High-mobility near-ultraviolet p-type conjugated polymer, preparation method therefor, and photoelectric use thereof

Abstract

The present invention relates to a high-mobility near-ultraviolet p-type conjugated polymer, a preparation method therefor, and a photoelectric use thereof. The conjugated polymer has significant technical characteristics and industrial application value. The main characteristics of the conjugated polymer comprise: a polymer skeleton consisting of a monocyclic structure, a simple synthesis process and easy scale-up, high hole mobility, and an absorption range concentrated in a near ultraviolet region of 350-580 nm. The preparation method of the present invention comprises: using benzene ring or thiophene monomers containing different substituents as starting materials, performing polymerization reaction under the action of a catalyst, and purifying the resulting polymerization product to obtain a high-mobility near-ultraviolet p-type conjugated polymer. By optimizing the polymerization process, large-scale synthesis of the polymer is further achieved. By means of these characteristics, such materials have broad application prospects in organic solar cells and perovskite solar cells, and are expected to become key materials for promoting the industrialization and development of organic photovoltaic and perovskite photovoltaic technologies.

Description

A class of high-mobility near-ultraviolet p-type conjugated polymers, their preparation methods, and optoelectronic applications Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, and more particularly to a class of high-mobility near-ultraviolet p-type conjugated polymers, their preparation methods, and optoelectronic applications. Background Technology

[0002] Organic optoelectronic materials are a class of semiconductor materials based on a π-conjugated framework, exhibiting structural diversity and tunable performance. By introducing different substituents, their optical properties, molecular orbital energy levels, and charge transport characteristics can be precisely controlled. With the rapid development of the organic electronics industry, organic optoelectronic materials have shown broad application prospects in fields such as organic light-emitting diodes (OLEDs), organic solar cells, organic field-effect transistors (FETs), organic photodetectors, chemical sensors, and perovskite solar cells. Due to their significant scientific value and enormous commercial potential, organic optoelectronic materials have become one of the research hotspots in materials science.

[0003] High-mobility near-ultraviolet conjugated polymers are a class of polymer materials with excellent charge transport properties, particularly suitable for applications such as semi-transparent organic solar cells and perovskite solar cells. These materials must meet the dual requirements of strong absorption in the near-ultraviolet region and high hole mobility. However, existing near-ultraviolet conjugated polymers often fail to achieve both simultaneously. Benzene and its derivatives occupy an important position in organic optoelectronic materials due to their simple synthesis, readily available raw materials, and low cost. The benzene ring, as a strongly aromatic copolymerizing unit, possesses significant electronic localization capabilities, which can effectively modulate the absorption spectrum of polymers into the near-ultraviolet region. By introducing halogen atoms, alkoxy groups, and other substituents onto the benzene ring, molecular aggregation behavior and energy level structure can be further adjusted. Simultaneously, non-covalent interactions (such as F...H–C, O...S) induce molecular planarization, promoting polymer crystallization and increasing hole mobility, thereby enhancing device performance. High-mobility near-ultraviolet conjugated polymers not only have significant scientific research value but also possess enormous potential for industrial applications. Summary of the Invention

[0004] The primary objective of this invention is to provide a class of high-mobility near-ultraviolet p-type conjugated polymers, which have advantages such as wide availability of raw materials, low price, simple synthesis, high yield, and easy preparation of derivative compounds.

[0005] Another object of the present invention is to provide a method for the preparation and scale-up synthesis of the above-mentioned type of high-mobility near-ultraviolet p-type conjugated polymer.

[0006] Another object of the present invention is to provide applications for the aforementioned class of high-mobility near-ultraviolet p-type conjugated polymers. These materials can be widely used in organic photovoltaics and perovskite photovoltaics.

[0007] The object of the present invention can be achieved by the following technical solutions:

[0008] The present invention provides a class of high-mobility near-ultraviolet p-type conjugated polymer materials, which are characterized in that they are shown as in Formula I:

[0009] Among them, A-J are fluorine atoms or hydrogen atoms, and the number of fluorine atoms is a natural number between 0 and 10; X is selected from oxygen, sulfur, and selenium atoms, and X may be the same or different; Y is selected from oxygen or sulfur atoms, and Y may be the same or different; R represents any one of substituents such as alkyl, acyl, amide, ester, aryl, aralkyl, heteroalkyl containing different heteroatoms or a combination thereof; R is connected to the benzene ring through an oxygen atom or a sulfur atom; n represents a natural number between 5 and 1000.

[0010] A method for preparing the above-mentioned high-mobility near-ultraviolet p-type conjugated polymer provided by the present invention includes the following steps: <000002了]]

[0011] Under the protection of an inert gas, a monomer with a chemical structure as in Formula II and a monomer with a chemical structure as in Formula III are mixed in a molar ratio of n (0 < n ≤ 1), and a palladium catalyst is added for a polymerization reaction. The reaction temperature is 80-120 °C, the reaction time is 1-72 hours, and the stirring rate is 100-3000 revolutions per minute. After the reaction is completed, it is purified by one or more of filtration, column chromatography, Soxhlet extraction or dialysis to obtain the high-mobility near-ultraviolet p-type conjugated polymer material.

[0012] An enlarged synthesis method for preparing the above-mentioned high-mobility near-ultraviolet p-type conjugated polymer provided by the present invention includes the following steps:

[0013] An enlarged synthesis method for preparing the above-mentioned high-mobility near-ultraviolet p-type conjugated polymer provided by the present invention includes the following steps:

[0014] First, calculate the volume of the solvent required for the enlarged synthesis, select a reaction flask with a volume of 1-8 times the required reaction solvent, and select a magnetic stirrer or a stirring rod with a length of one-half to three-fourths of the diameter of the reaction flask. Under the protection of an inert gas, a monomer with a chemical structure as in Formula II and a monomer with a chemical structure as in Formula III are mixed in the reaction flask, and then a polymerization reaction is carried out under the catalysis of a catalyst, and finally the high-mobility near-ultraviolet conjugated polymer material is purified. The catalyst includes a palladium catalyst; the molar ratio of the monomer with a chemical structure as in Formula II to the monomer with a chemical structure as in Formula III is greater than 0 and less than or equal to 1; the reaction temperature of the polymerization reaction is 80-120 °C, the reaction time is 1-72 hours, and the stirring rate is 100-3000 revolutions per minute. Further, the mixing method is physical mixing; the purification method includes one or more of filtration, column chromatography, Soxhlet extraction or dialysis.

[0015] This invention also includes the application of high-mobility near-ultraviolet p-type conjugated polymers in organic and perovskite solar cells, wherein the solar cells comprise the high-mobility near-ultraviolet p-type conjugated polymers provided by this invention. The organic and perovskite solar cells typically include a hole transport layer, an electron transport layer, and an active layer located between the hole transport layer and the electron transport layer. Furthermore, other functional layers, elements, or substrates may be selectively included in the solar cell devices as needed.

[0016] Compared with the prior art, the beneficial effects of the present invention are:

[0017] (1) The preparation method is simple, has a high yield and low cost: The preparation method provided by the present invention has the characteristics of simple process, high yield and low manufacturing cost, and is suitable for industrial production.

[0018] (2) The scale-up synthesis method is simple to operate and has good repeatability: The scale-up synthesis method provided by the present invention is simple to operate, has good repeatability, and is suitable for large-scale production.

[0019] (3) Molecular design optimization: This invention uses benzene ring units with strong aromatic properties as one of the main copolymerization units. By utilizing the strong electronic localization ability of benzene ring units, the absorption spectrum of the polymer is made to approach the near-ultraviolet region. At the same time, by introducing substituent groups on the benzene ring, not only can the polymer skeleton be stabilized, but also the molecular orbital energy levels can be effectively adjusted.

[0020] (4) Application of high-performance organic photovoltaic devices: The high-mobility near-ultraviolet p-type conjugated polymer provided by this invention can be widely used in the field of organic photovoltaics, especially for the preparation of high-performance semi-transparent organic photovoltaic devices.

[0021] (5) Application of high-performance perovskite photovoltaic devices: The high-mobility near-ultraviolet p-type conjugated polymer provided by this invention can be used as a hole transport layer in high-performance perovskite photovoltaic devices, showing excellent photoelectric performance and industrialization potential. Attached Figure Description

[0022] Figure 1 shows the absorption spectra of the polymers shown in Examples 1–11 and Comparative Examples 1–2.

[0023] Figure 2 is a schematic diagram of the chemical structure of L8-BO.

[0024] Figure 3 is a schematic diagram of the structure of a solar cell device based on the polymer material and L8-BO.

[0025] Figure 4 shows the voltage-current density curves of the solar cell based on the polymer material and L8-BO.

[0026] Figure 5 is a schematic diagram of the structure of a semi-transparent organic solar cell device based on polymer P3 and L8-BO as described in Example 3.

[0027] Figure 6 shows the voltage-current density curves of a semi-transparent solar cell based on the polymer material and L8-BO as the active layer.

[0028] Figure 7 shows the average visible light transmittance curve of a semi-transparent solar cell based on the polymer material and L8-BO as the active layer.

[0029] Figure 8 is a schematic diagram of the perovskite solar cell device based on the polymer material.

[0030] Figure 9 shows the voltage-current density curves of the perovskite solar cell based on the polymer material. Detailed Implementation

[0031] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments, but the implementation and protection of the present invention are not limited thereto. It should be noted that any processes not specifically described in detail below are those that can be implemented or understood by those skilled in the art with reference to the prior art.

[0032] The present invention can be practiced using conventional techniques in polymer chemistry within the relevant field. In the following examples, efforts have been made to ensure the accuracy of the figures used (including quantities, temperatures, reaction times, etc.), but some experimental errors and deviations should be considered. Temperatures used in the following examples are expressed in °C, and pressures are at or near atmospheric pressure. All solvents used are of analytical or chromatographic purity, and all reactions are carried out in an inert gas atmosphere. Unless otherwise stated, all reagents are commercially available.

[0033] Example 1

[0034] The following examples illustrate the preparation method of representative conjugated polymers of high-mobility near-ultraviolet conjugated polymers proposed in this invention, but the invention is not limited to the examples given.

[0035] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P1 are shown below:

[0036] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, tris(o-methoxyphenyl)phosphine, terpentine, cesium carbonate, and o-xylene were all purchased from commercial sources.

[0037] Preparation method 1 of polymer P1: Monomers M1 (800.00 mg, 1.33 mmol) and M2 (950.00 mg, 1.33 mmol) were weighed and added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (24.26 mg, 0.03 mmol), ligand tris(o-methylphenyl)phosphine (64.51 mg, 0.21 mmol), and anhydrous o-xylene (50 mL) were added. The mixture was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and trichloromethane. Finally, the obtained chloroform component was concentrated, precipitated again in methanol, filtered and dried to finally obtain 1.03 g of polymer, with a yield of 93%.

[0038] Method 2 for preparing polymer P1: Monomers M3 (368.90 mg, 1.33 mmol) and M5 (950.00 mg, 1.33 mmol) were weighed and added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (48.55 mg, 0.05 mmol), ligands tris(o-methoxyphenyl)phosphine (74.72 mg, 0.21 mmol), pentylene acid (135.37 mg, 1.33 mmol), and cesium carbonate (1.30 g, 3.98 mmol) were added and dissolved in anhydrous o-xylene (50 mL). The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and trichloromethane. Finally, the obtained chloroform component was concentrated, precipitated again in methanol, filtered and dried to obtain 1.10 g of polymer, with a yield of 99%.

[0039] Example 2

[0040] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P2 are shown below:

[0041] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, tris(o-methoxyphenyl)phosphine, terpentine, cesium carbonate, and o-xylene were all purchased from commercial sources.

[0042] Preparation method 1 of polymer P2: Monomers M4 (800.00 mg, 1.25 mmol) and M2 (896.06 mg, 1.25 mmol) were weighed and added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (22.90 mg, 0.03 mmol), ligand tris(o-methylphenyl)phosphine (60.88 mg, 0.20 mmol), and anhydrous o-xylene (50 mL) were added. The mixture was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.03 g of polymer, with a yield of 99%.

[0043] Method 2 for preparing polymer P2: Monomers M5 (368.90 mg, 1.17 mmol) and M2 (841.24 mg, 1.17 mmol) were weighed and added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (42.99 mg, 0.05 mmol), ligands tris(o-methoxyphenyl)phosphine (66.17 mg, 0.19 mmol), tertivalic acid (119.87 mg, 1.17 mmol), and cesium carbonate (1.15 g, 3.52 mmol) were added and dissolved in anhydrous o-xylene (50 mL). The mixture was stirred at 120 °C for 16 hours. After cooling to room temperature, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.00 g of polymer with a yield of 98%.

[0044] Example 3

[0045] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P3 are shown below:

[0046] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, tris(o-methoxyphenyl)phosphine, terpentine, cesium carbonate, and o-xylene were all purchased from commercial sources.

[0047] Preparation method 1 of polymer P3: After weighing monomers M4 (800.00 mg, 1.25 mmol) and M6 (1.04 g, 1.25 mmol), they were added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (22.90 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (60.88 mg, 0.20 mmol) were dissolved in anhydrous o-xylene (50 mL). The mixture was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.13 g of polymer, with a yield of 95%.

[0048] Method 2 for preparing polymer P3: After weighing monomers M5 (368.90 mg, 1.17 mmol) and M6 (927.95 mg, 1.17 mmol), they were added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (42.99 mg, 0.05 mmol), ligands tris(o-methoxyphenyl)phosphine (66.17 mg, 0.19 mmol), terpentine (119.87 mg, 1.17 mmol), and cesium carbonate (1.15 g, 3.52 mmol) were added and dissolved in anhydrous o-xylene (50 mL). The mixture was stirred at 120 °C for 16 hours. After cooling to room temperature, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.12 g of polymer, with a yield of 99%.

[0049] Scale-up synthesis of polymer P3: Example: Scale-up synthesis of polymer P3 was performed using method 1. Under nitrogen protection, Pd2(dba)3 (2.46 mg, 2.7 mmol) and P(o-tol)3 (6.54 mg, 21.5 mmol) were added to a solution of M4 (86.0 g, 134.4 mmol) and M6 (111.6 g, 134.4 mmol) in anhydrous o-xylene (1500 mL) solvent mixture. The reaction time was 48 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2–8 hours, followed by 2-bromothiophene and reacted for 2–8 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2–8 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 120.0 g of polymer, with a yield of 98%.

[0050] Example 4

[0051] As an example, the structural formula and synthesis method of comparative example P4 are shown below:

[0052] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0053] Preparation method 1 of polymer P4:

[0054] Monomers M7 (800.00 mg, 1.41 mmol) and M2 (1.01 g, 1.41 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (25.80 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (68.59 mg, 0.23 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.13 g of polymer, with a yield of 99%.

[0055] Example 5

[0056] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P5 are shown below:

[0057] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0058] Preparation method of polymer P5:

[0059] Monomers M8 (800.00 mg, 1.32 mmol) and M9 (985.69 mg, 13.2 mmol) were weighed and added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (24.11 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (64.10 mg, 0.21 mmol) were dissolved in anhydrous o-xylene (50 mL). The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.15 g of polymer, with a yield of 99%.

[0060] Example 6

[0061] As an example, the structural formula and synthesis method of Comparative Example P6 are shown below:

[0062] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0063] Preparation method of polymer P6:

[0064] Monomers M8 (800.00 mg, 1.32 mmol) and M2 (936.41 mg, 1.32 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (24.11 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (64.10 mg, 0.21 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.10 g of polymer, with a yield of 99%.

[0065] Example 7

[0066] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P7 are shown below:

[0067] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0068] Preparation method of polymer P7:

[0069] Monomers M4 (800.00 mg, 1.25 mmol) and M10 (931.02 mg, 1.25 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (22.90 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (60.88 mg, 0.20 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.03 g of polymer, with a yield of 99%.

[0070] Example 8

[0071] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P8 are shown below:

[0072] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0073] Preparation method of polymer P8:

[0074] Monomers M1 (800.00 mg, 1.32 mmol) and M10 (986.49 mg, 1.32 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (24.26 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (64.51 mg, 0.21 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.14 g of polymer, with a yield of 99%.

[0075] Example 9

[0076] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P9 are shown below:

[0077] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0078] Preparation method of polymer P9:

[0079] Monomers M12 (800.00 mg, 1.32 mmol) and M2 (949.44 mg, 1.32 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (26.49 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (64.51 mg, 0.21 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.10 g of polymer, with a yield of 99%.

[0080] Example 10

[0081] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P10 are shown below:

[0082] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0083] Preparation method of polymer P10:

[0084] Monomers M12 (800.00 mg, 1.15 mmol) and M2 (821.78 mg, 1.15 mmol) were weighed and added to a polymerization tube. In a glove box, catalyst Pd2(dba)3 (21.00 mg, 0.02 mmol) and ligand tris(o-methylphenyl)phosphine (55.83 mg, 0.18 mmol) were dissolved in anhydrous o-xylene (50 mL). The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.07 g of polymer, with a yield of 99%.

[0085] Example 11

[0086] As an example, the structural formula and synthesis method of the high-mobility near-ultraviolet conjugated polymer P11 are shown below:

[0087] In this embodiment, the catalysts tris(dibenzylideneacetone)palladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0088] Preparation method of polymer P11:

[0089] Monomers M13 (800.00 mg, 1.09 mmol) and M2 (781.49 mg, 1.09 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (19.97 mg, 0.02 mmol) and ligand tris(o-methylphenyl)phosphine (53.10 mg, 0.17 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling, the precipitate was collected in methanol and then placed in a Soxhlet extractor. Extraction was performed sequentially using methanol, acetone, n-hexane, dichloromethane, and chloroform. The chloroform fraction was then concentrated, precipitated again in methanol, filtered, and dried to obtain 1.03 g of polymer, with a yield of 98%.

[0090] Comparative Example 1

[0091] In contrast, a comparative example Q1 was designed with alkyl side chains directly connected to benzene ring units. Due to the lack of O···S non-covalent interactions, Q1 exhibits poor polymer backbone planarity and low hole mobility. The structural formula and synthetic method of Q1 are shown below:

[0092] In this comparative example, the catalysts tris(dibenzylideneacetone)dipalladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0093] Preparation method of polymer Q1:

[0094] Monomers M4 (800.00 mg, 1.41 mmol) and M14 (1.00 g, 1.41 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (25.80 mg, 0.03 mmol) and ligand tris(o-methylphenyl)phosphine (68.59 mg, 0.23 mmol) were dissolved in anhydrous o-xylene (50 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling to room temperature, the polymer was precipitated in methanol and then extracted in a Soxhlet extractor with methanol, acetone, n-hexane, and chloroform, respectively. The final product was concentrated, precipitated, filtered, and dried to obtain 1.01 g of polymer (90% yield).

[0095] Comparative Example 2

[0096] In contrast, a polymer Q2 containing a difluorobenzothiadiazole unit was designed. The difluorobenzothiadiazole unit exhibits strong quinone characteristics, resulting in a significant red shift in the absorption range of Q2, essentially covering the entire visible light spectrum, which is detrimental to improving the average visible light transmittance. The structural formula and synthesis method of Q2 are shown below:

[0097] In this comparative example, the catalysts tris(dibenzylideneacetone)dipalladium, tris(o-methylphenyl)phosphine, and o-xylene were all purchased from commercial sources.

[0098] Preparation method of polymer Q2:

[0099] Monomers M15 (93.00 mg, 0.14 mmol) and M2 (89.16 mg, 0.14 mmol) were weighed and added to a polymerization tube. Catalyst Pd2(dba)3 (2.57 mg, 0.003 mmol) and ligand tris(o-methylphenyl)phosphine (6.84 mg, 0.02 mmol) were dissolved in anhydrous o-xylene (3 mL) in a glove box. The reaction was stirred at 120 °C for 16 hours. After cooling to room temperature, 2-(tributyltin)thiophene was added and reacted for 2 hours, followed by 2-bromothiophene and reacted for 2 hours. Finally, a solution of N,N-diethylaminodithioate trihydrate was added and reacted for 2 hours. After cooling to room temperature, the polymer was precipitated in methanol and placed in a Soxhlet extractor for extraction with methanol, acetone, n-hexane, and chloroform, respectively. The final product was concentrated, precipitated, filtered, and dried to obtain 112 mg of polymer (90% yield).

[0100] Example 11

[0101] As an example, organic solar cell devices were fabricated using the high-mobility near-ultraviolet conjugated polymer P1–P10 from the above embodiments.

[0102] (1) Specific fabrication process of opaque devices:

[0103] A 30 nm layer of PEDOT:PSS was spin-coated onto ITO, followed by a 120 nm blended active layer. PFN-Br served as the cathode interface layer, and then 100 nm of Ag was deposited by evaporation, thus completing the fabrication of the polymer solar cell device. The polymer solar cell, from bottom to top, comprises a transparent conductive anode, an anode interface layer, a donor-acceptor active layer, a cathode interface layer, and a cathode, as shown in Figure 2. Voltage-current density curve tests were performed (see Figure 3). The test data are shown in Table 1 below, which presents the performance parameters of the polymer solar cell device using ITO / PEDOT:PSS / Active layer / PFN-Br / Ag.

[0104] As shown in Table 1, the positive solar cell device using the high-mobility near-ultraviolet conjugated polymer P1 described in Example 1 of this invention as the donor material and L8-BO as the acceptor material achieved a power conversion efficiency of 18.11%; the positive solar cell device using the high-mobility near-ultraviolet conjugated polymer P2 described in Example 2 of this invention as the donor material and L8-BO as the acceptor material achieved a power conversion efficiency of 18.75%. Compared with the high-performance donor materials PM6 (Sci. China Chem., 2020, 63, 325, Joule, 2019, 3, 3020) and D18 (Sci. Bull., 2020, 65, 272) reported in the literature, the polymers of the embodiments of this invention, while maintaining comparable efficiency, also have advantages such as novel structure, simple synthesis, high yield, scalability, and green preparation.

[0105] Table 1 Device parameters of organic solar cells

[0106] As shown in Table 1, the efficiency of the organic solar cell device based on the comparative polymer Q1 is only 8.01%. The alkyl side chain of the comparative polymer Q1 is directly connected to the benzene ring unit. Due to the lack of O…S non-covalent interaction to stabilize the polymer backbone, the thiophene and benzene ring in the Q1 molecule have a large twist angle, poor polymer backbone planarity, and low hole mobility, which is the main reason for the significant reduction in device efficiency.

[0107] Meanwhile, comparative example Q2 (Energy Environ. Sci., 2014, 7, 3040) has a similar polymer backbone and high mobility, thus achieving high short-circuit current density and fill factor in opaque devices. However, due to the strong quinone characteristics of the benzodithiazole unit, the highest occupied molecular orbital energy level shifts upward, resulting in a lower open-circuit voltage for the device. The polymer designed in this invention has a large optical band gap, deep energy levels, and an absorption range close to the near-ultraviolet region. This is beneficial for reducing the absorption of the donor material in the visible light region, thereby improving the average visible light transmittance of the semi-transparent device.

[0108] (2) Specific fabrication process of semi-transparent devices:

[0109] A 20 nm layer of PEDOT:PSS was spin-coated onto ITO, followed by a 100 nm layer of polymer donor and L8-BO blended photoactive layer. PFN-Br served as the cathode interface layer. 12 nm of Ag was then deposited, followed by a 35 nm layer of molybdenum oxide as the photocoupler layer, thus completing the fabrication of the semi-transparent solar cell device. The device structure is shown in Figure 5. Voltage-current density curves and transmittance were tested (see Figures 6–7). Table 2 shows the performance parameters of the semi-transparent organic solar cell device based on ITO / PEDOT:PSS / P:L8-BO / PFN-Br / Ag / MoO3. As shown in Table 2, the embodiments designed in this invention all have large optical band gaps (2.20–2.80 eV), and the corresponding semi-transparent devices can achieve high average visible light transmittance (40–60%) and light utilization (5–6%). In contrast, while Comparative Example Q1 has a larger optical bandgap (2.65 eV), its low mobility prevents it from simultaneously achieving high photoelectric conversion efficiency and average visible light transmittance. Comparative Example Q2, with its absorption range red-shifted to 720 nm and an optical bandgap of 1.72 eV, also fails to achieve high transmittance (23.5%), resulting in lower performance for its semi-transparent photovoltaic device. PM6 (1.80 eV) and D18 (1.95 eV), widely studied in this field, suffer from the same problem; their strong absorption characteristics in the visible light range prevent semi-transparent devices from achieving high average visible light transmittance, ultimately leading to low light utilization. These results demonstrate the high-mobility near-ultraviolet conjugated polymers involved in this patent's work as highly innovative. Their low cost, scalable synthesis, and high transmittance are distinctive features, giving them significant application potential in organic solar cells, particularly semi-transparent organic photovoltaic devices.

[0110] Table 2 Device parameters of semi-transparent organic solar cells

[0111] Example 12

[0112] To verify the performance of the high-mobility near-ultraviolet p-type conjugated polymer provided in this invention as a hole transport material, organic-inorganic lead halide perovskite solar cells were fabricated using the polymer materials of Examples 1–11 and commercially available Poly-TPD (purchased from Aladdin, model P475505-1g) as hole transport layers, respectively, and their photoelectric performance was characterized. The device structure of the perovskite solar cell is: ITO glass / hole transport layer / perovskite photoactive layer / C60 / BCP / metal electrode (gold, silver, copper, aluminum, etc.). In the fabrication process, a 20 nm thick hole transport material (Examples 1–11 or Poly-TPD) was first spin-coated onto the ITO glass; then, a perovskite photoactive layer (material MAPbI3, thickness 300–700 nm) was deposited; next, 5–20 nm of C60 and 5–20 nm of BCP were evaporated as electron transport layers; finally, a 100 nm metal electrode (such as silver or aluminum) was evaporated to complete the device fabrication. The device structure is shown in Figure 8, and the corresponding voltage-current density curve is shown in Figure 9. Table 3 shows a comparison of the key performance parameters of perovskite solar cells using Examples 1–11 and Poly-TPD as the hole transport layer. By comparing the performance parameters of Examples 1–11 and Poly-TPD, the hole transport material provided by this invention shows significant advantages in open-circuit voltage, short-circuit current density, and photoelectric conversion efficiency, fully demonstrating its excellent performance as a hole transport layer in perovskite solar cells.

[0113] Table 3 Device parameters of perovskite solar cells

[0114] The above embodiments are merely preferred embodiments of the present invention and are only used to explain the present invention, not to limit the present invention. Any changes, substitutions, modifications, etc., made by those skilled in the art without departing from the spirit and essence of the present invention should be within the protection scope of the present invention.

Claims

1. A class of high-mobility near-ultraviolet p-type conjugated polymers, characterized in that, Its chemical structure is shown in formula (I): Wherein, A–J are fluorine or hydrogen atoms, and the number of fluorine atoms is a natural number between 0 and 10; X is selected from the same or different oxygen, sulfur, and selenium atoms; Y is selected from the same or different oxygen or sulfur atoms; R represents any one of the substituents of alkyl, acyl, amide, ester, aryl, aralkyl, heteroalkyl containing different heteroatoms, or combinations thereof; Y is connected to R and a benzene ring at both ends; R is selected from any one of the substituents of alkyl, acyl, amide, ester, aryl, aralkyl, heteroalkyl containing heteroatoms, or combinations thereof; n represents a natural number between 5 and 1000.

2. The high-mobility near-ultraviolet p-type conjugated polymer according to claim 1, characterized in that, The conjugated polymer is composed entirely of monocyclic rings connected by carbon-carbon single bonds; there are non-covalent interactions between the monocyclic rings, which include one or more of F…H–C, F…S, O…S, O…Se, and O…H–C.

3. The high-mobility near-ultraviolet p-type conjugated polymer according to claim 1 or 2, characterized in that, The conjugated polymer is any one of the conjugated polymers shown in Formula I-1 to Formula I-16; wherein, R is selected from any one of alkyl, acyl, amide, ester, aryl, aralkyl, heteroalkyl containing heteroatoms or combinations thereof; Y is connected to R and benzene ring at both ends; n is a natural number between 5 and 1000; 4. A method for preparing the high-mobility near-ultraviolet p-type conjugated polymer according to any one of claims 1-3, characterized in that, Includes the following steps: Under inert gas protection, compound II and compound III are mixed and copolymerized in the presence of a catalyst. After purification, a conjugated polymer with the chemical structure of compound I is obtained. In both compound II and compound III, A–J are fluorine or hydrogen atoms, and the number of fluorine atoms is a natural number between 0 and 10. X is selected from oxygen, sulfur, and selenium atoms, and X may be the same or different. Y is selected from oxygen or sulfur atoms, and Y may be the same or different. Z1 in compound II is selected from one of trialkyltinyl, borate ester, and hydrogen (H), and Z2 in compound III is selected from one of hydrogen (H), bromine (Br), and iodine (I); or, Z1 in compound II is selected from one of hydrogen (H), bromine (Br), and iodine (I), and Z2 in compound III is selected from one of trialkyltinyl, borate ester, and hydrogen (H).

5. The preparation method according to claim 4, characterized in that, The solvent is selected from at least one of tetrahydrofuran, toluene, o-xylene, chlorobenzene, and dimethylformamide.

6. The preparation method according to claim 4, characterized in that, The catalyst is selected from one or more of tris(dibenzylacetone)palladium, tetra(triphenylphosphine)palladium, palladium chloride, or palladium acetate; the molar equivalent ratio of the compound of formula II to the compound of formula III is greater than 0 and less than or equal to 1.

7. The preparation method according to claim 4, characterized in that, The amount of compound II added to compound III satisfies the following condition: the molar ratio is between 1:10 and 10:

1.

8. The preparation method according to claim 4, characterized in that, The copolymerization reaction is carried out at a temperature of 80–120°C, for a reaction time of 1–48 hours, and with a stirring rate of 100–1000 rpm; the mixing method is physical mixing; the purification method includes one or more of filtration, column chromatography, Soxhlet extraction, and dialysis.

9. The high-mobility near-ultraviolet p-type conjugated polymer according to any one of claims 1–3 is used in organic photovoltaic or perovskite photovoltaic devices.

10. The application according to claim 9, characterized in that, The photovoltaic device is an organic solar cell or a perovskite solar cell; the cell includes an anode, a cathode, and one or more organic compound layers disposed between the anode and the cathode; the organic compound layer includes at least one of a hole transport layer, an active layer, and an electron transport layer, and at least one of the organic compound layers contains the high-mobility near-ultraviolet p-type conjugated polymer as described in claims 1–3.

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