Chlorinated heterocyclic aromatic imide n-type semiconductor material, method for preparing same, and use thereof

Abstract

The application discloses a chlorinated heterocyclic aromatic imide-based n-type semiconductor material and a preparation method and application thereof, and relates to the technical field of organic semiconductors. The structural formula of the chlorinated heterocyclic aromatic imide-based n-type semiconductor material is shown in the following formula: wherein X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is one of a single bond, a C2-C60 alkenyl group and a C3-C60 heterocyclic aromatic hydrocarbon; and n in the structural formula is a positive integer. The chlorinated heterocyclic aromatic imide-based n-type semiconductor material provided by the application takes a heterocyclic aromatic imide as a matrix, has excellent solubility and a good skeleton planar structure, and the introduction of chlorine atoms deepens the electronegativity of the heterocyclic aromatic imide-based n-type semiconductor material, so that the LUMO energy level of the n-type semiconductor material is lower and the photoelectric property is more excellent, thereby exhibiting good application potential in organic photoelectric devices.

Description

Technical Field

[0001] This invention relates to the field of organic semiconductor technology, and in particular to chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor materials, their preparation methods, and applications. Background Technology

[0002] Currently, organic conjugated polymer semiconductor materials have attracted widespread attention due to their advantages such as light weight, solution processability, easy tunability, and flexibility. Especially in fields such as organic field-effect transistors, organic electrochemical transistors, organic solar cells, organic thermoelectrics, and bioelectronics, p-type (hole-deficient) organic polymer materials have seen significant development in recent years. However, for n-type (electron-deficient) organic polymer semiconductor materials, the introduction of strongly electron-withdrawing groups usually increases the difficulty of material synthesis, and the strong steric hindrance effect brought by these groups themselves has caused the development of n-type materials to lag far behind that of p-type materials. Nevertheless, high-performance n-type polymer semiconductor materials play a crucial role in logic complementary circuits, organic thermoelectrics, and all-polymer solar cells. Therefore, there is an urgent need to develop high-performance n-type polymer semiconductor materials. The key to developing high-performance n-type polymers lies in the design and synthesis of highly electron-deficient building blocks. Currently, naphthalenediimide (NDI), perylenediimide (PDI), and bisthiopheneimide (BTI) are the main building blocks. However, the twisted molecular backbone of NDI and PDI-based polymers limits their electron mobility and absorption in the near-infrared region. Although BTI-based polymers have good planar framework structures, their LUMO (lowest unoccupied molecular orbital) energy level is relatively high (-3.30 eV), which easily leads to p-type characteristics and poor optoelectronic device performance.

[0003] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0004] Based on the shortcomings of existing materials, the purpose of this invention is to provide chlorinated heterocyclic aromatic imide-based n-type semiconductor materials, their preparation methods and applications, aiming to solve the problem that existing n-type semiconductor materials with good planar framework structures have high LUMO energy levels and corresponding poor optoelectronic device performance.

[0005] The technical solution of the present invention is as follows:

[0006] In a first aspect, the present invention provides a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material, wherein the structural formula of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material is:

[0007]

[0008] Where X is an oxygen atom, sulfur atom, or selenium atom; R is an alkyl or alkoxy group; Ar is a single bond, a C2-C60 alkenyl group, or a C3-C60 heterocyclic aromatic hydrocarbon; and n in the structural formula is a positive integer.

[0009] Optionally, R is selected from one of the following groups:

[0010]

[0011] Here, --- indicates the connection site.

[0012] Optionally, Ar is selected from one of the following groups:

[0013]

[0014] Where --- indicates the linking site; R' is a C1-C60 alkyl group.

[0015] A second aspect of the present invention provides a method for preparing the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material as described above, comprising the following steps:

[0016] Will (R″)3Sn-Ar-Sn(R″)3 and a catalyst are mixed and heated under an inert atmosphere to carry out a polymerization reaction, thereby obtaining the chlorinated heterocyclic aromatic imide-based n-type semiconductor material; wherein, X is an oxygen atom, a sulfur atom, or a selenium atom; R is an alkyl or alkoxy group; Ar is a single bond, a C2-C60 alkenyl group, or a C3-C60 heterocyclic aromatic group; and R″ is an alkyl group; or, ... (R″)3Sn-Ar-Sn(R″)3 and the catalyst are mixed and heated under an inert atmosphere to carry out a polymerization reaction to obtain the chlorinated heterocyclic aromatic imide-based n-type semiconductor material; wherein, X is an oxygen atom, sulfur atom or selenium atom; R is an alkyl or alkoxy group; Ar is a single bond, one of C2-C60 alkenyl and C3-C60 heterocyclic aromatic hydrocarbons, and R″ is an alkyl group.

[0017] Optionally, the catalyst comprises tris(dibenzylideneacetone)dipalladium and / or tris(o-methylphenyl)phosphine.

[0018] Optionally, the catalyst accounts for and (R″)3Sn-Ar-Sn(R″)3 total moles of 1% to 13%;

[0019] Or, the catalyst accounts for The total number of moles of (R″)3Sn-Ar-Sn(R″)3 is 1% to 13%.

[0020] Optionally, The preparation method includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error The compound is dehydrated in an anhydride and then amination reaction is carried out with R-NH2 to obtain... Wherein, R is an alkyl or alkoxy group.

[0021] Optionally, The preparation method includes the following steps: [The text abruptly ends here, likely due to an incomplete sentence or a formatting error Reaction with a brominating reagent yields

[0022] Wherein, R is an alkyl or alkoxy group.

[0023] A third aspect of the present invention provides the application of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material of the present invention as described above and / or the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material prepared by the preparation method of the present invention as described above in organic optoelectronic devices.

[0024] Optionally, the organic optoelectronic device includes an organic field-effect transistor, an organic electrochemical transistor, an organic thermoelectric device, or an organic solar cell.

[0025] Beneficial effects: The chlorinated heterocyclic aromatic imide-based n-type semiconductor material provided by this invention uses heterocyclic aromatic imide as the matrix. It has excellent solubility and a good framework planar structure. The introduction of chlorine atoms deepens the electrolytic deficiency of the heterocyclic aromatic imide-based n-type semiconductor material, resulting in a lower LUMO energy level and better photoelectric properties. Therefore, it shows good application potential in organic optoelectronic devices (such as organic solar cells, organic field-effect transistors, organic electrochemical transistors, or organic thermoelectric devices). Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the preparation process of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material in this invention.

[0027] Figure 2 The image shows the hydrogen nuclear magnetic resonance spectrum of compound 9 prepared in Example 1.

[0028] Figure 3 The image shows the carbon NMR spectrum of compound 9 prepared in Example 1.

[0029] Figure 4 The image shows the 1H NMR spectrum of compound 14 prepared in Example 1.

[0030] Figure 5 The image shows the carbon NMR spectrum of compound 14 prepared in Example 1.

[0031] Figure 6 The image shows the 1H NMR spectrum of P(ClBTI-BTI) prepared in Example 1.

[0032] Figure 7 The image shows the 1H NMR spectrum of P(ClBTI2-T) prepared in Example 1.

[0033] Figure 8 The image shows the 1H NMR spectrum of P(ClBTI2-BTI) prepared in Example 1.

[0034] Figure 9 The UV-Vis spectra of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) prepared in Example 1 in solution are shown.

[0035] Figure 10 The images show the UV-Vis spectra of the thin films P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) prepared in Example 1.

[0036] Figure 11 The cyclic voltammograms are for P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) prepared in Example 1.

[0037] Figure 12 The graph shows the transfer curve of an organic field-effect transistor with P(ClBTI-BTI) as the active layer prepared in Example 1.

[0038] Figure 13 The graph shows the transfer curve of an organic field-effect transistor with P(ClBTI2-T) as the active layer prepared in Example 1.

[0039] Figure 14 The graph shows the transfer curve of an organic field-effect transistor with P(ClBTI2-BTI) as the active layer prepared in Example 1.

[0040] Figure 15 The image shows the current-voltage curves of organic solar cells with P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) as active layers prepared in Example 1. Detailed Implementation

[0041] This invention provides chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor materials, their preparation methods, and applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0043] This invention provides a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material, wherein the structural formula of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material is as follows:

[0044]

[0045] Wherein, X is an oxygen atom, sulfur atom, or selenium atom (in this invention, X in different structural formulas is always an oxygen atom, sulfur atom, or selenium atom, and its meaning will not be repeated when X appears again below); R is an alkyl or alkoxy group (in this invention, R in different structural formulas is always an alkyl or alkoxy group, and its meaning will not be repeated when R appears again below); Ar is a single bond, a C2-C60 alkenyl group, or a C3-C60 heterocyclic aromatic hydrocarbon (in this invention, Ar in different structures is always a single bond, a C2-C60 alkenyl group, or a C3-C60 heterocyclic aromatic hydrocarbon, and its meaning will not be repeated when Ar appears again below); n in the structural formula is a positive integer (n is the degree of polymerization, ranging from 1 to 50, for example, n is 1, 2, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, or 50, etc.).

[0046] The chlorinated heterocyclic aromatic imide-based n-type semiconductor material provided in this invention has good solubility, a good planar framework structure, and superior photoelectric properties. Specifically, it uses a heterocyclic aromatic imide with excellent solubility and a good planar framework structure as a matrix. By introducing chlorine atoms, the electronegativity of the heterocyclic aromatic imide-based n-type semiconductor material is enhanced, resulting in a lower LUMO energy level and superior photoelectric properties in the prepared n-type semiconductor material. This demonstrates excellent application potential in organic optoelectronic devices (such as organic solar cells, organic field-effect transistors, organic electrochemical transistors, or organic thermoelectric devices).

[0047] In this embodiment of the invention, R is an alkyl or alkoxy group to ensure that the semiconductor material can be processed in solution, and Ar is selected from the above groups to enable the control of the photoelectric properties of the semiconductor material.

[0048] In some embodiments, R is selected from one of the following groups:

[0049]

[0050] Here, --- indicates the connection site.

[0051] In some embodiments, Ar is selected from one of the following groups:

[0052]

[0053] Wherein, --- indicates the linking site; R' is a C1-C60 alkyl (in this invention, R' in different structural formulas is all C1-C60 alkyl, and its meaning will not be repeated below when R' appears again); specifically, it can be a C1-C60 straight-chain alkyl (such as methyl, ethyl, propyl, etc.) or a C1-C60 cross-chain alkyl.

[0054] In some embodiments, the chemical structural formula of the chlorinated heterocyclic aromatic imide-based n-type polymer semiconductor material is one of the following structural formulas, but is not limited thereto:

[0055]

[0056] This invention also provides a method for preparing the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material as described above, wherein, as Figure 1 As shown, for Its preparation method includes the following steps:

[0057] S1, will (R″)3Sn-Ar-Sn(R″)3 and the catalyst are mixed and heated under an inert atmosphere to carry out a polymerization reaction to obtain the chlorinated heterocyclic aromatic imide-based n-type semiconductor material; wherein, R″ is an alkyl group (such as methyl, ethyl, propyl or butyl, etc. In this invention, R″ involved in different structural formulas are all alkyl groups, and its meaning will not be repeated when R″ appears again below).

[0058] for Its preparation method includes the following steps:

[0059] S2, will (R″)3Sn-Ar-Sn(R″)3 and the catalyst are mixed and heated under an inert atmosphere to carry out a polymerization reaction, thereby obtaining the chlorinated heterocyclic aromatic imide-based n-type semiconductor material.

[0060] The preparation method provided in this invention is simple and efficient. Specifically, the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material is prepared via a Stille coupling reaction. First, using a heterocyclic aromatic hydrocarbon imide with excellent solubility and a good planar framework structure as the matrix, the electronegativity of the heterocyclic aromatic hydrocarbon imide is further enhanced by the introduction of electronegative chlorine atoms. This results in an n-type semiconductor material with a lower LUMO energy level and superior photoelectric properties, thus exhibiting excellent application potential in organic optoelectronic devices (such as organic solar cells, organic field-effect transistors, organic electrochemical transistors, or organic thermoelectric devices).

[0061] In steps S1 and S2, in some embodiments, the following steps are further included after the polymerization reaction:

[0062] After the reaction solution is cooled following the polymerization reaction, it is filtered and extracted (e.g., by Soxhlet extraction) to obtain the chlorinated heterocyclic aromatic imide-based n-type semiconductor material.

[0063] In some embodiments, the catalyst comprises, but is not limited to, tris(dibenzylacetone)dipalladium and / or tris(o-methylphenyl)phosphine.

[0064] In some embodiments, the catalyst accounts for The catalyst comprises 1% to 13% of the total molar amount of (R″)3Sn-Ar-Sn(R″)3 (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, or 13%, etc.). The total number of moles of (R″)3Sn-Ar-Sn(R″)3 is 1% to 13% (e.g., it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12% or 13%, etc.).

[0065] In step S1, such as Figure 1 As shown, in some implementations, The preparation method includes the following steps:

[0066] S11, will The compound is dehydrated in an acid anhydride (specifically, acetic anhydride), and then subjected to an amination reaction with R-NH2 (specifically, this can be carried out under a protective atmosphere) to obtain...

[0067] In step S11, in some embodiments, The preparation method includes the following steps:

[0068] S111, will A brominating reagent (e.g., Br2) is added to a first solvent (e.g., glacial acetic acid) to react and yield... S112, Removed by a strong base with a strong affinity (such as n-butyllithium, i.e., n-BuLi). The Br at the α-position is then added, followed by the addition of trimethylchlorosilane. After the reaction, the product is obtained. (TMS is trimethylsilyl); S113, removed by strong base-strong affinity reagents (such as n-BuLi). Br in the middle, then add propyl chloroformate, and after the reaction, give S114, will When added to tetrabutylammonium fluoride, the reaction yields... S115, will Reaction with a brominating agent (e.g., N-bromosuccinimide) yields S116, will Through hydrocarbon activation in the presence of a metal catalyst (such as palladium dichloride for phenylcyanide), the following is obtained: S117, will Hydrolysis under alkaline conditions (where the alkali can be potassium hydroxide) yields...

[0069] In step S2, such as Figure 1 As shown, in some implementations, The preparation method includes the following steps:

[0070] S21, will Reacting with a brominating reagent (Br2) yields... In step S21, in some ways, The preparation method includes the following steps:

[0071] S211, will (The preparation method is described in steps S111 to S114 above.) Hydrogen is removed by a strong base weak nucleophilic lithium salt reagent (e.g., lithium bis(trimethylsilylamine), and then the compound is halogenated with a halogenating reagent (e.g., 1,2-dibromotetrachloroethane) under a protective atmosphere to obtain the compound. S212, With tin-modified monomers (e.g.) After being coupled via Stille in the presence of a metal catalyst (e.g., tetraphenylphosphine palladium), the following is obtained: S213, will After hydrolysis under alkaline conditions (the alkali can be potassium hydroxide), the following is obtained: S214, will After dehydration in an acid anhydride compound (e.g., acetic anhydride), followed by amination with R-NH2 under a protective atmosphere, the product is obtained.

[0072] This invention also provides an application of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material described above in organic optoelectronic devices. This invention further provides an application of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material prepared using the preparation method described above in this invention in organic optoelectronic devices. This invention also provides an application of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material described above and the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material prepared using the preparation method described above in this invention in organic optoelectronic devices.

[0073] In some embodiments, the organic optoelectronic device includes an organic field-effect transistor, an organic electrochemical transistor, an organic thermoelectric device, or an organic solar cell.

[0074] The present invention will be further described below through specific embodiments.

[0075] In the following embodiments, "1, 2, 3..." labeled below the structural formula represent "Compound 1, Compound 2, Compound 3". For example, ... Compound 1 is represented as The meanings of the remaining numbers follow the same logic.

[0076] Example 1

[0077] This embodiment provides three types of chlorinated heterocyclic aromatic imide-based n-type semiconductor materials and their preparation methods.

[0078] The structural formulas of the three chlorinated heterocyclic aromatic imide-based n-type semiconductor materials are as follows:

[0079]

[0080] The preparation method of chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor materials includes the following steps:

[0081] (1) Synthesis of compound 2

[0082]

[0083] Following the synthetic route for compounds 1 to 2 described above, compound 1 (20 g, 168.7 mmol) was dissolved in 200 mL of glacial acetic acid (HAc), and then bromine (135 g, Br2) was added. The mixture was reacted overnight at 80 °C. After cooling to room temperature, the mixture was slowly poured into an ice bath of potassium hydroxide solution, followed by extraction three times with dichloromethane. The product was then dried and filtered to obtain a white solid product (compound 2). No purification was required, and the reaction proceeded directly to the next step.

[0084] (2) Synthesis of compound 3

[0085]

[0086] Following the synthetic route of compounds 2 to 3, compound 2 (10 g, 28.1 mmol) was added to a 500 mL dry round-bottom flask. Under an argon atmosphere, the mixture was purged three times using a double-row tube. 250 mL of redistilled anhydrous tetrahydrofuran was added to the flask to dissolve compound 2. The system was then transferred to a cryogenic reaction vessel and gradually cooled to -78 °C. Under argon protection, 2.4 M n-butyllithium (24.6 mL, 59.01 mmol, n-BuLi) was slowly added dropwise to the reaction system. After the addition was complete, the reaction was continued for 1 h. Then, trimethylchlorosilane (6.4 g, 59.01 mmol, TMSCl) was added, and the cryogenic reaction vessel was removed. The reaction was allowed to proceed overnight at room temperature. TLC was used to confirm the completion of the reaction, and 10 mL of methanol was added to quench and terminate the reaction. The product was concentrated under reduced pressure to obtain an oily, viscous crude product. Subsequently, using petroleum ether as the eluent, impurities were separated by silica gel column chromatography to obtain a colorless oily liquid, namely compound 3 (9.4 g, yield 98%).

[0087] (3) Synthesis of compound 4

[0088]

[0089] Following the synthetic route for compounds 3 to 4, compound 3 (10 g, 29.25 mmol) was added to a 500 mL dry round-bottom flask. Under an argon atmosphere, the mixture was purged three times using a double-row tube system. 250 mL of anhydrous tetrahydrofuran was added to the flask to dissolve compound 3. The system was then transferred to a cryogenic reaction vessel and gradually cooled to -78 °C. Under argon protection, 2.4 M n-BuLi (18 mL, 43.88 mmol) was slowly added dropwise to the reaction system. After the addition was complete, the reaction was continued for 1 h. Then, propyl chloroformate (5.38 g, 43.88 mmol, ClCOOC3H7) was added, and the cryogenic reaction vessel was removed. The reaction was allowed to proceed overnight at room temperature. After the reaction was confirmed by TLC, 10 mL of methanol was added to quench and terminate the reaction. The crude product was then concentrated under reduced pressure to obtain an oily, viscous product. Finally, impurities were separated by silica gel column chromatography using petroleum ether as the eluent, and a colorless oily liquid, namely compound 4 (7.35 g, yield 72%), was obtained.

[0090] The proton NMR spectrum data of compound 4 are as follows:

[0091] 1H NMR (400MHz, CDCl3): δ (ppm): 4.31-4.28 (t, 2H, J = 6.8Hz), 1.85-1.80 (dd, 2H, J = 7.2Hz, J = 14.4Hz), 1.07-1.03 (t, 3H, J = 7.2Hz), 0.41 (s, 9H), 0.37 (s, 9H).

[0092] The carbon NMR spectrum data of compound 4 are as follows:

[0093] 13 C NMR (400MHz, CDCl3) δ (ppm): 164.06, 152.52, 139.29, 138.26, 132.72, 66.90, 22.02, 10.57, 1.01, 0.45.

[0094] (4) Synthesis of compound 5

[0095]

[0096] Following the synthetic route for compounds 4 to 5 described above, compound 4 (2 g, 5.73 mmol) was added to a 250 mL dry round-bottom flask, and the mixture was purged three times under an argon atmosphere using a double-row tube. 100 mL of redistilled anhydrous tetrahydrofuran was injected into the flask using a clean long syringe to dissolve compound 4. The system was then transferred to a cryogenic reaction vessel and cooled to -20 °C. A 1 M tetrabutylammonium fluoride (TBAF) tetrahydrofuran solution (11.46 mL, 11.46 mmol of TBAF) was slowly added dropwise to the reaction system. After the addition was complete, the cryogenic reaction vessel was removed, and the reaction was allowed to return to room temperature for 2 h. TLC was used to confirm the end of the reaction. The reaction was then quenched with 2 mL of methanol to terminate the reaction. The crude product was concentrated under reduced pressure to obtain an oily, viscous product. Impurities were then separated by silica gel column chromatography using petroleum ether as the eluent, ultimately yielding a colorless oily liquid, compound 5 (1.1 g, 94% yield).

[0097] The proton NMR spectrum data of compound 5 are as follows:

[0098] 1 H NMR (400MHz, CDCl3): δ (ppm): 8.13-8.12 (d, 1H, J = 3.6Hz), 7.19-7.18 (d, 1H, J = 3. 6Hz), 4.27-4.24 (t, 2H, J = 6.8Hz), 1.80-1.75 (m, 2H), 1.04-1.01 (t, 3H, J = 7.2Hz).

[0099] The carbon NMR spectrum data of compound 5 are as follows:

[0100] 13 C NMR (400MHz, CDCl3) δ (ppm): 161.38, 134.00, 130.10, 126.21, 122.39, 66.56, 22.03, 10.55.

[0101] (5) Synthesis of compound 6

[0102]

[0103] Following the synthetic route for compounds 5 to 6 described above, compound 5 (2 g, 9.77 mmol) was added to a 250 mL dry single-necked flask, followed by the addition of 100 mL of redistilled anhydrous tetrahydrofuran to dissolve it. Then, 20 mL of glacial acetic acid and N-bromosuccinimide (2.09 g, 11.72 mmol, NBS) were added, and the mixture was stirred at room temperature for 48 h. After TLC confirmation of the reaction's completion, an aqueous solution of sodium sulfite was added and stirred at room temperature for half an hour to remove residual NBS. Sodium bicarbonate was then added until the solution pH became alkaline. The aqueous phase was extracted three times with dichloromethane, and the organic phase was further dried to remove residual water. After filtration and concentration under reduced pressure, a brown, oily, viscous crude product was obtained. Impurities were then separated by silica gel column chromatography using pure petroleum ether as the eluent, finally yielding a colorless, oily liquid, compound 6 (2.49 g, 90% yield).

[0104] The proton NMR spectrum of compound 6 is as follows:

[0105] 1 H NMR (400MHz, CDCl3): δ (ppm): 8.13 (s, 1H), 4.28-4.24 (t, 2H, J = 6.8Hz), 1.82-1.73 (m, 2H), 1.04-1.00 (t, 3H, J = 7.2Hz).

[0106] The carbon NMR spectrum data of compound 6 are as follows:

[0107] 13 C NMR (400MHz, CDCl3) δ (ppm): 160.47, 133.48, 130.29, 127.37, 111.23, 66.84, 22.00, 10.54.

[0108] (6) Synthesis of Compound 7

[0109]

[0110] Following the synthetic route of compounds 6 to 7, compound 6 (0.3 g, 1.06 mmol) and palladium dichloride phenylcyanide (40 mg, 0.11 mmol, Pd(PhCN)Cl2) were added to a 10 mL single-necked flask. Under an argon atmosphere, the mixture was purged three times using a double-row tube. Then, 4 mL of anhydrous dimethyl sulfoxide (DMSO) was added to the flask using a clean long syringe. After stirring at room temperature for a while, silver fluoride (0.27 g, 2.12 mmol, AgF) was added under argon protection, and the mixture was heated and stirred at 60 °C for 3 h. After the reaction was determined by TLC, the mixture was poured directly into water, and the aqueous phase was repeatedly extracted with ethyl acetate. The organic phase was further washed with brine to completely remove the dimethyl sulfoxide. The mixture was then dried, filtered, and concentrated under reduced pressure to obtain a brown solid crude product. Subsequently, impurities were separated by silica gel column chromatography using a mixture of petroleum ether and dichloromethane (volume ratio of petroleum ether to dichloromethane 5:1) as the eluent, yielding a white solid compound, namely compound 7 (0.24 g, yield 40%).

[0111] The proton NMR spectrum data of compound 7 are as follows:

[0112] 1 H NMR (400MHz, CDCl3): δ (ppm): 4.16-4.13 (t, 4H, J = 6.8Hz), 1.66-1.60 (dd, 4H, J = 6.8Hz, J = 14.0Hz), 0.93-0.89 (t, 6H, J = 7.2Hz).

[0113] The carbon NMR spectrum data of compound 7 are as follows:

[0114] 13 C NMR (400MHz, CDCl3) δ (ppm): 159.61, 155.40, 152.71, 122.36, 95.11, 67.06, 21.75, 10.25.

[0115] (7) Synthesis of compound 8

[0116]

[0117] Following the synthetic route for compounds 7 to 8 described above, compound 7 (0.4 g, 0.71 mmol), KOH (0.2 g, 3.55 mmol), tetrahydrofuran (10 mL, THF), deionized water (5 mL), and ethanol (10 mL, EtOH) were added to a 50 mL single-necked flask and refluxed overnight at 100 °C. After the reaction was complete, the reaction solution was allowed to cool to room temperature and then concentrated under reduced pressure to remove tetrahydrofuran and ethanol. The remaining mixture was cooled to 0 °C, and hydrochloric acid was added to adjust the pH to acidic. A large amount of white solid powder precipitated out. The solid precipitate was then collected by filtration and dried overnight in a vacuum oven to obtain compound 8 (0.34 g, 100% yield).

[0118] (8) Synthesis of compound 9

[0119]

[0120] Following the synthetic route of compounds 8 to 9 described above, acetic anhydride (6 mL, Ac₂O) and compound 8 (0.35 g, 0.73 mmol) were added to a 25 mL single-necked flask under an argon atmosphere, and the mixture was heated (140 °C) and stirred under reflux for 4 h. After the reaction was complete, as the reaction flask gradually returned to room temperature, a solid precipitated out. This solid was directly filtered, and the filter cake was washed with methanol to obtain a light green solid product (no purification required, it can be used directly in the next step, and its structural formula is:

[0121] ).

[0122] 2-Octylateddodecylamine (0.15 g, 0.5 mmol), the above-mentioned light green solid product (0.18 g, 0.38 mmol), and 4-dimethylaminopyridine (61 mg, 0.5 mmol) were added to a 20 mL dry single-necked flask. Under an argon atmosphere, the mixture was purged three times using a double-row tube. Then, 10 mL of anhydrous 1,4-dioxane was added to the flask using a clean long syringe. The mixture was then refluxed at 100 °C overnight. Subsequently, 2 mL of acetic anhydride was added, and the temperature was raised to 140 °C for 3 h. After the reaction was complete, the mixture was concentrated under reduced pressure to obtain an oily viscous liquid. Impurities were then separated by silica gel column chromatography using a mixture of petroleum ether and dichloromethane (volume ratio of petroleum ether to dichloromethane 5:1) as the eluent to obtain a yellow solid compound, compound 9 (0.2 g, yield 71%).

[0123] The proton NMR spectrum of compound 9 is shown below. Figure 2 As shown, the 1H NMR spectrum data of compound 9 are as follows: 1H NMR (400MHz, CDCl3): δ (ppm): 4.11-4.09 (d, 2H, J = 7.2Hz), 1.89 (m, 1H), 1.39-1.25 (m, 32H), 0.91-0.87 (m, 6H).

[0124] The carbon NMR spectrum of compound 9 is shown below. Figure 3 As shown, the carbon NMR spectrum data of compound 9 are as follows: 13 C NMR(400MHz, CDCl3)δ(ppm):161.50,134.78,130.38,129.66,111.90,52.19,36.91, 31.94,31.92,31.52,29.93,29.66,29.58,29.53,29.37,29.32,26.38,22.70,14.14.

[0125] (9) Synthesis of compound 10

[0126]

[0127] Following the synthetic route of compounds 5 to 10 described above, compound 5 (2.21 g, 10.80 mmol) and 1,2-dibromotetrachloroethane (3.52 g, 10.80 mmol) were added to a 200 mL dry round-bottom flask. Under an argon atmosphere, the atmosphere was purged three times using a double-row tube. 60 mL of redistilled anhydrous diethyl ether was injected into the round-bottom flask using a clean long syringe to dissolve compound 5. The system was then transferred to a cryogenic reaction vessel and gradually cooled to -78 °C. Under argon protection, 1 M LiHMDS solution (10.80 mL, 10.80 mmol, lithium di(trimethylsilyl)amino) was added dropwise to the reaction system, and the reaction was continued for 20 min. The cryogenic reaction vessel was then removed, and the reaction was allowed to return to room temperature for 2 h. After the reaction was confirmed by TLC, 2 mL of methanol was added by syringe to quench and terminate the reaction. The mixture was then brought back to room temperature and concentrated under reduced pressure to obtain an oily, viscous crude product. Impurities were separated by silica gel column chromatography, and finally a colorless oily liquid, namely compound 10 (1.1 g, yield 80%), was obtained.

[0128] The proton NMR spectrum data of compound 10 are as follows:

[0129] 1 H NMR (400MHz, CDCl3): δ (ppm): 7.14 (s, 1H), 4.31-4.28 (t, 2H, J = 6.8Hz), 1.83-1.74 (m, 2H), 1.05-1.01 (t, 3H, J = 7.2Hz).

[0130] The carbon NMR spectrum data of compound 10 are as follows:

[0131] 13 C NMR (400MHz, CDCl3) δ (ppm): 161.40, 130.76, 124.97, 122.26, 117.65, 67.37, 21.95, 10.68.

[0132] (10) Synthesis of compound 11:

[0133]

[0134] Following the synthetic route of compounds 10 to 11 described above, compound 10 (0.5 g, 1.76 mmol), ethyl 2,5-bis(trimethyltin)thiophene[3,2-b]thiophene-3,6-dicarboxylate (0.38 g, 0.63 mmol), and tetrakis(triphenylphosphine)palladium (0.1 g, Pd(PPh3)4) were added to a 20 mL microwave-safe reaction tube. The tube was purged three times using a double-row tube under an argon atmosphere. Then, 6 mL of N,N-dimethylformamide (DMF) was added, and the tube was sealed. The microwave-safe reaction tube was placed in a microwave reactor, and the program was set to heat to 140 °C for 3 h. After cooling to room temperature, a black, viscous crude product was obtained by concentration. Then, using dichloromethane as the eluent, impurities were separated by silica gel column chromatography to obtain a gray solid compound, compound 11 (0.18 g, 40% yield).

[0135] The proton NMR spectrum data of compound 11 are as follows:

[0136] 1 H NMR (400MHz, CDCl3): δ (ppm): 7.36 (s, 2H), 4.31-4.26 (m, 4H), 4.11-4.08 (t, 4H, J = 6.8Hz), 1.5 4-1.49 (dd, 4H, J = 6.8Hz, J = 14.0Hz), 1.29-1.25 (t, 6H, J = 7.2Hz), 0.81-0.78 (t, 6H, J = 7.2Hz).

[0137] The carbon NMR spectrum data of compound 11 are as follows:

[0138] 13 C NMR (400MHz, CDCl3) δ (ppm): 161.63, 161.18, 142.91, 138.81, 137.95, 130.48, 126.39, 123.64, 122.95, 66.86, 61.57, 21.71, 13.90, 10.31.

[0139] (11) Synthesis of compound 12:

[0140]

[0141] Following the synthetic route for compounds 11 to 12 described above, compound 11 (0.5 g, 0.73 mmol), KOH (0.48 g, 7.3 mmol), tetrahydrofuran (20 mL, THF), deionized water (5 mL), and ethanol (20 mL, EtOH) were added to a 100 mL round-bottom flask and refluxed overnight at 100 °C. After the reaction was complete, the mixture was concentrated under reduced pressure to obtain a mixed solution. The remaining mixture was cooled to 0 °C, and hydrochloric acid was added to adjust the pH of the solution to acidic. A large amount of white solid powder precipitated out. The solid precipitate was then collected by filtration and dried overnight in a vacuum oven to obtain compound 12 (0.4 g, 100% yield).

[0142] (12) Synthesis of compound 13:

[0143]

[0144] Following the synthetic route of compounds 12 to 13 described above, under an argon atmosphere, compound 12 (0.4 g, 0.73 mmol) and acetic anhydride (6 mL, Ac₂O) were added to a 25 mL round-bottom flask, and the mixture was heated (140 °C) and stirred under reflux for 4 h. After the reaction was complete, upon cooling to room temperature, a solid precipitated out. This solid was directly filtered, and the filter cake was washed with methanol to obtain a light brown solid product (no purification required, it can be used directly in the next step, and its structural formula is:

[0145] ).

[0146] 2-Octylateddodecylamine (0.36 g, 1.2 mmol), the above light brown solid product (0.25 g, 0.48 mmol), and 4-dimethylaminopyridine (0.15 g, 1.2 mmol) were added to a 50 mL reaction flask. Under an argon atmosphere, the atmosphere was purged three times. Then, 15 mL of anhydrous 1,4-dioxane was injected into the reaction flask using a clean long syringe. The mixture was then heated (100 °C) under reflux and stirred overnight. 2 mL of acetic anhydride was added, and the temperature was raised to 140 °C for 3 h. After the reaction was complete, the mixture was concentrated under reduced pressure to obtain a yellow, viscous crude product. Subsequently, impurities were separated by silica gel column chromatography using a mixture of petroleum ether and dichloromethane (volume ratio of petroleum ether to dichloromethane 2:1) as the eluent to obtain a light yellow solid compound, compound 13 (0.5 g, yield 97%).

[0147] The proton NMR spectrum data of compound 13 are as follows:

[0148] 1H NMR (400MHz, CDCl3): δ (ppm): 7.33 (s, 2H), 4.31-4.30 (d, 4H, J = 6.8Hz), 1.94 (m, 2H), 1.36-1.25 (m, 64H), 0.91-0.86 (m, 12H).

[0149] The carbon NMR spectrum data of compound 13 are as follows:

[0150] 13 C NMR (400MHz, CDCl3) δ (ppm): 161.75, 160.56, 140.39, 137.91, 137.52, 129.71, 129.13, 125.09, 122.38, 5 0.04,36.62,31.93,31.92,31.55,30.04,29.68,29.66,29.60,29.55,29.37,29.34,26.34,22.70,14.14.

[0151] (13) Synthesis of compound 14:

[0152]

[0153] Following the synthetic route of compounds 13 to 14 described above, compound 13 (0.3 g, 0.28 mmol) was added to a 50 mL reaction flask, followed by 20 mL of chloroform, excess bromine (0.2 g), and a catalytic amount of ferric chloride (5 mg). The mixture was stirred at room temperature for 5 h. After the reaction was completed by TLC, an aqueous solution of sodium sulfite was added and stirred at room temperature for half an hour to remove residual bromine. The mixture was repeatedly extracted with dichloromethane, and the organic phase was further dried to remove residual water. The product was then filtered and the dichloromethane solvent was removed by rotary evaporation under reduced pressure to obtain a viscous crude product. Impurities were separated by silica gel column chromatography using a mixture of petroleum ether and dichloromethane (volume ratio of petroleum ether to dichloromethane 2:1) as the eluent to obtain an orange solid compound, compound 14 (0.34 g, yield 98%).

[0154] The proton NMR spectrum of compound 14 is shown below. Figure 4 As shown, the 1H NMR spectrum data of compound 14 are as follows: 1 H NMR (400MHz, CDCl3): δ (ppm): 4.30-4.29 (d, 4H, J = 6.8Hz), 1.91 (m, 2H), 1.35-1.25 (m, 64H), 0.91-0.87 (m, 12H).

[0155] The carbon NMR spectrum of compound 14 is shown below. Figure 5As shown, the carbon NMR spectrum data of compound 14 are as follows: 13 C NMR (400MHz, CDCl3) δ (ppm): 161.15, 160.30, 139.48, 138.11, 137.17, 130.75, 129.25, 125.18, 112.6 4,50.26,36.63,31.94,31.54,30.03,29.70,29.68,29.62,29.58,29.39,29.36,26.32,22.71,14.15.

[0156] (14) Synthesis of P(ClBTI-BTI):

[0157]

[0158] Following the synthetic route of reacting compound 9 and compound 15 (where Bu in the structural formula is butyl) to obtain P(ClBTI-BTI), compound 9 (0.035 g, 0.047 mmol), compound 15 (0.0515 g, 0.047 mmol), tris(dibenzylacetone)palladium (0.64 mg, 0.0007 mmol, Pd2(dba)3), and tris(o-tolyl)phosphine (1.70 mg, 0.0056 mmol, P(o-tolyl)3) were added to a dry microwave-safe reaction tube. The tube was purged three times using a double-row tube under an argon atmosphere, and then 3 mL of anhydrous toluene was added before sealing. The reaction tube was placed in a microwave reactor, and the program was set to heat to 140 °C for 3 h. After cooling to room temperature, 0.1 mL of 2-butyltin thiophene was added, and the reaction was carried out at 110 °C for 20 min. After returning to room temperature, 0.2 mL of 2-bromothiophene was added, and the reaction was continued at 110 °C for another 20 min. After the reaction was completed, the reaction solution was added dropwise to 80 mL of methanol, and the solid was collected by filtration. The solid was then extracted using a Soxhlet extractor with methanol, acetone, and n-hexane for 15 h each to remove small molecule fragments and residual catalyst. Finally, all the final products extracted with dichloromethane were collected, concentrated under reduced pressure, and then precipitated back into methanol solution. After filtration, P(ClBTI-BTI) was obtained, and its 1H NMR spectrum is shown below. Figure 6 As shown.

[0159] (15) Synthesis of P(ClBTI2-T):

[0160]

[0161] Following the synthetic route of reacting compounds 14 and 16 (where Me in the structural formula represents a methyl group) to obtain P(ClBTI2-T), compounds 14 (0.050 g, 0.0406 mmol), 16 (0.0167 g, 0.0406 mmol), Pd2(dba)3 (0.55 mg, 0.0006 mmol), and P(o-tolyl)3 (1.48 mg, 0.0049 mmol) were added to a dry microwave reaction tube. The tube was purged three times using a double-row tube under an argon atmosphere, followed by the addition of 3 mL of anhydrous toluene, and then the tube was sealed. The microwave reaction tube was placed in a microwave reactor, and the program was set to heat to 140 °C for 3 h. After cooling to room temperature, 0.1 mL of 2-butyltin thiophene was added, and the reaction was carried out at 110 °C for 20 min. After returning to room temperature, 0.2 mL of 2-bromothiophene was added, and the reaction was continued at 110 °C for another 20 min. After the reaction was complete, the reaction solution was added dropwise to 80 mL of methanol, and the solid was collected by filtration. Extraction was then performed using a Soxhlet extractor, with methanol, acetone, and n-hexane each for 15 h to remove small molecular fragments and residual catalyst; followed by dichloromethane extraction for 10 h to further remove low molecular weight fragments. Finally, the final product extracted with trichloromethane was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. After filtration, P(ClBTI2-T) was obtained, and its 1H NMR spectrum is shown below. Figure 7 As shown.

[0162] (16) Synthesis of P(ClBTI2-BTI):

[0163]

[0164] Following the synthetic route of P(ClBTI2-BTI) obtained by reacting compounds 14 and 15 (where Bu in the structural formula is butyl), compounds 14 (0.0584 g, 0.0475 mmol), 15 (0.052 g, 0.0475 mmol), Pd2(dba)3 (0.65 mg, 0.00071 mmol), and P(o-tolyl)3 (1.73 mg, 0.0057 mmol) were added to a dry microwave reaction tube. The tube was purged three times using a double-row tube under an argon atmosphere, followed by the addition of 3 mL of anhydrous toluene, and then the tube was sealed. The microwave reaction tube was placed in a microwave reactor, and the program was set to heat it to 140 °C for 3 h. After cooling to room temperature, 0.1 mL of 2-butyltin thiophene was added, and the reaction was carried out at 110 °C for 20 min. Then, after returning to room temperature, 0.2 mL of 2-bromothiophene was added, and the reaction was continued at 110 °C for another 20 min. After the reaction was complete, the reaction solution was added dropwise to 80 mL of methanol, and the solid was collected by filtration. Extraction was then performed using a Soxhlet extractor, with methanol, acetone, and n-hexane solvents for 15 h each to remove small molecular fragments and residual catalyst. Further extraction with dichloromethane for 10 h was used to remove low molecular weight fragments. Finally, the final product extracted with trichloromethane was collected, concentrated, and precipitated again into a methanol solution. After filtration, P(ClBTI2-BTI) was obtained, and its 1H NMR spectrum is shown below. Figure 8 As shown.

[0165] The performance of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) prepared in Example 1 was tested:

[0166] 1. UV-Vis spectra of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) were measured in solution (chloroform) and thin film forms, respectively. The results are as follows: Figure 9 and Figure 10 As shown. By Figure 9 It can be seen that the maximum absorption peaks of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) in solution are 571, 629, and 602 nm, respectively; from Figure 10 Calculations show that the optical band gaps of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) are 2.00, 1.82, and 1.90 eV, respectively.

[0167] 2. Electrochemical tests were performed on P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI), and the results are as follows: Figure 11 As shown. Analysis Figure 11It can be seen that the LUMO energy levels of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) are -3.50, -3.40, and -3.59 eV, respectively; and the HOMO energy levels of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) are -6.16, -5.90, and -6.12 eV, respectively.

[0168] The LUMO energy levels of the polymers PBTI (different from P(ClBTI-BTI) only in the absence of Cl), P(BTI2-T) (different from P(ClBTI2-T) only in the absence of Cl), and P(BTI2-BTI) (different from P(ClBTI2-BTI) only in the absence of Cl) without the introduction of chlorine atoms are -3.30, -3.30, and -3.50 eV, respectively. In contrast, the introduction of electronegative chlorine atoms effectively lowers the LUMO energy level of the polymer, which is more conducive to achieving unipolar n-type electron transport.

[0169] 3. Using P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) as semiconductor layers, organic field-effect transistors with top-gate bottom contacts were fabricated, and their electron mobility was tested using a Keithley S4200 semiconductor analyzer.

[0170] The organic field-effect transistor fabrication method is as follows:

[0171] The source and drain electrodes (both composed of a 3nm thick Cr layer and a 30nm thick Au layer stacked together) were photolithographically etched on borosilicate glass with intervals. The channel length (L) was 50μm and the channel width (W) was 5mm.

[0172] Subsequently, P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) were dissolved in chlorobenzene and spin-coated onto silicate glass containing source and drain electrodes. The glass was then heated to 120, 150, and 120°C respectively and annealed for 10 minutes to form a semiconductor layer (i.e., an active layer).

[0173] Next, the perfluorinated (1-butenyl vinyl ether) polymer was spin-coated onto the active layer and annealed at 100°C for 20 minutes to form a dielectric layer 400 nm thick.

[0174] Finally, aluminum is vapor-deposited onto the dielectric layer to form a 50nm thick gate, resulting in three types of organic field-effect transistors (the only difference being the material of the active layer, namely P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI)).

[0175] Test results are as follows Figures 12 to 14 The figure shows the transfer curves of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI), respectively. From the figure, the electron mobilities of P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) can be calculated to be 0.013, 0.29, and 0.48 cm⁻¹, respectively. 2 ·V -1 ·s -1 All of them exhibit single n-type charge migration characteristics.

[0176] 4. Using P(ClBTI-BTI), P(ClBTI2-T), and P(ClBTI2-BTI) as active layers, respectively, all polymer solar cells (ITO / PEDOT:PSS / active layer / PDNIT-F3N / Ag) were prepared.

[0177] The first method for preparing an all-polymer solar cell includes the following steps:

[0178] PEDOT:PSS was spin-coated onto ITO glass to form a hole transport layer;

[0179] PM6, PY-IT and P(ClBTI-BTI) were dissolved in o-xylene at a mass ratio of 1:0.95:0.05 and spin-coated onto the hole transport layer to obtain the active layer.

[0180] PDNIT-F3N was dissolved in methanol and spin-coated onto the active layer to form an electron transport layer;

[0181] Ag is vapor-deposited onto the electron transport layer to form the top electrode, resulting in an all-polymer solar cell, denoted as PM6:PY-IT:P(ClBTI-BTI).

[0182] Two other types of all-polymer solar cells were prepared, differing only in the third component material of the active layer, namely, replacing P(ClBTI-BTI) with P(ClBTI2-T) and P(ClBTI2-BTI) respectively. The two all-polymer solar cells are denoted as PM6:PY-IT:P(ClBTI2-T) and PM6:PY-IT:P(ClBTI2-BTI) respectively.

[0183] A control all-polymer solar cell was prepared, which differed from the first all-polymer solar cell only in the material of the active layer. The active layer did not contain P(ClBTI-BTI). The resulting control all-polymer solar cell was designated PM6:PY-IT.

[0184] PM6 is a polymer donor material with the following structural formula: PY-IT is a polymer acceptor material with the following structural formula:

[0185] The current-voltage curve test results of the three fully polymerized solar cells are as follows: Figure 15 As shown, PM6:PY-IT:P(ClBTI-BTI), PM6:PY-IT:P(ClBTI2-T), and PM6:PY-IT:P(ClBTI2-BTI) exhibit high energy conversion efficiencies of 17.27%, 18.24%, and 19.35%, respectively. In contrast, the standard PM6:PY-IT device has an energy conversion efficiency of only 15.84%. It can be observed that as the mobility of the chlorinated polymer material increases, the device efficiency of the corresponding all-polymer solar cell also increases. PM6:PY-IT:P(ClBTI2-BTI) achieves the highest energy conversion efficiency, which is also one of the highest values ​​for all-polymer solar cells currently available.

[0186] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material, characterized in that, The structural formula of the chlorinated heterocyclic aromatic imide-based n-type semiconductor material is: ； Where X is an oxygen atom, sulfur atom, or selenium atom; R is an alkyl or alkoxy group; Ar is... One of them, Indicates the linking site; R' is a C1-C60 alkyl group; n in the structural formula is a positive integer.

2. The chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material according to claim 1, characterized in that, R is selected from one of the following groups: ； in, Indicates the connection site.

3. A method for preparing the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material as described in claim 1, characterized in that, Includes the following steps: Will , The mixture is mixed with a catalyst and heated under an inert atmosphere to carry out a polymerization reaction, thereby obtaining the chlorinated heterocyclic aromatic imide-based n-type semiconductor material; wherein X is an oxygen atom, sulfur atom, or selenium atom; R is an alkyl or alkoxy group; and Ar is a... One of them, where R' is a C1-C60 alkyl group. Indicates the linking site, where R'' represents an alkyl group.

4. The preparation method according to claim 3, characterized in that, The catalyst comprises tris(dibenzylideneacetone)dipalladium and / or tris(o-methylphenyl)phosphine.

5. The preparation method according to claim 3, characterized in that, The catalyst accounts for and 1% to 13% of the total number of moles.

6. The preparation method according to claim 3, characterized in that, The preparation method includes the following steps: Will Reaction with a brominating reagent yields ; Wherein, R is an alkyl or alkoxy group.

7. The application of a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material as described in any one of claims 1-2 and / or a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material prepared by the preparation method described in any one of claims 3-6 in organic optoelectronic devices.

8. The application according to claim 7, characterized in that, The organic optoelectronic devices include organic field-effect transistors, organic electrochemical transistors, organic thermoelectric devices, or organic solar cells.

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