, a self-assembled monolayer hole transport material.
[0103]
[0104] Synthesis of compound 5c:
[0105] In a 100 mL double-necked flask, compounds 5a (2.00 g, 5.52 mmol), 5b (1.68 g, 6.62 mmol), Pd(pddf)Cl2 (0.40 g, 0.55 mmol), and KOAc (1.62 g, 16.56 mmol) were dissolved in 50 mL of 1,4-dioxane. The mixture was refluxed at 100 °C for 10 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 5:1, v / v) to give 2.14 g of compound 5c as a white solid, with a yield of 95%.
[0106] Synthesis of compound 5e:
[0107] In a 100 mL double-necked flask, compounds 5c (2.00 g, 4.88 mmol), 5d (1.75 g, 5.85 mmol), Pd(pddf)Cl2 (0.35 g, 0.49 mmol), and KOH (0.81 g, 14.64 mmol) were mixed in 50 mL of 1,4-dioxane and refluxed at 100 °C for 12 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 7:1, v / v) to give 1.95 g of compound 5e as a white solid, in 80% yield.
[0108] Synthesis of compound 5f:
[0109] In a 100 mL double-necked flask, compound 5e (2.00 g, 3.98 mmol), tetrabutylammonium bromide (TBAB, 0.09 g, 0.39 mmol), and 50% potassium hydroxide aqueous solution (1.59 g, 39.80 mmol) were placed in 30 mL of 1,4-dibromobutane and refluxed at 60 °C for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, volatile components were removed by concentration under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give 2.40 g of compound 5f as a white solid, with a yield of 95%.
[0110] Synthesis of compound formula 5g:
[0111] Compound 5f (2.0 g, 3.14 mmol) was reacted with triethyl phosphite (20 mL) in a 50 mL double-necked flask and refluxed at 170 °C for 24 hours under a nitrogen atmosphere. After the reaction was complete, the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give 1.96 g of compound 5f as a white solid, with a yield of 90%.
[0112] Synthesis of compound II-7-C4:
[0113] In a 100 mL three-necked flask, 5 g (2.00 g, 2.88 mmol) of the compound was dissolved in anhydrous dichloromethane (30 mL) under a nitrogen atmosphere, and trimethylsilane iodide (0.59 mL, 4.50 mmol) was added dropwise. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After the reaction was complete, the solvent was partially evaporated under reduced pressure. The residual liquid was dissolved in methanol (10 mL), and then distilled water (50 mL) was added dropwise until the solution became cloudy. The solid product was collected by suction filtration, washed with water and dried to give 1.72 g of compound II-7-C4 reddish-brown solid, yield 90%.1 H NMR (400 MHz, DMSO-d6) δ 8.67 (s, 1H), 8.52 (s,1H), 7.87 (d, J = 8.8 Hz, 2H), 7.81 (s, 3H), 7.78 (d, J = 8.8 Hz, 2H), 7.74(s, 1H), 7.70 (d, J = 8.6 Hz, 1H), 7.55 (d, J = 7.5 Hz, 1H), 7.38 (dd, J =16.9, 7.8 Hz, 3H), 7.27 (t, J = 7.3 Hz, 1H), 4.48 (t, J = 6.6 Hz, 2H), 2.98 –2.88 (m, 2H), 1.96 – 1.85 (m, 2H), 1.61 (d, J = 8.6 Hz, 4H), 1.56 (s, 6H), 1.23 (s, 2H).
[0114] Example 6: Synthesis of compound II-11-C4, a self-assembled monolayer hole transport material.
[0115]
[0116] Synthesis of compound 6c:
[0117] In a 100 mL double-necked flask, compounds 6a (2.00 g, 6.76 mmol), 5b (1.68 g, 6.62 mmol), Pd(pddf)Cl2 (0.40 g, 0.55 mmol), and KOAc (1.62 g, 16.56 mmol) were dissolved in 50 mL of 1,4-dioxane. The mixture was refluxed at 100 °C for 10 hours under a nitrogen atmosphere. After cooling to room temperature, the reaction solution was extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 5:1, v / v) to give compound 6c as a white solid in 91% yield.
[0118] Synthesis of compound 6e:
[0119] In a 100 mL double-necked flask, compound 6c (2.00 g, 5.83 mmol), compound 5d (1.75 g, 5.85 mmol), Pd(pddf)Cl2 (0.35 g, 0.49 mmol), and KOH (0.81 g, 14.64 mmol) were mixed in 50 mL of 1,4-dioxane and refluxed at 100 °C for 12 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and extracted three times with dichloromethane and water. The combined organic phases were dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 7:1, v / v) to give compound 6e as a white solid in 81% yield.
[0120] Synthesis of compound 6f:
[0121] In a 100 mL double-necked flask, compound 6e (2.00 g, 5.18 mmol), p-dibromobenzene (1.40 g, 6.00 mmol), tetrabutylammonium bromide (TBAB, 0.09 g, 0.39 mmol), and 50% potassium hydroxide aqueous solution (1.59 g, 39.80 mmol) were placed in a solution of 1,4-dioxane and refluxed at 60 °C for 6 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, volatile components were removed by concentration under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1, v / v) to give compound 6f as a white solid in 79% yield.
[0122] Synthesis of compound 6g:
[0123] Compound 6f (2.0 g, 3.38 mmol) was reacted with triethyl phosphite (20 mL) in a 50 mL double-necked flask and refluxed at 170 °C for 24 hours under a nitrogen atmosphere. After the reaction was complete, the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 1:1, v / v) to give compound 6 g as a white solid, in 90% yield.
[0124] Synthesis of compound II-7-C4:
[0125] In a 100 mL three-necked flask, 6 g (2.00 g, 3.15 mmol) of the compound was dissolved in anhydrous dichloromethane (30 mL) under a nitrogen atmosphere, and trimethylsilane iodide (0.59 mL, 4.50 mmol) was added dropwise. The reaction mixture was stirred at room temperature under a nitrogen atmosphere for 24 hours. After the reaction was complete, the solvent was partially evaporated under reduced pressure. The residual liquid was dissolved in methanol (10 mL), and then distilled water (50 mL) was added dropwise until the solution became cloudy. The solid product was collected by suction filtration, washed with water and dried to give 1.72 g of compound II-7-C4 reddish-brown solid, with a yield of 90%.1 H NMR (400 MHz, DMSO-d6) δ 8.54 (d, J = 8.3 Hz, 1H),8.23 (s, 3H), 7.99 (m, 2H), 7.96 (m, 2H), 7.89 (s, 1H), 7.77 (d, J = 8.3 Hz,1H), 7.75 (m, 5H), 7.49 (m, 3H), 7.38 (d, J = 8.8 Hz, 2H), 2.98 (t, J = 6.6Hz, 2H), 1.23 (t, J = 6.5 Hz, 2H).
[0126] Example 7: This example provides the application of compounds of formulas I-1-C3, II-1-C4, I-1-C4, and II-7-C4 prepared in Examples 1, 2, 3, and 5 in the fabrication of perovskite solar cells. Thermogravimetric analysis (TGA) was used to test the thermal stability of the samples. The alumina crucible was first tare and zeroed, and then approximately 5 mg of SAM sample was accurately weighed and placed in the crucible. Under a nitrogen atmosphere, the temperature was programmed to rise from 30 °C to 600 °C at a rate of 10 °C / min, and the mass change of the sample as a function of temperature was recorded. (See attached image.) Figure 5 Differential thermal scanning spectroscopy (DSC) images of the compounds of formula I-1-C3, II-1-C4, I-1-C4 and II-7-C4 prepared in this invention as self-assembled monolayer materials are shown. It can be seen that the thermal decomposition temperature of the four ion salt functionalized self-assembled monolayer materials is above 180°C, which is significantly higher than the heat treatment temperature (120°C) for battery preparation, and all of them have good thermal resistance.
[0127] Example 8: This example provides an application of the compound of formula II-7-C4 prepared in Example 5 in the fabrication of perovskite solar cells. Test light source: AM 1.5 (solar simulator-Oriel 91160-1000, 300W), data acquisition using a Keithley 2400 digital source meter. (Attached) Figure 6 The JV curves of perovskite solar cells fabricated using formula II-7-C4 as a self-assembled monolayer material according to the present invention are shown. The results indicate that, under positive scan, the short-circuit photocurrent density of the solar cell reaches 26.24 mA cm⁻¹. -2 The open-circuit voltage was 1.190 V, the fill factor (FF) was 87.07, and the photoelectric conversion efficiency reached 27.21%. Reverse scanning results showed that the short-circuit photocurrent density of the battery device reached 26.19 mA cm⁻¹. -2The open-circuit voltage is 1.190 V, the fill factor (FF) is 87.30, and the photoelectric conversion efficiency reaches 27.23%.
Claims
1. A self-assembled monolayer hole transport material functionalized with ion salts, characterized in that, The general structural formula is as follows: The "Ar1" group in general structural formula I is one of the following structural formulas: The "Ar2" group in general formula II is one of the following structural formulas: The bridging groups of general formulas I and II are one of the following structural formulas: In general structural formulas I and II, R is one of the following structural formulas: Where n is 1 or 2.
2. The ion salt-functionalized self-assembled monolayer hole transport material according to claim 1, characterized in that, The self-assembled monolayer hole transport material is one of the following compounds: Where n is 0, 1, or 2.
3. The method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to claim 1, characterized in that, The synthetic route is as follows: Where n is 0, 1, or 2; Includes the following steps: (a) Compound 1aa undergoes a Suzuki substitution reaction to generate intermediate 1cc; (b) The compound 1cc undergoes a Ullmann coupling reaction to generate intermediate 1dd; (c) Compound 1dd undergoes a substitution reaction with triethyl phosphite to generate intermediate 1ee; (d) Cause the compound 1ee to undergo a hydrolysis reaction to generate the target product (I), namely the ion salt-functionalized self-assembled monolayer hole transport material.
4. The method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to claim 1, characterized in that, The synthetic route is as follows: Where n is 0, 1, or 2; Includes the following steps: (e) To induce boron esterification of compound 2aa to generate intermediate 2cc; (f) The compound 2cc undergoes a Suzuki coupling reaction to generate intermediate 2ee; (g) Causes compound 2ee to undergo a Ullmann coupling reaction to generate intermediate 2ff; (h) Compound 2ff undergoes a substitution reaction with triethyl phosphite to generate intermediate 2gg; (i) Cause the compound 2gg to undergo a hydrolysis reaction to generate the target product II, i.e., a self-assembled monolayer material.
5. A method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to claim 3 or 4, characterized in that: The specific process of step (a) or step (e) is as follows: under nitrogen atmosphere, add compound 1aa, 1bb, palladium catalyst, base and solvent, or add compound 2aa, 2bb, palladium catalyst, base and solvent, and react at 100 °C for 8-12 h; after the reaction is completed, separate and purify to obtain compound 1cc or 2cc respectively; the molar ratio of compound 1aa or 2aa, 1bb or 2bb, palladium catalyst and base is 1:1.1-1.5:0.01-0.1:2-5.
6. A method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to claim 3 or 4, characterized in that: The specific process of step (b) or step (g) is as follows: under nitrogen atmosphere, compound 1cc or 2ee is reacted with the dibromo compound of the bridging group at 60 °C for 4-10 h under the catalysis of sodium hydroxide and tetrabutylammonium bromide; after the reaction, compound 1dd or 2ff is obtained by separation and purification respectively; the molar ratio of the reactant compound 1cc or 2ee to the dibromo compound of the two bridging groups, sodium hydroxide, and tetrabutylammonium bromide is 1:2~10:5-15:0.01-0.
1.
7. A method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to claim 3 or 4, characterized in that: The specific process of step (c) or step (h) is as follows: in a nitrogen atmosphere, compound 1dd or 2ff reacts with triethyl phosphite at 160 °C for 12-24 h; after the reaction is completed, compound 1ee or 2gg is obtained by separation and purification; the molar ratio of the reactant compound 1dd or 2ff to triethyl phosphite is 1:10-15.
8. A method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to any one of claims 3, characterized in that: The specific process of step (d) or step (i) is as follows: dissolve compound 1ee or 2gg in dichloromethane, add trimethylbromosilane under nitrogen atmosphere, react at room temperature for 5-24 h, after the reaction is completed, evaporate the solvent, dissolve the product in methanol, add distilled water to make a slurry, filter, and obtain compound I or compound II respectively; the molar ratio of compound 1ee or 2gg to trimethylbromosilane is 1:8~25.
9. The method for preparing an ion salt-functionalized self-assembled monolayer hole transport material according to claim 4, characterized in that: The specific process of step (f) is as follows: under nitrogen atmosphere, compound 2cc and 2dd are placed in 1,4-dioxane, alkali is added, and the reaction is carried out at 100 °C for 10-14 h. After the reaction is completed, compound 2ee is obtained by separation and purification. The molar ratio of compound 2cc to 2dd, palladium catalyst and alkali is 1:1.1-1.5:0.01-0.1:2-5.
10. The application of the ion salt functionalized self-assembled monolayer hole transport material according to claim 1 or 2 in perovskite solar cells.