Cyanoquinoxalinyl n-type polymer semiconductor material as well as preparation method and application thereof

Abstract

The invention provides a cyanation quinoxaline-based n-type polymer semiconductor material and a preparation method and application thereof, and the cyanation quinoxaline-based n-type polymer semiconductor material has a chemical structural general formula as follows: in the n-type polymer semiconductor material, quinoxaline is used as a matrix and has good solubility and a planar skeleton structure, and the structural formula is shown in the specification. The introduction of the cyano group significantly reduces the electricity shortage of the quinoxaline, so that the prepared n-type polymer semiconductor material has lower molecular front track energy level and more excellent photoelectric properties, thereby showing excellent application potential in the fields of organic field effect transistors, organic thermoelectricity or organic solar cells and the like.

Description

Technical Field

[0001] This invention relates to the field of organic semiconductor technology, and in particular to cyano-quinoxalin-based n-type polymer semiconductor materials, their preparation methods, and applications. Technical Background

[0002] In recent years, organic conjugated polymer semiconductor materials have attracted widespread attention in various fields due to their lightweight, solution processability, structural tunability, and flexibility. While significant progress has been made in p-type (hole-transporting) organic polymer materials, the development of n-type (electron-transporting) polymer semiconductor materials has lagged behind. This is mainly due to the synthetic challenges posed by the introduction of strong electron-withdrawing groups and the resulting steric hindrance effects. However, n-type polymer materials play an irreplaceable role in applications such as logic complementary circuits, organic thermoelectrics, and all-polymer solar cells; therefore, developing high-performance n-type polymer semiconductor materials has become an important research direction.

[0003] The core of designing such materials lies in constructing highly electron-deficient building blocks. Commonly used building blocks include naphthalenediimide (NDI), perylenediimide (PDI), and quinoxaline (Qx). Among these, NDI and PDI-based polymers suffer from limited electron mobility and near-infrared absorption due to the twisted structure of their molecular backbones. While Qx-based polymers possess good planarity, their high least unoccupied molecular orbital (LUMO) energy levels tend to exhibit p-type characteristics, which to some extent limits their application in n-type materials.

[0004] Therefore, developing novel electron-deficient building blocks to overcome the limitations of existing materials is an important way to promote the development of n-type polymer semiconductor materials. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a cyano-quinoxalin-based n-type polymer semiconductor material, its preparation method and application, in order to solve the problem of poor photoelectric properties of existing n-type polymer semiconductor materials.

[0006] The technical solution of the present invention is as follows:

[0007] A cyano-quinoxalinyl n-type polymeric semiconductor material, wherein its general chemical structural formula is: Ar is selected from any of the C3-C60 heterocyclic aromatic hydrocarbons with soluble side chains to achieve solution-processable materials and control their photoelectric properties.

[0008] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0009] As a preferred technical solution, in the cyano-quinoxalin-based n-type polymer semiconductor material, the Ar is selected from any one of the following chemical structural formulas:

[0010]

[0011] In the chemical structural formula, the dashed lines represent the connecting bonds of groups, and R is selected from alkyl or alkoxy side chains.

[0012] As a preferred technical solution, in the cyano-quinoxalin-based n-type polymer semiconductor material, the R in Ar is selected from any one of the following chemical structural formulas:

[0013]

[0014] As a preferred technical solution, the cyano-quinoxalin-based n-type polymeric semiconductor material has a chemical structural formula of one of the following:

[0015]

[0016] Secondly, a method for preparing a cyano-quinoxalin-based n-type polymeric semiconductor material, comprising the steps of:

[0017]

[0018] Compound 3 Or compound 6 Tin compounds The reaction products were obtained by polymerization of palladium-based catalysts and phosphine ligands under an argon atmosphere via oil bath heating (120°C).

[0019] After cooling to room temperature, the mixture is added dropwise to a poor solvent, followed by filtration and Soxhlet extraction to obtain the cyano-substituted quinoxalin-based n-type polymer semiconductor material. The poor solvent is methanol, ethanol, etc.

[0020] The method for preparing the cyano-quinoxalin-based n-type polymer semiconductor material, wherein the palladium catalyst is tris(dibenzylacetone)dipalladium and the phosphine ligand is 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl.

[0021] The method for preparing the cyano-quinoxalin-based n-type polymer semiconductor material, wherein the palladium catalyst accounts for 1-5% of the total molar ratio of compound 3 or 6 and tin compound, and the phosphine ligand accounts for 2-10% of the total molar ratio of compound 3 or 6 and tin compound.

[0022] As a preferred technical solution, in the preparation method of the cyano-quinoxalin-based n-type polymer semiconductor material, wherein compound 3 and compound 6 The preparation includes the following steps:

[0023]

[0024] Compound 1 and compound 2 react in an acidic solvent to give compound 3;

[0025] The acidic solvent is trifluoroacetic acid;

[0026]

[0027] Compound 4 and compound 5 react in an acidic solvent to give compound 6; the acidic solvent is acetic acid.

[0028] Thirdly, cyano-quinoxalin-based n-type polymer semiconductor materials are used in organic field-effect transistors or organic thermoelectric devices. For example, they can be used as semiconductor layer materials to fabricate organic field-effect transistors with top-gate and bottom-contact contacts; or as active layer materials in organic thermoelectric devices.

[0029] Beneficial effects: This invention provides a cyano-quinoxalin-based n-type polymeric semiconductor material, whose general chemical formula is: In this n-type polymer semiconductor material, quinoxaline serves as the matrix, exhibiting good solubility and a planar framework structure. The introduction of cyano groups significantly reduces the molecular frontier orbital energy levels of the quinoxaline-based n-type polymer, thus demonstrating excellent application potential in fields such as organic field-effect transistors or organic thermoelectrics. Attached Figure Description

[0030] Figure 1 The image shows the hydrogen nuclear magnetic resonance spectrum of compound 3 prepared in Example 1 of this invention.

[0031] Figure 2 This is the carbon NMR spectrum of compound 3 prepared in Example 1 of the present invention.

[0032] Figure 3 The image shows the hydrogen nuclear magnetic resonance spectrum of compound 6 prepared in Example 1 of this invention.

[0033] Figure 4 This is the carbon NMR spectrum of compound 6 prepared in Example 1 of the present invention.

[0034] Figure 5 The UV-Vis spectra of the polymers TDPP-QxCN, TDPP-CNQx, and the uncyano-modified quinoxalinyl polymer TDPP-Qx solution prepared in Example 1 of this invention are shown.

[0035] Figure 6The UV-Vis spectra of the polymer TDPP-QxCN, TDPP-CNQx and uncyano-modified quinoxaline-based polymer TDPP-Qx films prepared in Example 1 of this invention are shown.

[0036] Figure 7 Cyclic voltammetry diagrams of polymers TDPP-QxCN, TDPP-CNQx, and uncyano-modified quinoxalinyl polymer TDPP-Qx prepared in Example 1 of this invention.

[0037] Figure 8 This is a graph showing the organic field-effect transistor transfer curve of the polymer TDPP-QxCN prepared in Example 1 of the present invention.

[0038] Figure 9 This is a graph showing the organic field-effect transistor transfer curve of the polymer TDPP-CNQx prepared in Example 1 of the present invention.

[0039] Figure 10 This is a graph showing the organic field-effect transistor transfer curve of the polymer TDPP-Qx prepared in Example 1 of the present invention.

[0040] Figure 11 The graph shows the changes in conductivity, Seebeck coefficient, and power factor of the polymer TDPP-CNQx prepared in Example 1 of this invention as a function of doping concentration in organic thermoelectric processes. Detailed Implementation

[0041] This invention provides cyano-quinoxalin-based n-type polymeric 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 merely illustrative and not intended to limit the invention.

[0042] The cyano-quinoxalin-based n-type polymer semiconductor material provided by this invention has the following general chemical formula: Ar is selected from any one of the C3-C60 heterocyclic aromatic hydrocarbons with dissolved side chains, and n is an integer from 1 to 50.

[0043] In the n-type polymer semiconductor material provided by this invention, quinoxaline has good solubility and excellent planar framework structure. Using it as a matrix, the introduction of electron-deficient cyano groups deepens the electron deficiency of quinoxaline, resulting in a lower molecular frontier orbital energy level and better photoelectric properties in the prepared n-type polymer semiconductor material. This gives it excellent application potential in organic field-effect transistors or organic thermoelectric materials.

[0044] In some embodiments, the Ar is selected from any of the following chemical structural formulas:

[0045]

[0046] In the chemical structural formula, the dashed lines represent the connecting bonds of groups, and R is selected from alkyl or alkoxy side chains.

[0047] In some embodiments, the R in Ar is selected from any of the following chemical structures:

[0048]

[0049] In some embodiments, the chemical structural formula of the cyano-quinoxalin-based n-type polymeric semiconductor material is one of the following, but not limited to:

[0050]

[0051] In some embodiments, a method for preparing cyano-quinoxalin-based n-type polymeric semiconductor materials is also provided, comprising the steps of:

[0052] Compound 3 Or compound 6 Tin compounds The mixture of palladium-based catalysts and phosphine ligands was used. The relevant reaction products were obtained by polymerization in an oil bath under an argon atmosphere.

[0053] After the polymerization product is cooled, it is added dropwise to methanol, and then filtered and Soxhlet extracted sequentially to obtain the chlorinated heterocyclic aromatic imide-based n-type polymer semiconductor material.

[0054] In this invention, the cyano-quinoxalin-based n-type polymer semiconductor material is prepared by the classic Stille coupling reaction, the reaction process of which is as follows:

[0055]

[0056] In this invention, the palladium catalyst is tris(dibenzylacetone)dipalladium, and the phosphine ligand is one or both of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, but is not limited thereto. Preferably, the palladium catalyst is a combination of tris(dibenzylacetone)dipalladium and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl.

[0057] In this invention, the palladium catalyst accounts for 1-5% of the total molar ratio of compound 3 or 6 and the tin compound, and the phosphine ligand accounts for 2-10% of the total molar ratio of compound 3 or 6 and the tin compound. For example, 2%, 4%, 6%, 8%, and 10%, etc., preferably 2% palladium catalyst and 4% phosphine ligand.

[0058] In some embodiments, the compound 3 and compound 6 The preparation includes the following steps:

[0059] Compound 1 and compound 2 After thorough grinding, add the compound to trifluoroacetic acid in batches under ice bath conditions to obtain compound 3.

[0060] Compound 4 With compound 5 Dissolved in acetic acid, heated under reflux, and dehydrated to condense to give compound 6.

[0061] In some embodiments, the application of cyano-quinoxalin-based n-type polymeric semiconductor materials in organic field-effect transistors and organic thermoelectrics is also provided.

[0062] The present invention will be further explained and illustrated below through specific embodiments:

[0063] Example 1

[0064] A cyano-quinoxalin-based n-type polymeric semiconductor material is provided, wherein the cyano-quinoxalin-based n-type polymeric semiconductor material has the structure shown in Formula II:

[0065] Formula II;

[0067] The preparation method of the polymer with the structure shown in Formula II above includes the following steps:

[0068] (1) Synthesis of compound 3:

[0069]

[0070] Compound 1 (0.48 g, 4.51 mmol) and compound 2 (1 g, 3.76 mmol) were thoroughly ground and mixed, then added in portions to trifluoroacetic acid (40 mL) at low temperature. After reacting for 3 h, the mixture was poured into ice water and filtered to obtain the crude product. Compound 3 (0.35 g, 25%) was purified by column chromatography. 1 H NMR (400M, CDCl3): δ (ppm): 8.26 (s). 13 C NMR (400M, CDCl3): δ (ppm): 140.63, 138.38, 131.59, 124.62, 112.61.

[0071] (2) Synthesis of compound 6:

[0072]

[0073] Compound 4 (0.5 g, 1.58 mmol) and compound 5 (0.28 g, 1.9 mmol) were dissolved in 50 mL of acetic acid solution. The mixture was heated and stirred at 110 °C under an argon atmosphere and refluxed overnight. After the reaction was completed, the solvent was removed by concentration under reduced pressure. The crude product was separated by column chromatography to give compound 6 (0.34 g, yield: 65%). 1 H NMR (400M, CDCl3): δ (ppm): 9.20 (s). 13 C NMR (400M, CDCl3): δ (ppm): 149.09, 142.35, 132.64, 118.95, 113.69.

[0074] (3) Synthesis of polymer TDPP-QxCN:

[0075]

[0076] Compound 3 (0.0285 g, 0.084 mmol), compound 7 (0.1 g, 0.084 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3) (1.54 mg, 0.0017 mmol), and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (XPhos) (1.60 mg, 0.0034 mmol) were added to a dry reaction tube. The tube was purged three times using a double-row tube under an argon atmosphere, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in an oil bath and reacted at 120 °C for 24 min. After the reaction was complete, the mixture was allowed to return to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The mixture was filtered, and the solid was collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents each for 8 hours to remove small molecule fragments and residual catalysts. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The final polymer TDPP-QxCN was obtained by filtration.

[0077] (4) Synthesis of polymer TDPP-CNQx:

[0078]

[0079] Compound 6 (0.0285 g, 0.084 mmol), compound 7 (0.1 g, 0.084 mmol), Pd2(dba)3 (1.54 mg, 0.0017 mmol), and XPhos (1.60 mg, 0.0034 mmol) were added to a dry reaction tube. The tube was purged three times under an argon atmosphere using a double-row tube, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in an oil bath and reacted at 120 °C for 24 h. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer TDPP-CNQx.

[0080] (5) Synthesis of polymer IDT-QxCN

[0081]

[0082] Compound 3 (0.0335 g, 0.1 mmol), compound 8 (0.1 g, 0.1 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and XPhos (1.91 mg, 0.004 mmol) were added to a dry reaction tube. The tube was purged three times under an argon atmosphere using a double-row tube, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in an oil bath and reacted at 120 °C for 20 min. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer IDT-QxCN.

[0083] (6) Synthesis of polymer IDT-CNQx

[0084]

[0085] Compound 6 (0.0335 g, 0.1 mmol), compound 8 (0.1 g, 0.1 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and XPhos (1.91 mg, 0.004 mmol) were added to a dry reaction tube. The tube was purged three times under an argon atmosphere using a double-row tube, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in a microwave reactor and reacted at 140 °C for 4 h. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer IDT-CNQx.

[0086] (7) Synthesis of polymer BDT-QxCN

[0087]

[0088] Compound 3 (0.0335 g, 0.1 mmol), compound 9 (0.1052 g, 0.1 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and XPhos (1.91 mg, 0.004 mmol) were added to a dry reaction tube. The tube was purged three times under an argon atmosphere using a double-row tube, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in an oil bath and reacted at 120 °C for 20 min. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer BDT-QxCN.

[0089] (8) Synthesis of polymer BDT-CNQx

[0090]

[0091] Compound 6 (0.0335 g, 0.1 mmol), compound 9 (0.1052 g, 0.1 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and XPhos (1.91 mg, 0.004 mmol) were added to a dry reaction tube. The tube was purged three times using a double-row tube under an argon atmosphere, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in a microwave reactor and reacted at 140 °C for 3 h. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer BDT-CNQx.

[0092] (9) Synthesis of polymer BT-QxCN

[0093]

[0094] Compound 3 (0.0335 g, 0.1 mmol), compound 10 (0.083 g, 0.1 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and XPhos (1.91 mg, 0.004 mmol) were added to a dry reaction tube. The tube was purged three times under an argon atmosphere using a double-row tube, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in an oil bath and reacted at 120 °C for 20 min. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer BT-QxCN.

[0095] (10) Synthesis of polymer BT-CNQx

[0096]

[0097] Compound 6 (0.0335 g, 0.1 mmol), compound 10 (0.083 g, 0.1 mmol), Pd2(dba)3 (1.83 mg, 0.002 mmol), and XPhos (1.91 mg, 0.004 mmol) were added to a dry reaction tube. The tube was purged three times under an argon atmosphere using a double-row tube, followed by the addition of 5 mL of anhydrous toluene, and then the tube was sealed. The reaction tube was placed in a microwave reactor and reacted at 140 °C for 3 h. After the reaction was complete, the temperature was lowered to room temperature, and the polymer solution was added dropwise to 100 mL of methanol solution. The solid was then filtered and collected. The solid product was then subjected to Soxhlet extraction, with methanol, acetone, and n-hexane solvents, each for 8 h, to remove small molecule fragments and residual catalyst. Finally, the final fragment extracted with chloroform was collected, concentrated under reduced pressure, and then precipitated back into methanol solution. The residue was then filtered to obtain the final polymer BT-CNQx.

[0098] Example 2

[0099] The performance of the n-type polymers TDPP-QxCN, TDPP-CNQx, and the uncyano-modified quinoxalinyl polymer TDPP-Qx prepared in Example 1 was tested:

[0100] 1. The polymers TDPP-QxCN, TDPP-CNQx, and the uncyano-modified quinoxalinyl polymer TDPP-Qx were subjected to UV-Vis spectroscopy tests, such as... Figure 5 and Figure 6 As shown. Analysis Figure 5 It can be seen that the maximum absorption peaks of polymers TDPP-QxCN, TDPP-CNQx, and TDPP-Qx in solution are 976, 894, and 874 nm, respectively; analysis Figure 6 It can be seen that the optical band gaps of polymers TDPP-QxCN, TDPP-CNQx, and TDPP-Qx are 0.99, 1.11, and 1.22 eV, respectively.

[0101] 2. Electrochemical tests were performed on the polymers TDPP-QxCN, TDPP-CNQx, and the uncyano-modified quinoxalinyl polymer TDPP-Qx. The results are as follows: Figure 7 As shown. Analysis Figure 7 It is known that the LUMO energy levels of polymers TDPP-QxCN, TDPP-CNQx, and TDPP-Qx are -3.91, -3.93, and -3.35 eV, respectively; while the HOMO energy levels of polymers TDPP-QxCN, TDPP-CNQx, and TDPP-Qx are -5.47, -5.59, and -5.19 eV, respectively. In contrast, the introduction of electron-deficient cyano groups significantly lowers the LUMO energy levels of the newly synthesized polymers, which is more conducive to achieving unipolar n-type electron transport.

[0102] 3. Using the n-type polymer TDPP-QxCN, TDPP-CNQx, and the uncyano-modified quinoxalin-based polymer TDPP-Qx described in Example 1 as semiconductor layers, organic field-effect transistors with top-gate bottom contacts were fabricated. Electron mobility was tested using a Keithley S4200 semiconductor analyzer. The fabrication method of the organic field-effect transistors is as follows: The source and drain electrodes (composed of 3nm Cr and 30nm Au) were patterned using photolithography to form an electrode structure with a channel length (L) of 10, 20, 50, or 100 μm and a channel width (W) of 5000 μm. Subsequently, the patterned glass substrate was ultrasonically cleaned with isopropanol and acetone (20 minutes each), dried with nitrogen, and then treated with UV-ozone for 15 minutes. After transferring the substrate to a nitrogen glove box (O2, H2O concentration <0.1ppm), a polymer chloroform solution (5mg / mL) was spin-coated at 1500 rpm. -1 The active layer was formed in 45 seconds, followed by thermal annealing at 150°C for 20 minutes. Next, CYTOP dielectric material (CTL-809M:CT-SOLV180) was mixed at a 2:1 volume ratio, and spin-coated at 1500 rpm for 60 seconds to form a film approximately 500 nm thick, followed by annealing at 90°C for 30 minutes. Finally, an approximately 50 nm aluminum layer was deposited via thermal evaporation as the gate electrode to complete the device fabrication. Test results are as follows... Figure 8-10 The figure shows the transfer curves of polymers TDPP-QxCN, TDPP-CNQx, and TDPP-Qx, respectively. From the figure, the electron mobilities of polymers TDPP-QxCN, TDPP-CNQx, and TDPP-Qx can be calculated to be 0.04, 1.30, and 1.77 cm⁻¹, respectively. 2 ·V -1 ·s -1 Charge migration characteristics of a single n-type.

[0103] 4. The n-type polymers QxCN-DPP, CNQx-DPP, and uncyano-modified quinoxaline-based polymers Qx-DPP described in Example 1 were used as active layers in organic thermoelectric devices. The organic thermoelectric devices were fabricated on a borosilicate glass substrate. First, the substrate was ultrasonically cleaned sequentially with isopropanol and acetone (20 minutes each), followed by a 15-minute UV-ozone treatment. After transferring the substrate to a nitrogen glove box (O2 and H2O concentrations <0.1 ppm), a 30 nm gold electrode (100 μm length × 2000 μm width) was deposited by thermal evaporation using a mask. After thermal evaporation of 0.1 nm gold nanoparticles (Au-NPs), a polymer chloroform solution (5 mg / mL) was spin-coated at 1000 rpm. -1 Annealing at 150℃ for 20 minutes after 45 seconds. The doped thin film was prepared using a sequential doping process: 0.5-2 mg / mL of JLBI dopant solution was added. -1The solution (n-butyl acetate solvent) was spin-coated onto the semiconductor layer at 1500 rpm for 30 seconds, followed by heat annealing at 120°C for 15 seconds to activate the doping. Test results are as follows: Figure 11 As shown, the conductivity of TDPP-CNQx reaches 73.75 S / cm. -1 The conductivity of TDPP-QxCN and TDPP-Qx is only 0.01 cm⁻¹. -1 and 0.47S cm -1 .

[0104] 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 cyano-quinoxalin-based n-type polymeric semiconductor material, characterized in that, Its general chemical structural formula is: Wherein, n takes the value of an integer from 1 to 50, and Ar is selected from any one of the C3-C60 heterocyclic aromatic hydrocarbons with dissolved side chains.

2. The cyano-quinoxalin-based n-type polymer semiconductor material according to claim 1, characterized in that, The Ar is selected from any of the following chemical structural formulas: In the chemical structural formula, the dashed lines represent the connecting bonds of groups, and R is an alkyl or alkoxy side chain.

3. The cyano-quinoxalin-based n-type polymer semiconductor material according to claim 2, characterized in that, The R is selected from any of the following structures:

4. The cyano-quinoxalin-based n-type polymer semiconductor material according to claim 1, characterized in that, Its chemical structural formula is any one of the following:

5. A method for preparing the cyano-quinoxalin-based n-type polymeric semiconductor material as described in claim 1, characterized in that, Including the following steps: compound or compounds Tin compounds And palladium catalysts and phosphine ligands are mixed to obtain a mixture; The mixture was heated under an argon atmosphere, and after cooling, it was dropped into a poor solvent. The mixture was then filtered and Soxhlet extracted to obtain the cyano-quinoxalin-based n-type polymer semiconductor material.

6. The method for preparing the cyano-quinoxalin-based n-type polymeric semiconductor material according to claim 5, characterized in that, The palladium catalyst is tris(dibenzylideneacetone)dipalladium, and the phosphine ligand is 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl.

7. The method for preparing the cyano-quinoxalin-based n-type polymer semiconductor material according to claim 6, characterized in that, The palladium catalyst accounts for a portion of the compound. The total molar ratio of the tin compound is 1-5%; the phosphine ligand constitutes a significant portion of the compound. 2-10% of the total molar ratio of tin compounds; The palladium catalyst accounts for a portion of the compound. The total molar ratio of the tin compound is 1-5%; the phosphine ligand constitutes a significant portion of the compound. The total molar ratio of tin compounds is 2-10%.

8. The method for preparing the cyano-quinoxalin-based n-type polymeric semiconductor material according to claim 5, characterized in that, The compound The preparation method includes the following steps: compound With compounds The reaction was carried out in an acidic solvent to give the compound. The acidic solvent is trifluoroacetic acid.

9. The method for preparing the cyano-quinoxalin-based n-type polymeric semiconductor material according to claim 5, characterized in that, The compound The preparation method includes the following steps: compound With compounds The reaction was carried out in an acidic solvent to give the compound. The acidic solvent is acetic acid.

10. The application of a cyano-quinoxalin-based n-type polymeric semiconductor material as described in any one of claims 1-4 in organic field-effect transistors or organic thermoelectrics.

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