Chlorinated heterocyclic aromatic imide n-type semiconductor material and preparation method and application thereof

Abstract

The invention discloses a chlorinated heterocyclic aromatic imide n-type semiconductor material as well as a preparation method and application thereof, and relates to the technical field of organic semiconductors. The structural formula of the chlorinated heterocyclic aromatic imide n-type semiconductor material is # imgabs0 #, wherein X is an oxygen atom, a sulfur atom or a selenium atom; r is alkyl or alkoxy; 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. According to the chlorinated heterocyclic aromatic imide n-type semiconductor material provided by the invention, heterocyclic aromatic imide is taken as a matrix and has excellent solubility and a good skeleton plane structure, and introduction of chlorine atoms deepens the power shortage of the heterocyclic aromatic imide n-type semiconductor material, so that the conductivity of the semiconductor material is improved, and the conductivity of the semiconductor material is improved. The LUMO energy level of the n-type semiconductor material is lower, and the photoelectric property is more excellent, so that the n-type semiconductor material shows good application potential in organic photoelectric devices.

Description

Technical Field

[0001] The invention relates to the technical field of organic semiconductors, and in particular to a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material and a preparation method and application thereof. Background Art

[0002] At present, organic conjugated polymer semiconductor materials have attracted widespread attention due to their advantages such as light weight, solution processing, easy control, and flexibility. Especially in the fields of organic field effect transistors, organic electrochemical transistors, organic solar cells, organic thermoelectrics and bioelectronics, p-type (hole) organic polymer materials have made great progress in recent years. As for n-type (electron) organic polymer semiconductor materials, the introduction of strong electron-pulling groups usually leads to an increase in the difficulty of material synthesis, and the strong electron-pulling groups themselves bring about a large steric hindrance effect, which makes the development of n-type materials far behind that of p-type materials. However, high-performance n-type polymer semiconductor materials play a vital role in logic complementary circuits, organic thermoelectrics and all-polymer solar cells. Therefore, it is urgent 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 units. At present, naphthalene diimide (NDI), perylene diimide (PDI) and bithiophene imide (BTI) are mainly used. However, NDI and PDI-based polymers have a distorted molecular skeleton, which limits their electron mobility and absorption in the near-infrared region. For BTI-based polymers, although they have a good planar skeleton structure, their LUMO (lowest unoccupied molecular orbital) energy level is relatively high (-3.30 eV), which easily exhibits p-type characteristics and results in poor performance of optoelectronic devices.

[0003] Therefore, the prior art still needs to be improved and developed. Summary of the invention

[0004] Based on the above-mentioned deficiencies of the existing materials, the purpose of the present invention is to provide a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material and a preparation method and application thereof, aiming to solve the problem that the existing n-type semiconductor materials with a good planar skeleton structure have a high LUMO energy level and the corresponding optoelectronic device performance is poor.

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

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

[0007]

[0008] Wherein, X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is 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.

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

[0010]

[0011] Among them, --- represents the connection site.

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

[0013]

[0014] Wherein, --- represents the connection site; R' is a C1-C60 alkyl group.

[0015] The 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, which comprises the following steps:

[0016] Will (R″)3Sn-Ar-Sn(R″)3 and a catalyst are mixed, heated in an inert atmosphere, and polymerized to obtain the chlorinated heterocyclic aromatic hydrocarbon amide-based n-type semiconductor material; wherein X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is a single bond, a C2-C60 alkenyl group, and a C3-C60 heterocyclic aromatic hydrocarbon; and R″ is an alkyl group; or (R″)3Sn-Ar-Sn(R″)3 and a catalyst are mixed, heated in an inert atmosphere, and polymerized to obtain the chlorinated heterocyclic aromatic hydrocarbon amide-based n-type semiconductor material; wherein X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is a single bond, a C2-C60 alkenyl group, and a C3-C60 heterocyclic aromatic hydrocarbon; 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 1% to 13% of the total molar number of (R″)3Sn-Ar-Sn(R″)3;

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

[0020] Optionally, The preparation method comprises the following steps: Dehydration in anhydride compounds, followed by amination with R-NH2, yields Wherein, R is an alkyl group or an alkoxy group.

[0021] Optionally, The preparation method comprises the following steps: Reaction with bromination reagent to obtain

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

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

[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 hydrocarbon amide-based n-type semiconductor material provided by the present invention uses heterocyclic aromatic hydrocarbon amide as a matrix, has excellent solubility and a good skeleton planar structure, and the introduction of chlorine atoms deepens the electrical deficiency of the heterocyclic aromatic hydrocarbon amide-based n-type semiconductor material, so that the LUMO energy level of the n-type semiconductor material is lower and the photoelectric properties are more excellent, thereby showing good application potential in organic photoelectric devices (such as organic solar cells, organic field effect transistors, organic electrochemical transistors or organic thermoelectric devices, etc.). BRIEF DESCRIPTION OF THE DRAWINGS

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

[0027] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of compound 9 prepared in Example 1.

[0028] Figure 3 This is the carbon NMR spectrum of compound 9 prepared in Example 1.

[0029] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of compound 14 prepared in Example 1.

[0030] Figure 5 This is the carbon NMR spectrum of compound 14 prepared in Example 1.

[0031] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of P(ClBTI-BTI) prepared in Example 1.

[0032] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of P(ClBTI2-T) prepared in Example 1.

[0033] Figure 8 This is the hydrogen nuclear magnetic resonance spectrum of P(ClBTI2-BTI) prepared in Example 1.

[0034] Fig. 9 UV-visible spectra of P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) prepared in Example 1 in solution.

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

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

[0037] Fig.12 It is a transfer curve diagram of an organic field effect transistor using P(ClBTI-BTI) prepared in Example 1 as an active layer.

[0038] Fig.13 Graph showing the transfer curve of an organic field effect transistor using P(ClBTI2-T) prepared in Example 1 as an active layer.

[0039] Fig.14 It is a transfer curve diagram of an organic field effect transistor using P(ClBTI2-BTI) prepared in Example 1 as an active layer.

[0040] Fig.15 1 is a current-voltage curve of an organic solar cell using P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) prepared in Example 1 as an active layer. DETAILED DESCRIPTION

[0041] The present invention provides a chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material and a preparation method and application thereof. To make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0042] Unless otherwise defined, all technical terms and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0043] An embodiment of the present invention provides a chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material, wherein the structural formula of the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material is:

[0044]

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

[0046] The chlorinated heterocyclic aromatic hydrocarbon amide-based n-type semiconductor material provided in the embodiment of the present invention has good solubility, a good planar skeleton structure and excellent photoelectric performance. Specifically, a heterocyclic aromatic hydrocarbon amide with excellent solubility and a good planar skeleton structure is used as a matrix, and chlorine atoms are introduced to deepen the electrical deficiency of the heterocyclic aromatic hydrocarbon amide-based n-type semiconductor material, so that the LUMO energy level of the prepared n-type semiconductor material is lower and the photoelectric properties are better, thereby showing excellent application potential in organic photoelectric devices (such as organic solar cells, organic field effect transistors, organic electrochemical transistors or organic thermoelectric devices, etc.).

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

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

[0049]

[0050] Among them, --- represents the connection site.

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

[0052]

[0053] Wherein, --- represents a connection site; R' is a C1-C60 alkyl group (in the present invention, R' involved in different structural formulas are all C1-C60 alkyl groups, and hereinafter, when R' appears again, its meaning will not be repeated); specifically, it can be a C1-C60 straight-chain alkyl group (such as methyl, ethyl, propyl, etc.), or a C1-C60 branched-chain alkyl group.

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

[0055]

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

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

[0058] for The preparation method thereof comprises the following steps:

[0059] S2. (R″)3Sn-Ar-Sn(R″)3 and a catalyst are mixed, heated in an inert atmosphere, and polymerized to obtain the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material.

[0060] The preparation method provided by the embodiment of the present invention is simple and efficient, and the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material is prepared specifically by Stille coupling reaction. First, a heterocyclic aromatic hydrocarbon imide with excellent solubility and good skeleton planar structure is used as a matrix, and the introduction of electronegative chlorine atoms further deepens the electrical deficiency of the heterocyclic aromatic hydrocarbon imide, so that the prepared n-type semiconductor material has a lower LUMO energy level and better photoelectric performance, thereby showing excellent application potential in organic photoelectric devices (such as organic solar cells, organic field effect transistors, organic electrochemical transistors or organic thermoelectric devices, etc.).

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

[0062] After the reaction liquid after the polymerization reaction is cooled, it is filtered and extracted (such as Soxhlet extraction) to obtain the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material.

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

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

[0065] In step S1, Figure 1 As shown, in some embodiments, The preparation method comprises the following steps:

[0066] S11. Dehydration in an acid anhydride compound (specifically acetic anhydride) followed by an amination reaction with R-NH2 (specifically under a protective atmosphere) to obtain

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

[0068] S111, will and a brominating agent (e.g. Br2) are added to a first solvent (e.g. glacial acetic acid) to react to obtain S112, removal by strong base strong affinity reagent (such as n-butyl lithium, also known as n-BuLi) Br at the α position in the middle, then trimethylsilyl chloride is added, and after the reaction, the obtained (TMS is trimethylsilyl); S113, removal by strong base and strong affinity reagent (such as n-BuLi) Br in the solution, then propyl chloroformate is added to obtain S114, will Add to tetrabutylammonium fluoride, and after reaction, obtain S115, will Reaction with a bromination reagent (e.g. N-bromosuccinimide) yields S116, will Under the action of metal catalyst (such as benzocyanate palladium dichloride, etc.), it is activated by carbon hydrogen to obtain S117, will Hydrolyze under alkaline conditions (the base can be potassium hydroxide) to obtain

[0069] In step S2, Figure 1 As shown, in some embodiments, The preparation method comprises the following steps:

[0070] S21. Reaction with bromination reagent (Br2) to obtain In step S21, in some embodiments, The preparation method comprises the following steps:

[0071] S211, will (The preparation method thereof is shown in step S111 to step S114 above) A strong base weak nucleophilic lithium salt reagent (such as lithium bis(trimethylsilyl)amide) is used to extract hydrogen, and a halogenation reaction is carried out with a halogenating reagent (such as 1,2-dibromotetrachloroethane) under a protective atmosphere to obtain a compound S212, With tin monomers (such as ) is reacted with a metal catalyst (e.g., tetrakistriphenylphosphine palladium) by Stille coupling to obtain S213, will After hydrolysis under alkaline conditions (the base can be potassium hydroxide), S214, will After dehydration in an acid anhydride compound (such as acetic anhydride), and then amination reaction with R-NH2 under a protective atmosphere, the obtained

[0072] The embodiment of the present invention also provides an application of the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material as described above in an organic photoelectric device. The embodiment of the present invention also provides an application of the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material prepared by the preparation method as described above in the embodiment of the present invention in an organic photoelectric device. The embodiment of the present invention also provides an application of the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material as described above in the present invention and the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material prepared by the preparation method as described above in the embodiment of the present invention in an organic photoelectric device.

[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 by means of specific examples.

[0075] In the following examples, "1, 2, 3..." marked below the structural formula means "Compound 1, Compound 2, Compound 3". It means that compound 1 is The meanings of the remaining numbers are similar.

[0076] Example 1

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

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

[0079]

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

[0081] (1) Synthesis of Compound 2

[0082]

[0083] According to the synthetic route of compound 1 to compound 2, 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 and reacted at 80°C overnight. After cooling to room temperature, the mixture was slowly poured into an ice-bathed potassium hydroxide solution, then extracted three times with dichloromethane, and then dried and filtered to obtain a white solid product (i.e., compound 2), which was directly used for the next step without purification.

[0084] (2) Synthesis of Compound 3

[0085]

[0086] According to the synthetic route of compound 2 to compound 3, compound 2 (10 g, 28.1 mmol) was added to a 500 mL dry round-bottom flask, and the mixture was ventilated 3 times with a double-row tube under an argon atmosphere. 250 mL of redistilled anhydrous tetrahydrofuran was added to the round-bottom flask to dissolve compound 2, and the system was then moved to a low-temperature reaction tank, gradually cooled to -78 ° C, and 2.4 M n-butyl lithium (24.6 mL, 59.01 mmol, n-BuLi) was slowly added dropwise to the reaction system under argon protection. After the addition was complete, the reaction was continued for 1 h. Then trimethylsilyl chloride (6.4 g, 59.01 mmol, TMSCl) was added, and the low-temperature reaction tank was removed, and the reaction was restored to room temperature overnight. After the reaction was determined to be over by spotting, 10 mL of methanol was added to quench and terminate the reaction. The oily viscous crude product was obtained by concentration under reduced pressure. Then, impurities were separated by silica gel column chromatography using petroleum ether as eluent to obtain a colorless oily liquid, namely compound 3 (9.4 g, yield 98%).

[0087] (3) Synthesis of Compound 4

[0088]

[0089] According to the synthetic route of compound 3 to compound 4, compound 3 (10 g, 29.25 mmol) was added to a 500 mL dry round-bottom flask, and double-row pipes were used for ventilation 3 times under argon atmosphere. 250 mL of anhydrous tetrahydrofuran was added to the round-bottom flask to dissolve compound 3, and then the system was moved to a low-temperature reaction tank, gradually cooled to -78 ° C, and 2.4 M n-BuLi (18 mL, 43.88 mmol) was slowly added dropwise to the reaction system under argon protection. After the addition was completed, the reaction was continued for 1 h. Then propyl chloroformate (5.38 g, 43.88 mmol, ClCOOC3H7) was added, and the low-temperature reaction tank was removed, and the reaction was restored to room temperature overnight. After the reaction was completed as determined by dot plate, 10 mL of methanol was added to quench the reaction, and then the reaction was concentrated under reduced pressure to obtain an oily viscous crude product. Finally, petroleum ether was used as an eluent and impurities were separated by silica gel column chromatography to finally obtain a colorless oily liquid, namely compound 4 (7.35 g, yield was 72%).

[0090] The H NMR spectrum data of compound 4 is:

[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 C NMR spectrum data of compound 4 is:

[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] According to the synthetic route of compound 4 to compound 5, compound 4 (2g, 5.73mmol) was added to a 250mL dry round-bottom flask, and double-row tubes were ventilated 3 times under argon atmosphere. 100mL of redistilled anhydrous tetrahydrofuran was injected into the above round-bottom flask with a clean long needle to dissolve compound 4. Then the system was moved to a low-temperature reaction tank, cooled to -20°C, and a 1M tetrabutylammonium fluoride (TBAF) tetrahydrofuran solution (solution volume was 11.46mL, TBAF molar number was 11.46mmol) was slowly added dropwise to the reaction system. After the addition was completed, the low-temperature reaction tank was removed and the reaction was restored to room temperature for 2h. After the plate was determined to be finished, 2mL of methanol was added to quench and terminate the reaction. The oily viscous crude product was obtained by reduced pressure concentration, and then petroleum ether was used as an eluent, and impurities were separated by silica gel column chromatography to finally obtain a colorless oily liquid, i.e., compound 5 (1.1g, yield 94%).

[0097] The H NMR spectrum data of compound 5 is:

[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 C NMR spectrum data of compound 5 is:

[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] According to the synthetic route of compound 5 to compound 6, compound 5 (2g, 9.77mmol) was added to a 250mL dry single-mouth bottle, and then 100mL of redistilled anhydrous tetrahydrofuran was added to dissolve compound 5, followed by adding 20mL of glacial acetic acid and N-bromosuccinimide (2.09g, 11.72mmol, NBS), and stirred at room temperature for 48h. After the reaction was determined to be complete by spotting, an aqueous sodium sulfite solution was added and stirred at room temperature for half an hour to remove the residual NBS, and then sodium bicarbonate was added until the pH of the solution was alkaline. The aqueous phase was extracted three times with dichloromethane, and the organic phase was further dried to remove residual moisture. After filtration, the brown oily viscous crude product was concentrated under reduced pressure, and then pure petroleum ether was used as an eluent to separate impurities by silica gel column chromatography, and finally a colorless oily liquid, i.e., compound 6 (2.49g, yield 90%) was obtained.

[0104] The H NMR spectrum data of compound 6 is:

[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 C NMR spectrum data of compound 6 is:

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

[0111] The H NMR spectrum data of compound 7 is:

[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 C NMR spectrum data of compound 7 is:

[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] According to the synthetic route of compound 7 to compound 8, 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-mouth bottle and refluxed overnight at 100°C. After the reaction was completed, the reaction solution was cooled to room temperature and concentrated under reduced pressure to remove tetrahydrofuran and ethanol. After the residual mixed solution was cooled to 0°C, hydrochloric acid was added to adjust the pH of the solution to acidic, and a large amount of white solid powder was precipitated. The solid precipitate was then collected by filtration and dried overnight in a vacuum oven to obtain compound 8 (0.34 g, yield 100%).

[0118] (8) Synthesis of Compound 9

[0119]

[0120] According to the synthetic route of compound 8 to compound 9, acetic anhydride (6 mL, Ac2O) and compound 8 (0.35 g, 0.73 mmol) were added to a 25 mL single-mouth bottle under argon atmosphere, and heated (140°C) and refluxed for 4 h. After the reaction was completed, when the reaction bottle gradually returned to room temperature, solids precipitated, which were directly filtered and the filter cake was washed with methanol to obtain a light green solid product (no purification was required and it could be directly used in the next step, and its structural formula was:

[0121] ).

[0122] 2-Octyldodecylamine (0.15g, 0.5mmol), the above light green solid product (0.18g, 0.38mmol) and 4-dimethylaminopyridine (61mg, 0.5mmol) were added to a 20mL dry single-mouth bottle, and the double-row tube was ventilated 3 times under an argon atmosphere. Then, 10mL of anhydrous 1,4-dioxane was taken with a clean long needle and added to the above single-mouth bottle, and then refluxed at 100°C overnight, followed by adding 2mL of acetic anhydride, and the temperature was raised to 140°C for reaction for 3h. After the reaction was completed, the mixture was concentrated under reduced pressure to obtain an oily viscous liquid, and then a mixture of petroleum ether and dichloromethane (the volume ratio of petroleum ether to dichloromethane was 5:1) was used as an eluent, and impurities were separated by silica gel column chromatography to obtain a yellow solid compound, namely compound 9 (0.2g, yield 71%).

[0123] The H NMR spectrum of compound 9 is shown in Figure 2 As shown, the H NMR spectrum data of compound 9 is: 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 in Figure 3 As shown, the C NMR spectrum data of compound 9 is: 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] According to the synthetic route of compound 5 to compound 10, 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, and the mixture was ventilated three times using a double-row tube under an argon atmosphere. 60 mL of redistilled anhydrous ether was injected into the round-bottom flask using a clean long needle to dissolve compound 5. The system was then moved to a low-temperature reaction tank and gradually cooled to -78 °C. Under argon protection, 1 M LiHMDS solution (10.80 mL, 10.80 mmol, lithium bis(trimethylsilyl)amide) was added dropwise to the reaction system, and the reaction was continued for 20 min. The low-temperature reaction tank was then removed and the reaction was restored to room temperature for 2 h. After the reaction was completed as determined by spotting, 2 mL of methanol was added through a syringe to quench the reaction, and the temperature was restored to room temperature. The crude oily viscous product was obtained by concentrating under reduced pressure. The impurities were separated by silica gel column chromatography to finally obtain a colorless oily liquid, namely compound 10 (1.1 g, yield 80%).

[0128] The H NMR spectrum data of compound 10 is:

[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 C NMR spectrum data of compound 10 is:

[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] According to the synthetic route of compound 10 to compound 11, 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 tetrakistriphenylphosphine palladium (0.1 g, Pd(PPh3)4) were added to a 20 mL microwave reaction tube, and the tube was ventilated 3 times under an argon atmosphere, and then 6 mL of N,N-dimethylformamide (DMF) was added and capped. The microwave reaction tube was placed in a microwave reactor, and the program was set to heat it to 140 ° C for 3 hours. After cooling to room temperature, a black viscous crude product was obtained by concentration. Then, dichloromethane was used as an eluent, and impurities were separated by silica gel column chromatography to obtain a gray solid compound, namely compound 11 (0.18 g, yield 40%).

[0135] The H NMR spectrum data of compound 11 is:

[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 C NMR spectrum data of compound 11 is:

[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] According to the synthetic route of compound 11 to compound 12, 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 at 100°C overnight. After the reaction was completed, the mixture was concentrated under reduced pressure to obtain a mixed solution. After the residual mixed solution was cooled to 0°C, hydrochloric acid was added to adjust the pH of the solution to acidic, and a large amount of white solid powder was precipitated. The solid precipitate was then collected by filtration and dried in a vacuum oven overnight to obtain compound 12 (0.4 g, yield 100%).

[0142] (12) Synthesis of compound 13:

[0143]

[0144] According to the synthetic route of compound 12 to compound 13, compound 12 (0.4 g, 0.73 mmol) and acetic anhydride (6 mL, Ac2O) were added to a 25 mL round-bottom flask under argon atmosphere, and heated (140°C) and refluxed for 4 h. After the reaction was completed, solids were precipitated when cooled to room temperature. The solids were directly filtered and the filter cake was washed with methanol to obtain a light brown solid product (no purification was required and it could be directly used in the next step). Its structural formula is:

[0145] ).

[0146] 2-Octyldodecylamine (0.36g, 1.2mmol), the above light brown solid product (0.25g, 0.48mmol) and 4-dimethylaminopyridine (0.15g, 1.2mmol) were added to a 50mL reaction bottle, and the air was evacuated 3 times under an argon atmosphere, and 15mL of anhydrous 1,4-dioxane was injected into the above reaction bottle with a clean long needle. Then heated (100°C) and refluxed and stirred overnight, and then 2mL of acetic anhydride was added, and the temperature was raised to 140°C for 3h. After the reaction was completed, the yellow viscous crude product was obtained by concentration under reduced pressure, and then a mixture of petroleum ether and dichloromethane (the volume ratio of petroleum ether to dichloromethane was 2:1) was used as an eluent, and impurities were separated by silica gel column chromatography to obtain a light yellow solid compound, i.e., compound 13 (0.5g, yield 97%).

[0147] The H NMR spectrum data of compound 13 is:

[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 C NMR spectrum data of compound 13 is:

[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] According to the synthetic route of compound 13 to compound 14, compound 13 (0.3g, 0.28mmol) was added to a 50mL reaction bottle, and then 20mL chloroform was added, and then an excess of bromine (0.2g) and a catalytic amount of ferric chloride (5mg) were added, and stirred at room temperature for 5h. After the plate was judged to be finished, an aqueous sodium sulfite solution was added and stirred at room temperature for half an hour to remove the residual bromine. The mixed solution was repeatedly extracted with dichloromethane for many times, and then the organic phase was further dried to fully remove the residual moisture, and then filtered and the dichloromethane solvent was removed by vacuum rotary evaporation to obtain a viscous crude product, and then a mixed solution of petroleum ether and dichloromethane (the volume ratio of petroleum ether to dichloromethane was 2: 1) was used as an eluent, and impurities were separated by silica gel column chromatography to obtain an orange solid compound, i.e., compound 14 (0.34g, yield 98%).

[0154] The H NMR spectrum of compound 14 is shown in Figure 4 As shown, the H NMR spectrum data of compound 14 is: 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 in Figure 5As shown, the C NMR spectrum data of compound 14 is: 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] According to the synthetic route of P(ClBTI-BTI) obtained by reacting the above-mentioned compound 9 and compound 15 (Bu in its structural formula is butyl), compound 9 (0.035 g, 0.047 mmol), compound 15 (0.0515 g, 0.047 mmol), tri(dibenzylideneacetone)dipalladium (0.64 mg, 0.0007 mmol, Pd2(dba)3) and tri(o-tolyl)phosphine (1.70 mg, 0.0056 mmol, P(o-tolyl)3) were added to a dry microwave reaction tube, and the tube was ventilated 3 times using a double-row tube under an argon atmosphere, and then 3 mL of anhydrous toluene was added and the tube was sealed. The 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-butyltinthiophene was added and the mixture was reacted at 110°C for 20 min. After the mixture returned to room temperature, 0.2 mL of 2-bromothiophene was added and the mixture was reacted at 110°C for 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 with a Soxhlet extraction apparatus. The solid was extracted with methanol, acetone, and n-hexane solvents for 15 h each to remove small molecular fragments and residual catalysts. Finally, all the final products extracted with dichloromethane were collected, concentrated under reduced pressure, and then precipitated into a methanol solution again. P(ClBTI-BTI) was obtained after filtration. Its hydrogen nuclear magnetic resonance spectrum is shown in FIG. Figure 6 shown.

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

[0160]

[0161] According to the synthetic route of P(ClBTI2-T) obtained by reacting the above-mentioned compound 14 and compound 16 (Me in its structural formula is methyl), compound 14 (0.050 g, 0.0406 mmol), compound 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, and the tube was ventilated three times using a double-row tube under an argon atmosphere, followed by the addition of 3 mL of anhydrous toluene and the cap 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 hours. After cooling to room temperature, 0.1 mL of 2-butyltinthiophene was added and reacted at 110°C for 20 minutes; then after returning to room temperature, 0.2 mL of 2-bromothiophene was added and continued to react at 110°C for 20 minutes. After the reaction is completed, the reaction solution is added dropwise to 80 mL of methanol, and the solid is collected by filtration. Then, a Soxhlet extraction apparatus is used for extraction. Methanol, acetone, and n-hexane solvents are used for extraction for 15 hours each to remove small molecular fragments and residual catalysts; and dichloromethane is used for extraction for 10 hours to further remove low molecular weight fragments. Finally, the final product extracted with chloroform is collected, concentrated under reduced pressure, and then precipitated into a methanol solution again. After filtration, P(ClBTI2-T) is obtained, and its hydrogen nuclear magnetic resonance spectrum is shown as follows: Figure 7 shown.

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

[0163]

[0164] According to the synthetic route of P(ClBTI2-BTI) obtained by reacting the above-mentioned compound 14 and compound 15 (Bu in its structural formula is butyl), compound 14 (0.0584 g, 0.0475 mmol), compound 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, and the tube was ventilated 3 times using a double-row tube under an argon atmosphere, followed by adding 3 mL of anhydrous toluene and then capping. The microwave reaction tube was placed in a microwave reactor and the program was set to heat it to 140°C for 3 hours. After cooling to room temperature, add 0.1 mL of 2-butyltinthiophene and react at 110°C for 20 minutes; then after returning to room temperature, add 0.2 mL of 2-bromothiophene and continue to react at 110°C for 20 minutes. After the reaction is completed, add the reaction solution dropwise into 80 mL of methanol and collect the solid by filtration. Then use a Soxhlet extraction device to extract with methanol, acetone and n-hexane solvents for 15 hours each to remove small molecule fragments and residual catalysts; then use dichloromethane for 10 hours to further remove low molecular weight fragments. Finally, collect the final product extracted with chloroform, concentrate it, and precipitate it into methanol solution again. After filtration, P(ClBTI2-BTI) is obtained, and its nuclear magnetic resonance hydrogen spectrum is as shown below Figure 8 shown.

[0165] The performance tests were performed on P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) prepared in Example 1:

[0166] 1. UV-visible spectra of P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) were tested in the form of solution (solvent: chloroform) and film. The results are as follows: Fig. 9 and Fig.10 As shown. Fig. 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; Fig.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). The results are as follows: Fig.11 Analysis Fig.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; 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 (the only difference from P(ClBTI-BTI) is that it does not contain Cl), P(BTI2-T) (the only difference from P(ClBTI2-T) is that it does not contain Cl) and P(BTI2-BTI) (the only difference from P(ClBTI2-BTI) is that it does not contain 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 can effectively reduce the LUMO energy level of the polymer, which is more conducive to the realization of unipolar n-type electron transport.

[0169] 3. P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) were used as semiconductor layers to prepare top-gate and bottom-contact organic field-effect transistors, and the electron mobility was tested using a Keithley S4200 semiconductor analyzer.

[0170] Among them, the preparation method of the organic field effect transistor is as follows:

[0171] The source and drain electrodes (the source and drain electrodes are composed of a stacked 3nm thick Cr layer and a 30nm thick Au layer) are photolithographically spaced on borosilicate glass, and the channel length (L) is 50μm and the channel width (W) is 5mm.

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

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

[0174] Finally, aluminum was evaporated onto the dielectric layer to form a 50nm thick gate, and three types of organic field-effect transistors were obtained (the only difference was the material of the active layer, namely P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI)).

[0175] Test results such as Figure 12 to Figure 14 As shown in the figure, the transfer curves of P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) are shown respectively. From the figure, it can be calculated that the electron mobility of P(ClBTI-BTI), P(ClBTI2-T) and P(ClBTI2-BTI) are 0.013, 0.29 and 0.48 cm 2 ·V -1 ·s -1 , which are all charge migration characteristics of a single n-type.

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

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

[0178] PEDOT:PSS was spin-coated on 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 an active layer;

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

[0181] Ag was evaporated on the electron transport layer to form a top electrode, and an all-polymer solar cell was obtained, which was denoted as PM6:PY-IT:P(ClBTI-BTI).

[0182] Two other all-polymer solar cells were prepared, the only difference being the third component material of the active layer, i.e., P(ClBTI-BTI) was replaced by P(ClBTI2-T) and P(ClBTI2-BTI), respectively. The two all-polymer solar cells were recorded as PM6:PY-IT:P(ClBTI2-T) and PM6:PY-IT:P(ClBTI2-BTI), respectively.

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

[0184] Among them, PM6 is a polymer donor material with the structural formula: PY-IT is a polymer receptor material with the structural formula

[0185] The current-voltage curve test results of three fully polymerized solar cells are shown in Figure 2. Fig.15 As shown, PM6:PY-IT:P(ClBTI-BTI), PM6:PY-IT:P(ClBTI2-T) and PM6:PY-IT:P(ClBTI2-BTI) have energy conversion efficiencies of up to 17.27%, 18.24% and 19.35% respectively. The energy conversion efficiency of the standard device of PM6:PY-IT is only 15.84%. It can be found that with the increase of the mobility of the chlorinated polymer material, the device efficiency of the corresponding all-polymer solar cell increases accordingly. Among them, the energy conversion efficiency of PM6:PY-IT:P(ClBTI2-BTI) reaches the highest, which is also one of the highest values ​​of the efficiency of all-polymer solar cells at present.

[0186] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material, characterized in that: The structural formula of the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material is: Wherein, X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is 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.

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: Among them, --- represents the connection site.

3. The chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material according to claim 1, characterized in that: Ar is selected from one of the following groups: Wherein, --- represents the connection site; R' is a C1-C60 alkyl group.

4. A method for preparing the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material as claimed in claim 1, characterized in that: The steps include: Will (R″)3Sn-Ar-Sn(R″)3 and a catalyst are mixed, heated in an inert atmosphere, and polymerized to obtain the chlorinated heterocyclic aromatic hydrocarbon imide-based n-type semiconductor material; wherein X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is a single bond, a C2-C60 alkenyl group, and a C3-C60 heterocyclic aromatic hydrocarbon; and R″ is an alkyl group; or, Will (R″)3Sn-Ar-Sn(R″)3 and a catalyst are mixed, heated in an inert atmosphere, and polymerized to obtain the chlorinated heterocyclic aromatic hydrocarbon amide-based n-type semiconductor material; wherein X is an oxygen atom, a sulfur atom or a selenium atom; R is an alkyl group or an alkoxy group; Ar is a single bond, a C2-C60 alkenyl group, and a C3-C60 heterocyclic aromatic hydrocarbon; and R″ is an alkyl group.

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

6. The preparation method according to claim 4, characterized in that: The catalyst accounts for and 1% to 13% of the total molar number of (R″)3Sn-Ar-Sn(R″)3; Or, the catalyst accounts for and 1% to 13% of the total molar number of (R″)3Sn-Ar-Sn(R″)3.

7. The preparation method according to claim 4, characterized in that: The preparation method comprises the following steps: Will Dehydration in anhydride compounds, followed by amination with R-NH2, yields Wherein, R is an alkyl group or an alkoxy group.

8. The preparation method according to claim 4, characterized in that: The preparation method comprises the following steps: Will Reaction with bromination reagent to obtain Wherein, R is an alkyl group or an alkoxy group.

9. Use of the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material according to any one of claims 1 to 3 and / or the chlorinated heterocyclic aromatic hydrocarbon imido-based n-type semiconductor material prepared by the preparation method according to any one of claims 4 to 8 in an organic optoelectronic device.

10. The use according to claim 9, characterized in that: The organic photoelectric device includes an organic field effect transistor, an organic electrochemical transistor, an organic thermoelectric device or an organic solar cell.

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