Semiconductor polymers and their preparation methods and applications, semiconductor-doped composites and their applications

Abstract

The present application provides a semiconductor polymer, a preparation method and application thereof, a semiconductor doped composite and application thereof. The general structural formula of the semiconductor polymer is: #imgabs0#R is an alkyl group, A1 is a nitrogen-containing first electron acceptor unit, A2 is a nitrogen-containing second electron acceptor unit, the structures of A1 and A2 are different, and n is a positive integer. The semiconductor polymer provided in the present application is a bipolar semiconductor material having both p-type and n-type transport properties. At the same time, the semiconductor polymer introduces a quinone pyrazine structure into the main chain of the dual-acceptor polymer molecule. The quinone pyrazine structure has multiple active sites and is highly stable, which can support the modification of the dual-acceptor polymer structure. This makes the semiconductor polymer not only extremely easy to achieve effective chemical doping, but also highly compatible with different types of chemical dopants.

Description

Technical Field

[0001] The present application belongs to the technical field of organic semiconductor materials, and more specifically, relates to semiconductor polymers and preparation methods and applications thereof, and semiconductor doped composites and applications thereof. Background Art

[0002] Semiconducting polymers have attracted considerable attention due to their wide applications in organic field-effect transistors (OFETs), organic photovoltaics (OPVs), and other electronic devices. Compared to inorganic semiconductors, organic semiconducting polymers possess unique solution processability and are poised to play a leading role in cutting-edge applications such as flexible wearables, implantable devices, electronic skin, and artificial intelligence.

[0003] However, the carrier concentration of organic semiconductor polymers is exponentially lower than that of inorganic semiconductors. Besides modifying the molecular structure to adjust the frontier orbital energy levels to achieve high carrier mobility, chemical doping is the most effective method for exponentially enhancing the carrier concentration of organic semiconductor polymers, compensating for their carrier concentration deficit.

[0004] Quinone units have unique structural advantages in promoting molecular orbital hybridization, enhancing intermolecular forces, and facilitating molecular self-assembly. Consequently, conjugated polymers containing quinone units are gaining increasing attention and are currently recognized as the most suitable chemical structure for organic semiconducting polymers. However, the currently widely used quinone configuration suffers from low stability, and the resulting organic semiconducting polymers struggle to achieve efficient chemical doping, significantly limiting their potential in cutting-edge applications. Summary of the Invention

[0005] Based on this, one purpose of the present application is to provide a semiconductor polymer to solve the technical problems in the prior art that the currently widely used quinone configuration has low stability and the corresponding organic semiconductor polymer is difficult to achieve efficient chemical doping effects, thus greatly restricting the role that organic semiconductor polymers can play in cutting-edge applications.

[0006] Another object of the present application is to provide a method for preparing the above-mentioned semiconductor polymer.

[0007] Another object of the present application is to provide a semiconductor-doped composite containing the above-mentioned semiconductor polymer.

[0008] Another object of the present application is to provide applications of the semiconductor doping composite.

[0009] To achieve the above objectives, the technical solution adopted in this application is:

[0010] A semiconductor polymer, the general structural formula of the semiconductor polymer is:

[0011]

[0012] R is an alkyl group, A1 is a nitrogen-containing first electron acceptor unit, A2 is a nitrogen-containing second electron acceptor unit, A1 and A2 have different structures, and n is a positive integer.

[0013] Optionally, R is a C1-C60 alkyl group.

[0014] Optionally, A1 is any one of the following structural formulas:

[0015] and / or,

[0016] A2 is any one of the following structural formulas:

[0017]

[0018] And, a method for preparing a semiconductor polymer, for preparing any of the semiconductor polymers described above, the preparation method comprising the following steps:

[0019] S10: Under the protection of an inert gas, compound I and a halogenated alkane are mixed to carry out a nucleophilic addition reaction of the carbonyl group to obtain a mixture B, wherein the mixture B contains compound II;

[0020] The structure of compound I is:

[0021]

[0022] The structural formula of halogenated alkanes is X1-R, where X1 is bromine or iodine and R is an alkyl group;

[0023] The structure of compound II is:

[0024]

[0025] S20: Under inert gas protection, mixing mixture B with the first catalyst, adding trimethyltin chloride solution or tributyltin chloride under cooling and stirring conditions to carry out a substitution reaction to obtain mixture C, wherein mixture C contains compound III;

[0026] The structure of compound III is:

[0027] or

[0028] S30: Under inert gas protection, the mixture C, X2-A1-A2-A1-X2, tris(dibenzylideneacetone)dipalladium and tri(o-methylphenyl)phosphine are mixed and polymerized to obtain a mixture D; X2 in X2-A1-A2-A1-X2 is bromine or iodine;

[0029] S40: Purifying the mixture D to obtain a semiconductor polymer.

[0030] Optionally, before step S20, the following steps are further included:

[0031] Purifying the mixture B to obtain compound II;

[0032] The mixture B in step S20 is replaced by compound II; and / or,

[0033] Step S20 satisfies at least one of the following conditions:

[0034] The first catalyst is an alkyl lithium catalyst;

[0035] The cooling temperature is -78℃ to -85℃.

[0036] Optionally, before step S30, the following steps are further included:

[0037] Purifying the mixture C to obtain compound III;

[0038] The mixture C in step S30 is replaced by compound III; and / or,

[0039] The reaction temperature of the polymerization reaction is 85°C-145°C.

[0040] And, application of the above-mentioned semiconductor polymer in field effect transistor devices.

[0041] And, a semiconductor doped composite comprises a dopant and any of the semiconductor polymers described above, wherein the dopant is any one of an ionic dopant, a p-type dopant and an n-type dopant.

[0042] Optionally, the dopant includes any one of Zn(C6F5)2, TBAI, and TeNF.

[0043] And, application of the semiconductor doping compound in field effect transistor devices.

[0044] The beneficial effects of this application are:

[0045] 1. The semiconducting polymer provided in this application is a bipolar semiconductor material with both p-type and n-type transport properties. The semiconducting polymer introduces a quinone pyrazine structure into the main chain of the dual-receptor polymer molecule. The quinone pyrazine structure has multiple active sites and is highly stable, which can support the modification of the dual-receptor polymer structure. This makes the semiconducting polymer not only extremely easy to achieve effective chemical doping, but also highly compatible with different types of chemical dopants. Compared with the prior art, the semiconducting polymer of this application is a bipolar semiconductor material with strong stability, can achieve effective doping, and is compatible with a variety of chemical dopants, which is conducive to the semiconductor polymer playing a wide range of roles in cutting-edge applications.

[0046] 2. The preparation method of the semiconducting polymer provided in this application rationally designs the reaction process of each step based on the structural characteristics and material properties, resulting in a simple synthesis path and strong operational feasibility;

[0047] 3. The semiconducting polymers provided in this application can be applied to field-effect transistor devices. Especially when used in combination with dopants, they can effectively increase the carrier concentration and carrier mobility, thereby improving the electrical performance of the device.

[0048] 4. The semiconductor doped composite provided in this application is a bipolar semiconductor material that is highly compatible with three types of dopants, namely ionic dopants, p-type dopants and n-type dopants. The semiconductor polymer doped with each type of dopant can greatly improve the carrier mobility and achieve effective doping. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] The present invention will be further described below with reference to the accompanying drawings and embodiments, in which:

[0050] Figure 1 is the hydrogen spectrum of compound II in Example 1;

[0051] Figure 2 is the carbon spectrum of compound II in Example 1;

[0052] Figure 3 is the hydrogen spectrum of compound III of Example 1;

[0053] Figure 4 is the carbon spectrum of compound III of Example 1;

[0054] Figure 5 This is the hydrogen spectrum of the comonomer 3,6-bis(5-bromopyridine-2-)-2,5-bis(2-octyldodecyl)-2,5-dihydropyrrolo[3,4-o]pyrrole-1,4-dione of Example 1;

[0055] Figure 6The carbon spectrum of the comonomer 3,6-bis(5-bromopyridine-2-)-2,5-bis(2-octyldodecyl)-2,5-dihydropyrrolo[3,4-o]pyrrole-1,4-dione of Example 1;

[0056] Figure 7 This is a structural diagram of a semiconductor polymer applied to a field effect transistor device;

[0057] Figure 8 A diagram showing the structure of a field effect transistor device using a semiconductor doping compound;

[0058] Figure 9 This is a performance test diagram of the undoped and doped semiconductor polymer of Example 1 applied to a field effect transistor device. DETAILED DESCRIPTION

[0059] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, this application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0060] The present invention provides a semiconductor polymer, the general structural formula of which is:

[0061]

[0062] R is an alkyl group, A1 is a nitrogen-containing first electron acceptor unit, A2 is a nitrogen-containing second electron acceptor unit, A1 and A2 have different structures, and n is a positive integer.

[0063] The semiconductor polymer provided in the embodiments of the present application is a bipolar semiconductor material having both p-type and n-type semiconductor transport properties. The semiconductor polymer in the embodiments of the present application introduces a quinone pyrazine structure into the main chain of the dual-acceptor polymer molecule. A1 and A2 are both nitrogen-containing electron acceptor units. The quinone pyrazine structure has multiple active sites and is highly stable, which can support the modification of the dual-acceptor polymer structure. This makes the semiconductor polymer not only extremely easy to achieve effective chemical doping, but also highly compatible with different types of chemical dopants.

[0064] Optionally, R is a C1-C60 alkyl group. If the carbon number of the R alkyl group is too large, for example, greater than C60, it will produce significant steric hindrance, affecting the synthesis reaction and the solubility of the semiconducting polymer, and thus affecting the application of the semiconducting polymer. Therefore, R can be a C1-C60 alkyl group, which can be a linear alkyl group or a branched alkyl group.

[0065] Optionally, A1 is any one of the following structural formulas:

[0066]

[0067] Optionally, A2 is any one of the following structural formulas:

[0068]

[0069] A1 and A2 are nitrogen-containing heterocyclic compounds respectively. The formed -A1-A2-A1- can form a stable main chain with the quinone pyrazine structure and can be easily doped with different types of dopants, thereby exhibiting a bipolar semiconductor material.

[0070] Compared with the prior art, the semiconductor polymer of the embodiment of the present application is a bipolar semiconductor material with strong stability, can achieve effective doping, and is compatible with various types of chemical dopants, which is conducive to the semiconductor polymer playing a wide range of roles in cutting-edge applications.

[0071] The present invention also provides a method for preparing the semiconductor polymer, comprising the following steps:

[0072] S10: Under the protection of an inert gas, compound I and a halogenated alkane are mixed to carry out a nucleophilic addition reaction of the carbonyl group to obtain a mixture B, wherein the mixture B contains compound II;

[0073] The structure of compound I is:

[0074]

[0075] The structural formula of halogenated alkanes is X1-R, where X1 is bromine or iodine and R is an alkyl group;

[0076] The structure of compound II is:

[0077]

[0078] Alternatively, the preparation method of Compound I comprises the following steps:

[0079] S11: Under the protection of an inert gas, 1,4-diacetylpiperazine-2,5-dione and 5-bromo-2-formylthiophene are dissolved in a first solvent, a basic amine catalyst is added under heating conditions, the mixture is reacted under heat preservation and stirring conditions, and the mixture is cooled to obtain a mixture A;

[0080] S12: The mixture A is filtered, washed and dried to obtain compound I.

[0081] The purpose is to synthesize compound I containing a quinone pyrazine structural unit and provide a reaction raw material with a quinone pyrazine structure for subsequent synthetic reactions.

[0082] The first solvent can be selected from anhydrous N,N-dimethylformamide. 1,4-diacetylpiperazine-2,5-dione and 5-bromo-2-formylthiophene have high solubility in N,N-dimethylformamide, and N,N-dimethylformamide does not participate in the reaction during the process, providing a good liquid environment for the synthesis reaction.

[0083] Optionally, the basic amine catalyst is any one of piperidine, pyridine, quinoline, primary amine and secondary amine.

[0084] The method of adding the basic amine catalyst is:

[0085] Under heating conditions, add the basic amine catalyst dropwise.

[0086] The main function of adding alkaline amine catalysts dropwise is to regulate the reaction rate, avoid excessive reaction, difficulty in controlling the reaction process, side reactions that generate impurities, or cause personal injury and other problems.

[0087] Optionally, the heating temperature is 115° C.-130° C., which provides sufficient energy for the synthesis reaction and does not cause the reaction to be too intense.

[0088] After the reaction is completed, the mixture is cooled to room temperature to obtain mixture A.

[0089] Mixture A contains compound I, which exists in the form of a solid. Solid-liquid separation is achieved by filtration to obtain a solid compound I, which is then washed with a detergent to remove soluble impurities, and then dried in a vacuum drying oven to obtain purified compound I.

[0090] The detergent for the washing treatment can be acetone. 1,4-diacetylpiperazine-2,5-dione and 5-bromo-2-formylthiophene are soluble in acetone, while the generated compound I is insoluble in acetone, and the unreacted raw materials can be removed.

[0091] Optionally, in step S10, during the reaction, compound I and alkyl halide are dissolved in a second solvent, and a nucleophilic addition reaction of the carbonyl group is carried out in an alkaline environment under heating and stirring conditions, and after cooling, a mixture B is obtained.

[0092] Optionally, the second solvent is anhydrous N,N-dimethylformamide. Compound I and halogenated alkane have good solubility in N,N-dimethylformamide, and N,N-dimethylformamide does not participate in the synthesis reaction, thus providing a good solution environment.

[0093] Optionally, the alkaline environment is formed by adding an anhydrous alkaline compound, and the alkaline compound can be any one of potassium carbonate, potassium phosphate, potassium tert-butoxide, sodium tert-butoxide, sodium hydroxide and potassium hydroxide.

[0094] The heating temperature for nucleophilic addition is 95°C-105°C, which provides sufficient energy for the nucleophilic addition reaction and the reaction will not be too intense.

[0095] After the reaction is completed, the mixture is cooled to room temperature to obtain a mixture B containing compound II, which is the target intermediate product.

[0096] Optionally, after obtaining the mixture B, the mixture B is further purified to obtain compound II, thereby removing impurities to prevent the impurities from affecting further reactions and product yield.

[0097] Optionally, the method for purifying the mixture B comprises the following steps:

[0098] The mixture B was filtered and concentrated by evaporation to obtain a mixture B1;

[0099] The mixture B1 was purified by column chromatography using n-hexane as the eluent to obtain a mixture B2;

[0100] The mixture B2 was recrystallized in anhydrous methanol to obtain compound II.

[0101] Silica gel columns can be used for column chromatography, which has good separation effects.

[0102] S20: Under inert gas protection, mixing mixture B with the first catalyst, adding trimethyltin chloride solution or tributyltin chloride under cooling and stirring conditions to carry out a substitution reaction to obtain mixture C, wherein mixture C contains compound III;

[0103] The structure of compound III is:

[0104] or

[0105] It can be understood that if the mixture B is purified, the mixture B in step S20 is replaced by the compound II obtained by the purification process to increase the reaction rate and reduce side reactions.

[0106] Optionally, compound II is first mixed with a third solvent to form a solution of compound II, and the first catalyst is added under cooling and stirring conditions, followed by adding trimethyltin chloride solution or tributyltin chloride. The temperature is then raised to room temperature and a substitution reaction is carried out under stirring to obtain mixture C.

[0107] Optionally, the third solvent is extra dry tetrahydrofuran.

[0108] Optionally, the first catalyst is an alkyllithium catalyst, which may be, for example, n-butyllithium or tert-butyllithium. Since tert-butyllithium is relatively active and easily ignites when exposed to air, n-butyllithium is preferred for safety reasons.

[0109] During application, the alkyl lithium is dissolved in a hexane solvent to prepare an alkyl lithium hexane solution. The concentration of the alkyl lithium hexane solution can be selected to be 1.0 mol / L-2.5 mol / L.

[0110] Since alkyl lithium is active and easily reactive, in some embodiments, alkyl lithium is added dropwise to regulate the reaction rate and avoid situations such as excessive reaction, difficulty in controlling the reaction process, and the generation of side reactions.

[0111] Optionally, the cooling temperature is -78°C to -85°C, that is, the first catalyst, trimethyltin chloride solution or tributyltin chloride are added at a low temperature of -78°C to -85°C to avoid violent reaction and splashing of the solution after the first catalyst, trimethyltin chloride solution or tributyltin chloride are added.

[0112] The trimethyltin chloride solution is a solution prepared with hexane as a solvent, and the concentration of the trimethyltin chloride is in the range of 1.0 mol / L-1.5 mol / L.

[0113] Add trimethyltin chloride solution or tributyltin chloride, then raise the temperature to room temperature and react under stirring for 10-14 hours.

[0114] After the reaction is completed, deionized water is added to quench the reaction to obtain a mixture C. The mixture C has an inorganic phase and an organic phase, and compound III is dissolved in the organic phase.

[0115] Optionally, after obtaining the mixture C, the mixture C is further purified to obtain compound III, so as to remove impurities and prevent the impurities from affecting the reactions in subsequent steps.

[0116] Optionally, the method for purifying the mixture C comprises the following steps:

[0117] The organic phase in the mixture C was dried with anhydrous sodium sulfate and evaporated to obtain a solid substance C1;

[0118] The solid substance C1 was recrystallized from anhydrous methanol to obtain compound III.

[0119] S30: Under the protection of inert gas, the mixture C, X2-A1-A2-A1-X2, tris(dibenzylideneacetone)dipalladium and tri(o-methylphenyl)phosphine are mixed and a polymerization reaction is carried out to obtain a mixture D; X2 in X2-A1-A2-A1-X2 is bromine or iodine.

[0120] It can be understood that if the mixture C is purified, the mixture C in step S30 is replaced by compound III, thereby reducing impurities and side reactions.

[0121] Alternatively, compound III, X2-A1-A2-A1-X2, tris(dibenzylideneacetone)dipalladium and tri(o-methylphenyl)phosphine are dissolved in a fourth solvent and mixed, and then a polymerization reaction is carried out under heating and stirring conditions to obtain a mixture D.

[0122] Optionally, the fourth solvent is ultra-dry toluene.

[0123] Optionally, the polymerization reaction is heated at a temperature of 85° C.-145° C. to provide sufficient energy for the reaction and promote the reaction to proceed in the forward direction.

[0124] S40: Purifying the mixture D to obtain a semiconductor polymer.

[0125] Optionally, the method for purifying the mixture D comprises the following steps:

[0126] The mixture D was added to anhydrous methanol to precipitate a precipitate, and solid D1 was obtained by solid-liquid separation.

[0127] Solid D1 was extracted with anhydrous methanol, acetone, and n-hexane in sequence using a Soxhlet extractor to remove impurities to obtain a semiconductor polymer.

[0128] The inert gas in each of the above steps can be nitrogen or argon, etc., to protect the synthesis process from being exposed to the air, so as to prevent the raw materials or intermediates from being oxidized and affecting the normal progress of the synthesis reaction.

[0129] In one embodiment, the first solvent and the second solvent are DMF, the alkaline amine catalyst is triethylamine, the anhydrous alkaline substance is potassium carbonate, the third solvent is tetrahydrofuran, the fourth solvent is ultra-dry toluene, and the alkyl lithium is n-butyl lithium. The reaction equations of steps S10-S40 of the preparation method are as follows:

[0130]

[0131] The preparation method of the semiconductor polymer provided in the embodiment of the present application rationally designs the reaction process of each step according to the structural characteristics and material properties, and the synthesis path is simple and the operation feasibility is strong.

[0132] The above-mentioned semiconductor polymer can be applied to field effect transistor devices, especially when used in combination with dopants, which can effectively increase the carrier concentration and carrier mobility, thereby improving the electrical performance of the device.

[0133] An embodiment of the present application further provides a semiconductor doped composite, comprising a dopant and any of the semiconductor polymers described above, wherein the dopant is any one of an ionic dopant, a p-type dopant, and an n-type dopant.

[0134] Dopants can be incorporated into semiconductor polymers through conventional doping methods, and the conductive properties can be significantly improved.

[0135] Optionally, the dopant includes any one of Zn(C6F5)2, TBAI, and TeNF, where TBAI, Zn(C6F5)2, and TeNF are ionic dopants, p-type dopants, and n-type dopants, respectively.

[0136] The semiconductor doped composite provided in the embodiments of the present application is a bipolar semiconductor material that is highly compatible with three types of dopants, namely ionic dopants, p-type dopants and n-type dopants. The semiconductor polymer doped with each type of dopant can significantly improve the carrier mobility and achieve effective doping. It can be applied to field effect transistor devices to improve the electrical performance of field effect transistor devices.

[0137] The following examples are used to illustrate this.

[0138] Example 1

[0139] The structural formula of the semiconducting polymer of this embodiment is:

[0140]

[0141] The method for preparing the semiconducting polymer of this embodiment comprises the following steps:

[0142] S1: Under nitrogen gas protection, in a 100-ml three-necked reaction flask, 1.98 g of 1,4-diacetylpiperazine-2,5-dione and 4.78 g of 5-bromo-2-formylthiophene were dissolved in 50 ml of anhydrous N,N-dimethylformamide solution to obtain a reaction mixture I. The reaction mixture I was heated to 120° C., and 4.05 g of triethylamine was added dropwise to the reaction flask. The reaction was carried out at 120° C. with stirring for about 12 hours, and then cooled to room temperature to obtain a mixture A.

[0143] S2: The mixture A was filtered, and the solid obtained by filtration was washed three times with acetone, and then dried in a vacuum drying oven to obtain 4.15 g of compound I (yield: 90.19%).

[0144] S3: Under nitrogen gas protection, in a 100-ml three-necked reaction flask, 1.15 g of compound I, 1.93 g of 2-ethylhexyl bromide and 1.73 g of anhydrous potassium carbonate were dissolved in 50 ml of anhydrous N,N-dimethylformamide solution to obtain a reaction mixture II. The reaction mixture II was heated to 100°C and kept stirring uniformly to carry out the reaction. After about 12 hours, it was cooled to room temperature to obtain a mixture B.

[0145] S4: Filter the mixture B, evaporate and concentrate the filtrate, and then purify it by column chromatography using n-hexane as the eluent using a silica gel column. Subsequently, recrystallize it in anhydrous methanol to obtain 1.05 g of pure compound II (yield: 61.35%).

[0146] The hydrogen spectrum and carbon spectrum of compound II are as follows: Figure 1 and Figure 2 As shown, the structure of compound II was confirmed by H NMR and C NMR, and the results were as follows: H spectrum (400 MHz, deuterated chloroform), chemical shift (ppm), 7.06–6.99 (m, 6H), 4.44–4.35 (m, 4H), 1.93–1.86 (m, 2H), 1.62–1.36 (m, 16H), 1.00 (t, J = 7.2, 7.6 Hz, 6H), 0.94 (t, J = 6.8, 7.2 Hz, 6H). Carbon spectrum (101 MHz, deuterated chloroform), chemical shift (ppm), 157.88, 140.66, 129.94, 129.20, 128.56, 118.72, 116.46, 70.88, 38.59, 30.74, 29.04, 24.15, 23.20, 14.19, 11.15.

[0147] S5: Under nitrogen gas protection, 1.05 g of compound II was placed in a 100 ml ultra-dry three-necked reaction flask, and 30 ml of ultra-dry tetrahydrofuran solvent was added to obtain a reaction mixture III. After the reaction mixture III was cooled to -78°C, 1.35 ml of a 2.5 M n-butyl lithium hexane solution was added dropwise to the reaction mixture III, followed by stirring at -78°C for 2 hours. Then, 3.83 ml of a 1 M trimethyltin chloride hexane solution was injected into the three-necked reaction flask at one time, the reaction temperature was gradually raised to room temperature, and the reaction was stirred for about 12 hours. Deionized water was added to quench the reaction to obtain a mixture C.

[0148] S6: Extract the mixture C, dry the organic phase obtained by extraction with anhydrous sodium sulfate, and then evaporate and concentrate. Recrystallize the solid obtained by evaporation and concentration with anhydrous methanol to obtain 910 mg of pure compound III (yield: 69.77%).

[0149] The hydrogen spectrum and carbon spectrum of compound III are as follows: Figure 3 and Figure 4 As shown, the structure of compound III was confirmed by H NMR and C NMR, and the results were as follows: H spectrum (400 MHz, deuterated chloroform), chemical shift (ppm), 7.40 (d, J = 3.2 Hz, 2H), 7.20 (s, 2H), 7.18 (d, J = 3.2 Hz, 2H), 4.50 (dd, J = 10.8, 6.0 Hz, 2H), 4.42 (dd, J = 10.8, 6.4 Hz, 2H), 1.96–1.84 (m, 2H), 1.59–1.34 (m, 16H), 1.01 (t, J = 7.2 Hz, 6H), 0.95 (d, J = 6.8 Hz, 6H), 0.39 (s, 18H). Carbon spectrum (101 MHz, deuterated chloroform), chemical shift (ppm), 158.06, 144.78, 144.65, 134.50, 131.31, 128.49, 115.86, 70.48, 38.78, 30.78, 29.08, 24.16, 23.12, 14.16, 11.17, -8.35.

[0150] S7: Under nitrogen gas protection, in a 50-ml ultra-dry single-necked reaction bottle, 127.9 mg of compound III, 151.4 mg of 3,6-bis(5-bromopyridine-2-)-2,5-di(2-octyldodecyl)-2,5-dihydropyrrolo[3,4-and]pyrrole-1,4-dione, 2.75 mg of tris(dibenzylideneacetone)dipalladium and 7.30 mg of tris(o-methylphenyl)phosphine were dissolved in 10 ml of ultra-dry toluene solvent to obtain a reaction mixture IV. The reaction mixture IV was heated to 110° C. and stirred for 8 hours, and then cooled to room temperature to obtain a mixture D.

[0151] S8: Pour mixture D into 250 ml of anhydrous methanol to precipitate and obtain a solid-liquid mixture. Filter the solid-liquid mixture, add the filtered solid to a Soxhlet extractor, and use anhydrous methanol, acetone, and n-hexane to remove impurities in sequence. Finally, use chloroform to obtain 160 mg of the target semiconductor polymer (yield 77.51%).

[0152] The molecular weight and molecular weight distribution of the semiconducting polymer were confirmed by GPC, and the results were as follows: the number average molecular weight was 60.992 kg / mole, and the distribution coefficient was 1.61.

[0153] The semiconductor polymer prepared in Example 1 was divided into four groups. The first group was not doped, and the second, third, and fourth groups were doped with TBAl, Zn(C6F5)2, and TeNF, respectively, to obtain one group of semiconductor polymers and three groups of semiconductor-doped composites. These semiconductor polymers and semiconductor-doped composites were applied to field-effect transistor devices, respectively. The structures of the field-effect transistor devices are shown in FIG. Figure 7 and Figure 8 shown.

[0154] The performance tests of the above field effect transistor devices were carried out respectively, and the test results are as follows Figure 9 and as shown in Table 1.

[0155]

[0156] Depend on Figure 9 As can be seen from the test results in Table 1, the hole mobility and electron mobility of the doped semiconductor polymer are significantly improved compared with the undoped semiconductor polymer, especially the improvement in electron mobility is very significant. TBAl, Zn(C6F5)2, and TeNF are ionic dopants, p-type dopants, and n-type dopants, respectively. That is, the semiconductor polymer of the embodiment of the present application can be effectively doped with three types of dopants, and the carrier mobility is significantly improved after doping, and it has hole transport and electron transport properties.

[0157] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A semiconducting polymer, characterized in that: The general structural formula of the semiconductor polymer is: R is an alkyl group, A1 is a nitrogen-containing first electron acceptor unit, A2 is a nitrogen-containing second electron acceptor unit, A1 and A2 have different structures, and n is a positive integer; Said A1 is any one of the following structural formulas: and / or, Said A2 is any one of the following structural formulas:

2. The semiconducting polymer according to claim 1, wherein: The R is a C1-C60 alkyl group.

3. A method for preparing a semiconducting polymer, characterized in that: For preparing the semiconducting polymer according to claim 1 or 2, the preparation method comprises the following steps: S10: Under the protection of an inert gas, compound I and a halogenated alkane are mixed to carry out a nucleophilic addition reaction of the carbonyl group to obtain a mixture B, wherein the mixture B contains compound II; The structure of the compound I is: The structural formula of the halogenated alkane is X1-R, wherein X1 is bromine or iodine, and R is an alkyl group; The structure of the compound II is: S20: Under inert gas protection, mixing the mixture B with the first catalyst, adding trimethyltin chloride solution or tributyltin chloride under cooling and stirring conditions to carry out a substitution reaction to obtain a mixture C, wherein the mixture C contains compound III; The structure of the compound III is: or S30: Under inert gas protection, the mixture C, X2-A1-A2-A1-X2, tris(dibenzylideneacetone)dipalladium and tri(o-methylphenyl)phosphine are mixed to carry out a polymerization reaction to obtain a mixture D; wherein X2 in the X2-A1-A2-A1-X2 is bromine or iodine; S40: Purifying the mixture D to obtain the semiconductor polymer.

4. The method for preparing a semiconducting polymer according to claim 3, wherein: Before step S20, the following steps are also included: Purifying the mixture B to obtain compound II; The mixture B in step S20 is replaced by the compound II; and / or, Step S20 satisfies at least one of the following conditions: The first catalyst is an alkyl lithium catalyst; The cooling temperature is -78°C to -85°C.

5. The method for preparing a semiconducting polymer according to claim 3, wherein: Before step S30, the following steps are also included: Purifying the mixture C to obtain the compound III; The mixture C in step S30 is replaced by the compound III; and / or, The reaction temperature of the polymerization reaction is 85°C-145°C.

6. Use of the semiconducting polymer according to claim 1 or 2 in a field effect transistor device.

7. A semiconductor doped composite, characterized in that: The invention comprises a dopant and the semiconductor polymer according to claim 1 or 2, wherein the dopant is any one of an ionic dopant, a p-type dopant and an n-type dopant.

8. The semiconductor doped composite according to claim 7, wherein: The dopant includes any one of Zn(C6F5)2, TBAI, and TeNF.

9. Use of the semiconductor doped composite according to claim 7 or 8 in a field effect transistor device.

Images