A vinyl-containing self-assembly material and its application

Abstract

This invention relates to the field of solar cell materials technology, and discloses a vinyl-containing self-assembled material and its applications. The self-assembled material has the structure shown in (I). The vinyl-containing self-assembled material of this invention can undergo a cross-linking reaction under heating conditions to form a dense, uniform, and morphologically stable thin film, thereby greatly improving the stability of the device. It can be used to prepare organic solar cells for application in automotive, building, or Internet of Things devices. (I)

Description

Technical Field

[0001] This invention relates to the field of solar cell materials technology, and more specifically to a vinyl-containing self-assembly material and its applications. Background Technology

[0002] Organic solar cells have attracted much attention due to their flexibility, lightweight nature, and ability to be printed to fabricate large-area devices. Currently, the power conversion efficiency of single-junction devices has exceeded 20%, demonstrating their enormous application potential. Organic solar cells employ a "sandwich" layer-by-layer stacked structure, with hole transport layers and electron transport layers on either side of the active layer. These layers are used to modify the work function of the electrodes, reduce charge recombination at the interface, and thus improve device performance.

[0003] PEDOT:PSS is currently widely used as a hole transport layer material in organic solar cells. However, due to its strong acidity and hygroscopicity, PEDOT:PSS exhibits poor stability. Furthermore, PEDOT:PSS shows absorption in the infrared region and a high HOMO level, which limits the short-circuit current density (J / L). SC ) and open-circuit voltage (V OC The enhancement of ).

[0004] Self-assembled monolayers (SAMs) containing anchoring groups have attracted widespread attention due to their advantages such as low production cost, negligible optical and electrical losses, easy tuning of energy levels and surface properties, conformal coverage on rough surfaces, and simple deposition on large-area substrates. The structure of a SAM molecule typically consists of three parts: end groups with hole transport capabilities, anchoring groups that can be chemically adsorbed onto the substrate, and bridging groups between the two.

[0005] For example, CN 116655682 A discloses a self-assembled monolayer hole transport material based on diphenylamine, its synthesis method, and its application in inverted perovskite solar cells. Using diphenylamine, which has excellent hole transport properties, as the core, the hole transport performance of the material is guaranteed. The interfacial dipole and passivation properties are regulated by adjusting the contact groups at the diphenylamine-perovskite interface. The butyl phosphate anchoring group enables complete coverage and stable self-assembly of the material on the substrate surface. When applied as a hole transport layer in inverted perovskite solar cells, this material achieves a photoelectric conversion efficiency of >21% without doping, demonstrating broad application prospects.

[0006] CN116874529A discloses a self-assembled monolayer hole transport material based on alkyl polyphosphate anchoring groups, its synthesis method, and its application in inverted perovskite solar cells. Using carbazole or 3,6-diphenylcarbazole, which have excellent hole transport properties, as the parent core, the anchoring groups are improved from traditional alkyl monophosphates to alkyl diphosphates and triphosphates, achieving complete coverage and stable self-assembly of the material on the substrate surface.

[0007] However, the hole transport layer based on SAM molecules is usually a very thin monolayer, which makes it difficult to form a uniform and stable film during preparation. Its photoelectric performance lifetime is short, which limits its commercialization in organic solar cell devices. Summary of the Invention

[0008] This invention addresses the problem of insufficient photoelectric stability in hole transport materials by providing a self-assembled small molecule material containing vinyl groups. When used as a hole-selective layer material in organic solar cell devices, this material can form a uniform and stable thin film through cross-linking, thereby improving the stability of the device.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] A vinyl-containing self-assembly material having a structure as shown in formula (I):

[0011] (I)

[0012] in:

[0013] n is selected from 0, 1, 2, 3, 4, 5, or 6;

[0014] -Z- is selected from non-existent, single bond, -O-, -S-, or CR1R2;

[0015] R1 and R2 are independently selected from -H, -D, and alkyl groups having 1 to 6 carbon atoms.

[0016] In some embodiments, n is selected from 1 or 3, and the vinyl-containing self-assembly material has the following general formula structure:

[0017] .

[0018] In some implementations, -Z- is selected from non-existent, single bond, -O-, -S-, or C(CH3)2.

[0019] Furthermore, R1 and R2 are independently selected from -H, -D, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.

[0020] In some embodiments, the self-assembling material is selected from any of the following structures:

[0021]

[0022]

[0023] .

[0024] The present invention also provides an organic solar cell, the organic solar cell comprising at least one hole selection layer, the hole selection layer material comprising the vinyl-containing self-assembly material as described above.

[0025] In the self-assembled material described in this invention, vinyl groups can undergo self-crosslinking under heating conditions, thereby making the prepared hole-selective layer dense and uniform, thus improving the photoelectric stability of organic solar cells.

[0026] In some embodiments, the organic solar cell comprises, from bottom to top, an anode layer, a hole-selective layer, a photoactive layer, an electron transport layer, and a cathode layer, wherein the hole-selective layer is made of a vinyl-containing self-assembly material as described above.

[0027] In some embodiments, the material of the anode layer is selected from FTO or ITO;

[0028] In some embodiments, the photoactive layer comprises a donor material and an acceptor material. The donor material is preferably selected from one or more of PBDB-T, PM6, PM7, D18, D18-Cl, PBQx-Cl, and PTQ10, but is not limited thereto. The acceptor material is selected from Y6, L8-BO, N3, BTP-eC9, and PC. 61 BM, PC 71 One or more of BM, but not limited to these;

[0029] In some embodiments, the mass ratio of donor material to acceptor material in the photoactive layer is selected from 0.8:1.8 to 1.8:0.8. Further, the mass ratio is 1:1 to 1:1.8; even further, the mass ratio is 1:1 to 1:1.5; and even further, the mass ratio is 1:1 to 1:1.2.

[0030] In some embodiments, the material of the electron transport layer is selected from one or more of PDINN, PDINO, PFN-Br, PNDIT-F3N-Br, or PNDIT-F3N, but is not limited thereto.

[0031] In some embodiments, the cathode layer material is selected from zinc (Zn), silver (Ag), aluminum (Al), gold (Au), nickel (Ni), or alloys of the above metals.

[0032] Furthermore, the organic solar cell also includes a substrate. In one embodiment, the substrate is disposed on one side of the anode and on a different side from the active layer. In another embodiment, the substrate is disposed on one side of the cathode and on a different side from the active layer.

[0033] In one embodiment, a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance can be used as the substrate. Specifically, a glass substrate, a thin-film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include, but is not limited to, single-layer or multi-layer films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), parylene, etc., and substrates commonly used in organic solar cells may also be used.

[0034] To improve the performance of the organic solar cell device described in this invention, the organic solar cell may further include other functional layers.

[0035] The present invention also provides a method for preparing the aforementioned organic solar cell, comprising the steps of:

[0036] Step 1: Clean the conductive glass containing the anode layer;

[0037] Step 2: Dissolve the vinyl-containing self-assembly material as described above in an organic solvent to prepare a hole-selective layer solution. Spin-coat the hole-selective layer solution uniformly onto a conductive glass containing an anode layer. Allow the mixture to stand at 100-150°C for 5-20 minutes to obtain the hole-selective layer.

[0038] Step 3: Prepare a photoactive layer by spin-coating a photoactive material onto the surface of the hole selection layer under an inert atmosphere, followed by annealing.

[0039] Step 4: Spin-coat the electron transport layer material onto the photoactive layer to obtain the electron transport layer;

[0040] Step 5: In a vacuum environment, cathode material is deposited on the surface of the electron transport layer to obtain a cathode layer, which is then encapsulated to obtain the organic solar cell.

[0041] More specifically, the present invention also provides a method for preparing the aforementioned organic solar cell, comprising the following steps:

[0042] Step 1: Clean the ITO conductive glass with detergent, rinse it clean, and then ultrasonically clean it with deionized water, acetone, and isopropanol for 10-20 minutes. Then dry it with nitrogen and treat it in a plasma cleaner for 1-10 minutes.

[0043] Step 2: Dissolve the vinyl-containing self-assembly material in methanol or ethanol to prepare a hole-selective layer solution. The concentration of the vinyl-containing self-assembly material in methanol or ethanol is 0.2-1 mg / ml. Spin-coat the hole-selective layer solution uniformly onto ITO conductive glass at a spin-coating speed of 2000-4000 rpm / min for 20-40 s to obtain the hole-selective layer. Place the device with the hole-selective layer on a hot stage at 100-150℃ for 5-20 min to allow for a cross-linking reaction.

[0044] Step 3: In a glove box (inert gas atmosphere), the photoactive layer material is uniformly spin-coated onto the hole transport layer at a speed of 1800-4000 rpm to obtain the photoactive layer.

[0045] Step 4: After hot annealing on a hot plate at 80-120℃ for 5-20 minutes, uniformly spin-coat the electron transport layer material onto the photoactive layer at a spin speed of 1800-4000 rpm to obtain the electron transport layer.

[0046] Step 5: In high vacuum (1×10⁻⁶) -6 The cathode material is deposited onto the electron transport layer in a millibar (mbar) atmosphere to obtain the cathode layer.

[0047] Step 6: The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0048] This invention also provides the application of the described organic solar cells in automotive, building, or Internet of Things (IoT) devices. Photovoltaics include, but are not limited to, automotive and building-integrated photovoltaics, indoor photovoltaics, and marine photovoltaics.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The vinyl-containing self-assembly material of the present invention can undergo a cross-linking reaction under heating conditions to form a dense, uniform, and morphologically stable thin film, thereby greatly improving the stability of the device. Attached Figure Description

[0051] Figure 1 The diagram shows the structure of the organic solar cell devices prepared for Application Examples 1-6 and Comparative Application Example 1.

[0052] Figure 2 T80 curves for the organic solar cells prepared in Application Example 1 and Comparative Application Example 1. Detailed Implementation

[0053] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Modifications or equivalent substitutions made by those skilled in the art based on their understanding of the technical solutions of this invention, without departing from the spirit and scope of the invention, should be covered within the protection scope of this invention.

[0054] Example 1 Synthesis of compound (3)

[0055]

[0056] Synthesis of compound 3-3:

[0057] Accurately weigh compound 3-1 (658 mg, 3 mmol) and compound 3-2 (22.6 g, 120 mmol), and add them to a 100 mL three-necked flask, tetrabutylammonium bromide (97 mg, 0.3 mmol), and 8 mL of 50% potassium hydroxide aqueous solution. Purge with nitrogen three times, raise the temperature to 70 °C, and react for 3 h. After cooling the reaction solution to room temperature, quench the reaction in water, extract with ethyl acetate, and remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:EA = 8:1 (v / v)) to give approximately 782 mg of compound 3-3, yield 79.8%. MALDI-TOF-MS: 326.52.

[0058] Synthesis of compounds 3-4:

[0059] Compound 3-3 (653 mg, 2 mmol) was accurately weighed and added to a 25 mL three-necked flask. After dissolving in 10 mL of triethyl phosphite, the mixture was reacted in an oil bath preheated to 160 °C for 1 h. Triethyl phosphite was removed by vacuum distillation, followed by purification by column chromatography (PE:EA = 1:2 (volume ratio)) to obtain approximately 739 mg of compound 3-4, with a yield of 96.5%. MALDI-TOF-MS: 383.11.

[0060] Synthesis of compound (3):

[0061] Accurately weigh compounds 3-4 (383 mg, 1 mmol) and add them to a 25 ml three-necked flask. Add 10 ml of anhydrous 1,4-dioxane to dissolve the compounds, purge with nitrogen three times, and slowly add 3 ml of trimethylbromosilane. Then raise the temperature to 70 °C and react for 2 h. Remove excess solvent by vacuum distillation, then dissolve the product in methanol and transfer it to a beaker. Add an appropriate amount of water until a solid precipitates, stir for 30 min, and then filter. Approximately 248 mg of compound (3) was obtained, yield: 75.6%. MALDI-TOF-MS: 327.85.

[0062] Example 2: Synthesis of compound (4)

[0063]

[0064] Synthesis of compound 4-2:

[0065] Accurately weigh compound 3-1 (658 mg, 3 mmol) and compound 4-1 (25.9 g, 120 mmol) and add them to a 100 mL three-necked flask, along with tetrabutylammonium bromide (97 mg, 0.3 mmol) and 8 mL of 50% potassium hydroxide aqueous solution. Purge with nitrogen three times, raise the temperature to 70 °C, and react for 3 h. After cooling the reaction solution to room temperature, quench the reaction in water, extract with ethyl acetate, and remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:EA = 10:1 (v / v)) to give approximately 821 mg of compound 4-2, yield 77.2%. MALDI-TOF-MS: 354.35.

[0066] Synthesis of compound 4-3:

[0067] Compound 4-2 (709 mg, 2 mmol) was accurately weighed and added to a 25 mL three-necked flask. After dissolving in 10 mL of triethyl phosphite, the mixture was reacted in an oil bath preheated to 160 °C for 1 h. Triethyl phosphite was removed by vacuum distillation, followed by purification by column chromatography (PE:EA = 1:2 (volume ratio)) to obtain approximately 785 mg of compound 4-3, with a yield of 95.3%. MALDI-TOF-MS: 411.74.

[0068] Synthesis of compound (4):

[0069] Accurately weigh compound 4-3 (412 mg, 1 mmol) and add it to a 25 mL three-necked flask. Add 10 mL of anhydrous 1,4-dioxane to dissolve it, purge with nitrogen three times, and slowly add 3 mL of trimethylbromosilane. Then raise the temperature to 70 °C and react for 2 h. Remove excess solvent by vacuum distillation, then dissolve the product in methanol and transfer it to a beaker. Add an appropriate amount of water until a solid precipitates, stir for 30 min, and then filter. Approximately 273 mg of compound (4) was obtained, yield: 76.7%. MALDI-TOF-MS: 355.94.

[0070] Example 3: Synthesis of compound (5)

[0071]

[0072] Synthesis of compound 5-2:

[0073] Accurately weigh compound 5-1 (1.02 g, 3 mmol) and compound 3-2 (22.6 g, 120 mmol), and add them to a 100 mL three-necked flask, tetrabutylammonium bromide (97 mg, 0.3 mmol), and 8 mL of 50% potassium hydroxide aqueous solution. Purge with nitrogen three times, raise the temperature to 70 °C, and react for 3 h. After cooling the reaction solution to room temperature, quench the reaction in water, extract with ethyl acetate, and remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:EA = 10:1 (v / v)) to give approximately 982 mg of compound 5-2, yield 73.0%. MALDI-TOF-MS: 448.25.

[0074] Synthesis of compound 5-3:

[0075] Compound 5-2 (896 mg, 2 mmol) was accurately weighed and added to a 25 mL three-necked flask. After dissolving in 10 mL of triethyl phosphite, the mixture was reacted in an oil bath preheated to 160 °C for 1 h. Triethyl phosphite was removed by vacuum distillation, followed by purification by column chromatography (PE:EA = 1:2 (volume ratio)) to obtain approximately 871 mg of compound 5-3, with a yield of 86.2%. MALDI-TOF-MS: 505.38.

[0076] Synthesis of compound 5-5:

[0077] Compound 5-3 (758 mg, 1.5 mmol) and bis(triphenylphosphine)palladium dichloride (77 mg, 0.11 mmol) were accurately weighed and added to a 50 mL three-necked flask. 20 mL of toluene was added and stirred to dissolve the compound. The mixture was purged with nitrogen three times, and the reaction was stirred for 15 minutes. Then, compound 5-4 (1.14 g, 3.6 mmol) was added, and the reaction was carried out at 90 °C for 3 hours. The reaction solution was cooled to room temperature, quenched with potassium fluoride aqueous solution, stirred for 10 minutes, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. The solution was then purified by column chromatography (PE:DCM = 1:3 (v / v)) to give approximately 467 mg of compound 5-5, with a yield of 77.9%. MALDI-TOF-MS: 399.55.

[0078] Synthesis of compound (5):

[0079] Accurately weigh compound 5-5 (400 mg, 1 mmol) and add it to a 25 mL three-necked flask. Add 10 mL of anhydrous 1,4-dioxane to dissolve it, purge with nitrogen three times, and slowly add 3 mL of trimethylbromosilane. Then raise the temperature to 70 °C and react for 2 h. Remove excess solvent by vacuum distillation, then dissolve the product in methanol and transfer it to a beaker. Add an appropriate amount of water until a solid precipitates, stir for 30 min, and then filter. Approximately 255 mg of compound (5) was obtained, yield: 74.3%. MALDI-TOF-MS: 343.09.

[0080] Example 4: Synthesis of compound (6)

[0081]

[0082] Synthesis of compound 6-1:

[0083] Accurately weigh compound 5-1 (1.02 g, 3 mmol) and compound 4-1 (25.9 g, 120 mmol), and add them to a 100 mL three-necked flask. Add tetrabutylammonium bromide (97 mg, 0.3 mmol), 8 mL of 50% potassium hydroxide aqueous solution, and purge with nitrogen three times. Raise the temperature to 70 °C and react for 3 h. After cooling the reaction solution to room temperature, quench it in water and extract with ethyl acetate. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:EA = 8:1 (v / v)) to give approximately 1.01 g of compound 6-1, yield 70.9%. MALDI-TOF-MS: 476.22.

[0084] Synthesis of compound 6-2:

[0085] Compound 6-1 (952 mg, 2 mmol) was accurately weighed and added to a 25 mL three-necked flask. After dissolving in 10 mL of triethyl phosphite, the mixture was reacted in an oil bath preheated to 160 °C for 1 h. Triethyl phosphite was removed by vacuum distillation, followed by purification by column chromatography (PE:EA = 1:2 (volume ratio)) to obtain approximately 982 mg of compound 6-2, with a yield of 92.1%. MALDI-TOF-MS: 533.34.

[0086] Synthesis of compound 6-3:

[0087] Accurately weigh compound 6-2 (800 mg, 1.5 mmol) and bis(triphenylphosphine)palladium dichloride (77 mg, 0.11 mmol) into a 50 mL three-necked flask. Add 20 mL of toluene and stir to dissolve. Purge with nitrogen three times and stir for 15 minutes. Then add compound 5-4 (1.14 g, 3.6 mmol) and react at 90 °C for 3 h. Cool the reaction solution to room temperature, quench with potassium fluoride aqueous solution, stir for 10 minutes, extract with ethyl acetate, dry to anhydrous magnesium sulfate, remove solvent by vacuum distillation, and then purify by column chromatography (PE:DCM = 1:3 (v / v)) to obtain approximately 485 mg of compound 6-3, yield 75.6%. MALDI-TOF-MS: 427.53.

[0088] Synthesis of compound (6):

[0089] Accurately weigh compound 6-3 (427 mg, 1 mmol) and add it to a 25 mL three-necked flask. Add 10 mL of anhydrous 1,4-dioxane to dissolve it, purge with nitrogen three times, and slowly add 3 mL of trimethylbromosilane. Then raise the temperature to 70 °C and react for 2 h. Remove excess solvent by vacuum distillation, then dissolve the product in methanol and transfer it to a beaker. Add an appropriate amount of water until a solid precipitates, stir for 30 min, and then filter. Approximately 289 mg of compound (6) was obtained, yield: 77.8%. MALDI-TOF-MS: 371.68.

[0090] Example 5: Synthesis of compound (7)

[0091]

[0092] Synthesis of compound 7-2:

[0093] Accurately weigh compound 7-1 (1.07 g, 3 mmol) and compound 3-2 (22.6 g, 120 mmol), and add them to a 100 mL three-necked flask. Add tetrabutylammonium bromide (97 mg, 0.3 mmol), 8 mL of 50% potassium hydroxide aqueous solution, and purge with nitrogen three times. Raise the temperature to 70 °C and react for 3 h. After cooling the reaction solution to room temperature, quench it in water and extract with ethyl acetate. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:EA = 15:1 (v / v)) to give approximately 1.12 g of compound 7-2, yield 80.3%. MALDI-TOF-MS: 464.53.

[0094] Synthesis of compound 7-3:

[0095] Compound 7-2 (929 mg, 2 mmol) was accurately weighed and added to a 25 mL three-necked flask. After dissolving in 10 mL of triethyl phosphite, the mixture was reacted in an oil bath preheated to 160 °C for 1 h. Triethyl phosphite was removed by vacuum distillation, followed by purification by column chromatography (PE:EA = 1:2 (v / v)) to obtain approximately 922 mg of compound 7-3, with a yield of 88.4%. MALDI-TOF-MS: 521.37

[0096] Synthesis of compound 7-4:

[0097] Compound 7-3 (782 mg, 1.5 mmol) and bis(triphenylphosphine)palladium dichloride (77 mg, 0.11 mmol) were accurately weighed and added to a 50 mL three-necked flask. 20 mL of toluene was added and stirred to dissolve the compound. The mixture was purged with nitrogen three times, and the reaction was stirred for 15 minutes. Then, compound 5-4 (1.14 g, 3.6 mmol) was added, and the reaction was carried out at 90 °C for 18 h. The reaction solution was cooled to room temperature, quenched with potassium fluoride aqueous solution, stirred for 10 minutes, and then extracted with ethyl acetate. The solution was dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. The solution was then purified by column chromatography (PE:DCM = 1:3 (v / v)) to give approximately 486 mg of compound 7-4, with a yield of 78.1%. MALDI-TOF-MS: 415.64

[0098] Synthesis of compound (7):

[0099] Accurately weigh compound 7-4 (416 mg, 1 mmol) and add it to a 25 mL three-necked flask. Add 10 mL of anhydrous 1,4-dioxane to dissolve it, purge with nitrogen three times, and slowly add 3 mL of trimethylbromosilane. Then raise the temperature to 70 °C and react for 2 h. Remove excess solvent by vacuum distillation, then dissolve the product in methanol and transfer it to a beaker. Add an appropriate amount of water until a solid precipitates, stir for 30 min, and then filter. Approximately 273 mg of compound (7) was obtained, yield: 75.9%. MALDI-TOF-MS: 359.85.

[0100] Example 6: Synthesis of compound (8)

[0101]

[0102] Synthesis of compound 8-1:

[0103] Accurately weigh compound 7-1 (1.07 g, 3 mmol) and compound 4-1 (25.9 g, 120 mmol), and add them to a 100 mL three-necked flask. Add tetrabutylammonium bromide (97 mg, 0.3 mmol), 8 mL of 50% potassium hydroxide aqueous solution, and purge with nitrogen three times. Raise the temperature to 70 °C and react for 3 h. After cooling the reaction solution to room temperature, quench it in water and extract with ethyl acetate. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:EA = 5:1 (v / v)) to give approximately 1.16 g of compound 8-1, yield 78.4%. MALDI-TOF-MS: 492.32.

[0104] Synthesis of compound 8-2:

[0105] Compound 8-1 (985 mg, 2 mmol) was accurately weighed and added to a 25 mL three-necked flask. After dissolving in 10 mL of triethyl phosphite, the mixture was reacted in an oil bath preheated to 160 °C for 1 h. Triethyl phosphite was removed by vacuum distillation, followed by purification by column chromatography (PE:EA = 1:2 (v / v)) to obtain approximately 904 mg of compound 8-2, with a yield of 82.3%. MALDI-TOF-MS: 549.38

[0106] Synthesis of compound 8-3:

[0107] Compound 8-2 (824 mg, 1.5 mmol) and bis(triphenylphosphine)palladium dichloride (77 mg, 0.11 mmol) were accurately weighed and added to a 50 mL three-necked flask. 20 mL of toluene was added and stirred to dissolve the compound. The mixture was purged with nitrogen three times, and the reaction was stirred for 15 minutes. Then, compound 5-4 (1.14 g, 3.6 mmol) was added, and the reaction was carried out at 90 °C for 18 h. The reaction solution was cooled to room temperature, quenched with potassium fluoride aqueous solution, stirred for 10 minutes, and then extracted with ethyl acetate. The solution was dried over anhydrous magnesium sulfate, and the solvent was removed by vacuum distillation. The solution was then purified by column chromatography (PE:DCM = 1:3 (v / v)) to give approximately 528 mg of compound 8-3, with a yield of 79.3%. MALDI-TOF-MS: 443.78

[0108] Synthesis of compound (8):

[0109] Accurately weigh compound 8-3 (444 mg, 1 mmol) and add it to a 25 mL three-necked flask. Add 10 mL of anhydrous 1,4-dioxane to dissolve it, purge with nitrogen three times, and slowly add 3 mL of trimethylbromosilane. Then raise the temperature to 70 °C and react for 2 h. Remove excess solvent by vacuum distillation, then dissolve the product in methanol and transfer it to a beaker. Add an appropriate amount of water until a solid precipitates, stir for 30 min, and then filter. Approximately 290 mg of compound (8) was obtained, yield: 74.9%. MALDI-TOF-MS: 387.16.

[0110] Fabrication and Characterization of Organic Solar Cell Devices

[0111] Application Example 1

[0112] The glass slide coated with strip-shaped ITO (anode) was ultrasonically cleaned for 20 min in sequence with alkaline solution, deionized water, acetone, isopropanol and ethanol. After cleaning, the ITO glass was dried and treated with ozone for 20 min. Then, the hole-selective layer solution (compound (3) was dissolved in methanol solution with a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The solution was then heated at 110 ℃ for 15 min on a hot stage to induce a crosslinking reaction and obtain the hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. The prepared photoactive layer solution (donor material PM6 and acceptor material BTP-eC9 were dissolved in chloroform at a mass ratio of 1:1.2 with a total concentration of 16 mg / mL and 0.3% CN was added as an additive) was spin-coated on the hole-selective layer at 3000 rpm for 30 seconds. The solution was then placed on a hot stage at 90 ℃ for annealing for 10 min to obtain the photoactive layer. Subsequently, an electron transport layer, made of PDINN material, was spin-coated onto the photoactive layer. Then, a 110 nm thick silver electrode was deposited on the electron transport layer via vacuum evaporation, resulting in the structure shown below. Figure 1 As shown, this is an organic solar cell of ITO / compound (3) / PM6:BTP-eC9 / PDINN / Ag.

[0113] Application Example 2

[0114] The glass plate coated with strip-shaped ITO (anode) was ultrasonically cleaned for 20 min in sequence with alkaline solution, deionized water, acetone, isopropanol and ethanol. After cleaning, the ITO glass was dried and treated with ozone for 20 min. Then, the hole-selective layer solution (compound (4) was dissolved in methanol solution with a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The plate was then heated at 110 ℃ for 15 min to induce a crosslinking reaction and obtain the hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. The prepared photoactive layer solution (donor material PM6 and acceptor material BTP-eC9 were dissolved in chloroform at a mass ratio of 1:1.2 with a total concentration of 16 mg / mL and 0.3% CN was added as an additive) was spin-coated on the hole-selective layer at 3000 rpm for 30 seconds. The plate was then annealed at 90 ℃ for 10 min to obtain the photoactive layer. An electron transport layer was then spin-coated onto the photoactive layer, with the electron transport layer material selected from PDINN. A 110 nm thick silver electrode was then deposited on the electron transport layer by vacuum evaporation to obtain an organic solar cell with the structure ITO / compound (4) / PM6:BTP-eC9 / PDINN / Ag.

[0115] Application Example 3

[0116] Glass slides coated with strip-shaped ITO (anode) were ultrasonically cleaned for 20 min each time with alkaline solution, deionized water, acetone, isopropanol, and ethanol. After cleaning, the ITO glass was dried and then treated with ozone for 20 min. Then, a hole-selective layer solution (compound (5) was dissolved in methanol solution with a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The solution was then heated at 110 °C for 15 min on a hot stage to induce a crosslinking reaction and obtain a hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. The prepared photoactive layer solution (donor material PM6 and acceptor material BTP-eC9 were dissolved in chloroform at a mass ratio of 1:1.2 with a total concentration of 16 mg / mL and 0.3% CN was added as an additive) was spin-coated on the hole-selective layer at 3000 rpm for 30 seconds. The solution was then annealed on a hot stage at 90 °C for 10 min to obtain a photoactive layer. An electron transport layer was then spin-coated onto the photoactive layer, with the electron transport layer material selected from PDINN. A 110 nm thick silver electrode was then deposited on the electron transport layer by vacuum evaporation to obtain an organic solar cell with the structure ITO / compound (5) / PM6:BTP-eC9 / PDINN / Ag.

[0117] Application Example 4

[0118] The glass slide coated with strip-shaped ITO (anode) was ultrasonically cleaned for 20 min in sequence with alkaline solution, deionized water, acetone, isopropanol and ethanol. After cleaning, the ITO glass was dried and treated with ozone for 20 min. Then, the hole-selective layer solution (compound (6) was dissolved in methanol solution with a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The solution was then heated at 110 ℃ for 15 min on a hot stage to induce a crosslinking reaction and obtain the hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. The prepared photoactive layer solution (donor material PM6 and acceptor material BTP-eC9 were dissolved in chloroform at a mass ratio of 1:1.2 with a total concentration of 16 mg / mL and 0.3% CN was added as an additive) was spin-coated on the hole-selective layer at 3000 rpm for 30 seconds. The solution was then annealed on a hot stage at 90 ℃ for 10 min to obtain the photoactive layer. An electron transport layer was then spin-coated onto the photoactive layer, with the electron transport layer material selected from PDINN. A 110 nm thick silver electrode was then deposited on the electron transport layer by vacuum evaporation to obtain an organic solar cell with the structure ITO / compound (6) / PM6:BTP-eC9 / PDINN / Ag.

[0119] Application Example 5

[0120] The glass slide coated with strip-shaped ITO (anode) was ultrasonically cleaned for 20 min in sequence with alkaline solution, deionized water, acetone, isopropanol and ethanol. After cleaning, the ITO glass was dried and treated with ozone for 20 min. Then, the hole-selective layer solution (compound (7) was dissolved in methanol solution with a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The solution was then heated at 110 ℃ for 15 min on a hot stage to induce a crosslinking reaction and obtain the hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. The prepared photoactive layer solution (donor material PM6 and acceptor material BTP-eC9 were dissolved in chloroform at a mass ratio of 1:1.2 with a total concentration of 16 mg / mL and 0.3% CN was added as an additive) was spin-coated on the hole-selective layer at 3000 rpm for 30 seconds. The solution was then placed on a hot stage at 90 ℃ for annealing for 10 min to obtain the photoactive layer. An electron transport layer was then spin-coated onto the photoactive layer, with the electron transport layer material selected from PDINN. A 110 nm thick silver electrode was then deposited on the electron transport layer by vacuum evaporation to obtain an organic solar cell with the structure ITO / compound (7) / PM6:BTP-eC9 / PDINN / Ag.

[0121] Application Example 6

[0122] The glass slide coated with strip-shaped ITO (anode) was ultrasonically cleaned for 20 min in sequence with alkaline solution, deionized water, acetone, isopropanol and ethanol. After cleaning, the ITO glass was dried and treated with ozone for 20 min. Then, the hole-selective layer solution (compound (8) was dissolved in methanol solution with a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The solution was then heated at 110 °C for 15 min on a hot stage to induce a crosslinking reaction and obtain the hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. The prepared photoactive layer solution (donor material PM6 and acceptor material BTP-eC9 were dissolved in chloroform at a mass ratio of 1:1.2 with a total concentration of 16 mg / mL and 0.3% CN was added as an additive) was spin-coated on the hole-selective layer at 3000 rpm for 30 seconds. The solution was then placed on a hot stage at 90 °C for annealing for 10 min to obtain the photoactive layer. An electron transport layer was then spin-coated onto the photoactive layer, with the electron transport layer material selected from PDINN. A 110 nm thick silver electrode was then deposited on the electron transport layer by vacuum evaporation to obtain an organic solar cell with the structure ITO / compound (8) / PM6:BTP-eC9 / PDINN / Ag.

[0123] Comparative Application Example 1

[0124] Glass slides coated with strip-shaped ITO (anode) were sequentially ultrasonicated for 20 min each with alkaline solution, deionized water, acetone, isopropanol, and ethanol. After cleaning, the ITO glass was dried and then treated with ozone for 20 min. Subsequently, a hole-selective layer solution (containing compound (Ref) dissolved in methanol solution at a concentration of 0.2 mg / mL) was spin-coated at 2500 rpm for 20 seconds. The solution was then annealed at 80 °C for 10 min on a hot stage to obtain the hole-selective layer. The device was then transferred to a glove box under a nitrogen atmosphere. A prepared photoactive layer solution (containing donor material PM6 and acceptor material BTP-eC9 dissolved in chloroform at a mass ratio of 1:1.2, with a total concentration of 16 mg / mL, and 0.3% CN added by volume as an additive) was spin-coated onto the hole-selective layer at 3000 rpm for 30 seconds. The solution was then annealed at 90 °C for 10 min to obtain the photoactive layer. An electron transport layer, made of PDINN, was then spin-coated onto the photoactive layer. A 110 nm thick silver electrode was then deposited on the electron transport layer by vacuum evaporation to obtain an organic solar cell with the structure ITO / compound (Ref) / PM6:BTP-eC9 / PDINN / Ag.

[0125]

[0126] The organic solar cell device was tested under sunlight. T80 means that the organic solar cell device was placed in an N2 glove box and continuously illuminated with an LED light source. A multi-channel solar cell degradation test system was used to apply the load corresponding to the mpp (maximum power point) at both ends of the device to keep it in continuous operation. The device performance was measured every 10 minutes. The time required for the photoelectric conversion efficiency of the device to drop to 80% of its initial value was measured (T80). For details, please refer to Table 1.

[0127] Table 1. T80 data for different organic solar cells in application examples.

[0128] Serial Number Hole transport materials T80(h) Application Example 1 Compound (3) 395 Application Example 2 Compound (4) 356 Application Example 3 Compound (5) 349 Application Example 4 Compound (6) 366 Application Example 5 Compound (7) 346 Application Example 6 Compound (8) 371 Comparative Application Example 1 Compound (Ref) 167

[0129] As can be seen from the data in Table 1, the vinyl-containing hole transport material according to the present invention can form a uniform and stable film through cross-linking. Compared with the device prepared by the vinyl-free hole transport material in Comparative Example 1, its device lifetime T80 is significantly improved. Figure 2 The T80 curves of Application Example 1 (compound (3)) and Comparative Application Example 1 (compound (Ref)) also show that the battery prepared by the self-assembled material containing vinyl groups of the present invention has higher photoelectric performance stability and longer device life.

[0130] The above embodiments further illustrate the content of this application, but should not be construed as limiting this application. Modifications and substitutions made to the methods, steps, or conditions of this application without departing from the spirit and substance of this application are all within the scope of this application. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

Claims

1. A self-assembling material containing vinyl groups, characterized in that, The self-assembly material has the structure shown in formula (I): in: n is selected from 1, 2, or 3; -Z- is selected from single bond, -O-, or -S-.

2. The vinyl-containing self-assembly material according to claim 1, characterized in that, n is selected from 1 or 3.

3. The vinyl-containing self-assembly material according to claim 1, characterized in that, The self-assembly material is selected from any one of the following structures:

4. An organic solar cell, said organic solar cell comprising at least one hole-selective layer, characterized in that, The hole selection layer material includes the vinyl-containing self-assembly material as described in any one of claims 1-3.

5. An organic solar cell, said organic solar cell comprising, from bottom to top, an anode layer, a hole-selective layer, a photoactive layer, an electron transport layer, and a cathode layer, characterized in that, The material of the hole selection layer is selected from the vinyl-containing self-assembly material according to any one of claims 1-3.

6. The organic solar cell according to claim 5, characterized in that, The material of the anode layer is selected from FTO or ITO; The photoactive layer comprises a donor material and an acceptor material. The donor material is preferably one or more selected from PBDB-T, PM6, PM7, D18, D18-Cl, PBQx-Cl, and PTQ10, and the acceptor material is selected from Y6, L8-BO, N3, BTP-eC9, and PC. 61 BM, PC 71 One or more of BM; The material of the electron transport layer is selected from one or more of PDINN, PDINO, PFN-Br, PNDIT-F3N-Br, or PNDIT-F3N; The cathode layer material is selected from one or more alloys of zinc, silver, aluminum, gold, and nickel.

7. A method for preparing an organic solar cell, characterized in that, Including the following steps: Step 1: Clean the conductive glass containing the anode layer; Step 2: Dissolve the vinyl-containing self-assembly material according to any one of claims 1-3 in an organic solvent to prepare a hole-selective layer solution, uniformly spin-coat the hole-selective layer solution onto a conductive glass containing an anode layer, and allow it to stand at 100-150°C for 5-20 minutes to obtain a hole-selective layer. Step 3: Prepare a photoactive layer by spin-coating a photoactive material onto the surface of the hole selection layer under an inert atmosphere, followed by annealing. Step 4: Spin-coat the electron transport layer material onto the photoactive layer to obtain the electron transport layer; Step 5: In a vacuum environment, cathode material is deposited on the surface of the electron transport layer to obtain a cathode layer, which is then encapsulated to obtain the organic solar cell.

8. The application of the organic solar cell according to any one of claims 4-6 in automotive, building or Internet of Things devices.

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