A polymer based on beta-position cyano-substituted thiophene and its preparation method and application
Patent Information
- Application Number
- CN202510363915.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-26
- Publication Date
- 2026-09-29
AI Technical Summary
[0005]传统的强耦合的D-A体系往往因为形成强的电荷转移态激子，电荷分离很难发生
[0044]本发明通过在噻吩给体单元β位点上引入氰基单元，通过调控D/A部分的给受电子能力、扭曲角度、组成比例、环境介质等因素来调节耦合程度，获得以下方面的效果：
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of semiconductor material preparation technology, specifically relating to the design and synthesis of a novel donor dicyanothiophene unit and a series of electron transport polymer semiconductor materials based on dicyanothiophene, their preparation methods, and their applications in organic phototransistors. Background Technology
[0002] With in-depth research and the development of new materials, fields such as organic flexible electronics, energy conversion, and high-efficiency sensing have experienced rapid development. n-type organic semiconductor materials play an irreplaceable role in modern electronics and optoelectronics technologies. Currently, a large number of DA conjugated polymers with a main chain backbone composed of alternating donor and acceptor units have been successfully synthesized and used in optoelectronic application research. Thiophene units and their derivatives, in particular, represent almost the entire range of selectable donor units.
[0003] Because DA conjugated polymers possess relatively high highest occupied orbital (HOMO) levels, they tend to exhibit p-type or bipolar transport characteristics. To address this issue, a strategy has been developed to construct DA polymers with weak D units, which help maintain lower HOMO levels. Typically, introducing electron-withdrawing groups into the electron-donating moiety can transfer weak D units. Compared to the widely studied fluorine and chlorine-substituted weak donor units, β-cyano-substituted thiophene derivatives have been relatively neglected. The cyano group is a more potent electron-withdrawing group; introducing it into the polymer can lower the frontier orbital level, modulating the polymer's band gap and charge density. Furthermore, thiophene derivatives obtained by introducing a strong electron-withdrawing group at the β-position of thiophene exhibit high direct arylation activity in their α-H bonds, and the cyano group can adjust the planarity of the copolymer. Therefore, β-cyano-substituted thiophene derivatives can serve as CH-activated monomers, enabling the direct arylation condensation polymerization of high-performance conjugated polymers.
[0004] Organic phototransistors (OPTs) have attracted much attention due to their wide application in fluorescence imaging, medical monitoring, and optical communication. As an important optoelectronic device, OPTs offer advantages such as low dark current, low noise response, and high photosensitivity. In traditional phototransistors, the photoactive layer typically employs a heterogeneous thin film composed of multiple components. This structure utilizes the different electron affinity and ionization potentials between the donor and acceptor components to drive exciton separation. In contrast, achieving both good photosensitivity and carrier transport performance using only a single active layer material is extremely rare. This is mainly because organic semiconductor materials have weak intermolecular forces and low dielectric constants, resulting in tightly bound electron-hole pairs after photon absorption. Strong Coulomb interactions make it difficult for these electron-hole pairs to spontaneously dissociate into freely moving carriers.
[0005] Traditional strongly coupled DA systems often suffer from charge separation difficulties due to the formation of strong charge-transfer excitons. Therefore, design strategies are needed to weaken this coupling effect, thereby enabling the synthesis of single-component active layer materials. Summary of the Invention
[0006] The purpose of this invention is to provide an n-type organic semiconductor polymer semiconductor material based on dicyanothiophene. The polymer provided by this invention exhibits a lower energy level and excellent air stability. The polymer is synthesized using a direct arylation polycondensation method, which features high atom utilization and mild reaction conditions. The resulting polymer material can be further fabricated into a single-component organic phototransistor, possessing both high electron mobility and significant photoresponse characteristics, overcoming the fabrication bottleneck of traditional heterojunction devices. Furthermore, it can be fabricated into a bottom-gate, bottom-contact structure device, which, under visible light modulation, can simulate neural synaptic plasticity, achieving functions such as short-term to long-term memory conversion.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] In a first aspect, the present invention provides an n-type conjugated polymer containing a dicyanothiophene structure, the structure of which is shown in Formula II:
[0009]
[0010] In Formula II:
[0011] A is an electron acceptor group, which has one of the following structures:
[0012]
[0013] in:
[0014] X1 represents a substituent group consisting of H, F, or Cl atoms;
[0015] X2 represents a heteroatom-conjugated aromatic ring, a fused ring formed by heteroatoms, a thiophene group, a selenophene group, a pyridine group, a furan group, a thiazole group, or a thiophene group; the heteroatoms are O, S, or Se;
[0016] R represents a straight-chain or branched alkyl, alkoxy, alkylthio, or silyl group having 1-28 carbon atoms;
[0017] n represents the degree of aggregation, and is a natural number ranging from 10 to 40.
[0018] Furthermore, the polymer is selected from one or more of the following structures:
[0019]
[0020] Secondly, the present invention also provides a method for preparing the above-mentioned polymer, comprising the following steps:
[0021] S1,3,6-dibromothiophene[3,2-B]thiophene reacts with CuCN to give a cyano-substituted intermediate;
[0022] S2, the cyano-substituted intermediate, and monomer A undergo an arylation polycondensation reaction in a Pd2(dba)3 / CuI catalytic system; wherein monomer A is a brominated monomer of compounds A1-A6, which can be represented as follows:
[0023] S3. The reaction solution obtained in step S2 is subjected to gradient purification to obtain an n-type conjugated polymer containing a dicyanothiophene structure.
[0024] The synthesis route is as follows:
[0025]
[0026] In step S1, the reaction conditions are: temperature 135-145℃ and time 11-13h.
[0027] Step S1 also includes post-treatment; the post-treatment process is carried out as follows: after the reaction is complete, excess water is added to quench the reaction, and after stirring for a period of time, the precipitate is filtered; the crude product is washed with water, then extracted with a dichloromethane / water system to separate the organic phase, dried with magnesium sulfate, filtered, and then evaporated to dryness before column chromatography; the eluent is n-hexane:dichloromethane = 1:1, to obtain a pale yellow solid 2CNTT, whose structural formula is [insert structural formula here].
[0028] In step S2, the Pd2(dba)3 / CuI catalytic system comprises: 0.02 equivalents of tris(dibenzylacetone)dipalladium (Pd2(dba)3), 0.2 equivalents of cuprous iodide (CuI), 0.08 equivalents of tris(3-methoxyphenyl)phosphine (P(o-OMePh)3), 0.3 equivalents of pentylene acid (PivOH), and 3 equivalents of cesium carbonate (Cs2CO3).
[0029] The reaction conditions are as follows: dry environment, ultra-dry toluene as solvent, reaction temperature at toluene reflux temperature (90-140℃), and time of 6-72h.
[0030] In step S3, the gradient purification involves Soxhlet extraction with methanol, acetone, n-hexane, ethyl acetate, and chloroform in sequence. Further purification with chlorobenzene is performed after the chloroform purification.
[0031] Step S3 further includes: precipitating the components dissolved in chloroform and chlorobenzene into methanol, filtering, and vacuum drying to obtain polymers of the corresponding components.
[0032] Thirdly, the present invention also provides an organic phototransistor device, comprising a single-component active layer; the single-component active layer is formed from one or more of the above-mentioned polymers.
[0033] The single-component active layer can achieve the regulation of source and leakage current by light intensity and wavelength without the need for blending with other materials or adding additives.
[0034] The organic phototransistor device described above exhibits photoresponsivity and electron mobility under 400-700nm visible light illumination.
[0035] As a specific embodiment of the present invention, the organic phototransistor device has a bottom-gate bottom-contact structure, comprising: an n-type doped Si wafer substrate (gate); a 300nm SiO2 dielectric layer; an OTS-modified surface; a spin-coated polymer semiconductor layer (thickness 50-500nm); and patterned gold source / drain electrodes (30nm Au / 3nm Ti).
[0036] The fabrication method of the above-mentioned organic phototransistor device includes the following steps:
[0037] (1) Select n-type heavily doped Si wafer as substrate, which contains a 300nm thick SiO2 dielectric layer and bottom gate electrode;
[0038] (2) A 30 nm thick Au source and drain electrode was patterned on the surface of the dielectric layer SiO2 using photolithography, and a 3 nm thick Ti film was used as the adhesion layer to obtain the substrate.
[0039] (3) After the substrate was cleaned with Piranha solution and cooled to room temperature, it was cleaned with deionized water, acetone and isopropanol in sequence and dried with N2. Then it was baked in a vacuum drying oven at 80°C for 1 hour. After being treated with O2 plasma, octadecyltrichlorosilane (OTS) was added dropwise and reacted at 120°C for 3 hours. Subsequently, it was cleaned with chloroform, hexane and isopropanol and dried.
[0040] (4) Dissolve the above polymer in chlorobenzene at a concentration of 5 mg / mL, and stir and heat to 90°C. The solution needs to be preheated for more than 3 minutes before spin coating. Spin coat the solution onto the OTS-treated substrate at 4000 rpm and anneal at 150°C for 30 minutes to prepare a thin film. After cleaning and drying, the remaining preparation process is completed in a glove box to obtain a transistor. The obtained transistor can be used for characteristic analysis without further packaging.
[0041] Fourthly, the present invention also provides a photodetector comprising the aforementioned polymer.
[0042] Fifthly, the present invention also provides a neuromorphic device comprising the aforementioned polymer. The neuromorphic device has multiple functions, including: postsynaptic current after excitation, double-pulse facilitation, and conversion of short-term memory to long-term memory.
[0043] Compared with the prior art, the beneficial effects achieved by the present invention are:
[0044] This invention introduces a cyano unit at the β site of the thiophene donor unit and adjusts the coupling degree by regulating factors such as the electron-donating and accepting ability, twist angle, composition ratio, and environmental medium of the D / A portion, achieving the following effects:
[0045] 1) In the thiophene structure, the substitution of the strong electron-withdrawing group at the β position can enhance the acidity of the adjacent α-H and improve the reactivity. Therefore, conjugated polymers containing dicyanothiophene units can be obtained by direct arylation polymerization, which improves the atom utilization rate and the possibility of large-scale preparation, and reduces the synthesis steps and the difficulty of commercial application.
[0046] 2) The introduction of strong electron-withdrawing groups lowers the overall energy level of polymer molecules. All the successfully synthesized polymer semiconductor materials listed exhibit single electron transport characteristics. At the same time, the deepened energy level improves the stability of the materials in an air environment.
[0047] 3) The charge density is regulated, and the exciton binding energy of polymer semiconductor materials is effectively reduced, which is beneficial to the separation of excitons and the utilization of photogenerated charge carriers; at the same time, the degree of conjugation and planarity are regulated, and the chemical stability and molecular stacking microstructure of the conjugated polymer based on this building block are improved.
[0048] 4) Transistor devices based on several polymer semiconductor materials of 2CNTT have different photoresponse characteristics, indicating that incident light can also be an effective way to control the carrier concentration in the channel. Attached Figure Description
[0049] Figure 1 The monomer 1 (2CNTT) prepared in Example 1 1 H NMR spectrum.
[0050] Figure 2 Monomer 1 prepared in Example 1 13 C10 NMR spectrum.
[0051] Figure 3 The high-resolution mass spectrum of monomer 1 prepared in Example 1 is shown.
[0052] Figure 4 The device structure of an organic phototransistor made from the polymer semiconductor material prepared in Examples 1-3 is shown.
[0053] Figure 5 High-temperature gel permeation chromatography of the polymer semiconductor material P1 prepared in Example 1.
[0054] Figure 6 The UV-Vis absorption spectra of the polymer semiconductor material P1 prepared in Example 1 in chloroform solution and thin film states are shown.
[0055] Figure 7 The transfer characteristics and light-dark response curves of organic phototransistors made from the polymer semiconductor material P1 prepared in Example 1 are shown.
[0056] Figure 8 High-temperature gel permeation chromatography of the polymer semiconductor material P2 prepared in Example 2.
[0057] Figure 9 The UV-Vis absorption spectra of the polymer semiconductor material P2 prepared in Example 2 in chloroform solution and thin film states are shown.
[0058] Figure 10 The transfer characteristics and light-dark response curves of organic phototransistors made from the polymer semiconductor material P2 prepared in Example 2 are shown.
[0059] Figure 11 High-temperature gel permeation chromatography of the polymer semiconductor material P3 prepared in Example 3.
[0060] Figure 12 The UV-Vis absorption spectra of the polymer semiconductor material P3 prepared in Example 3 in chloroform solution and thin film states are shown.
[0061] Figure 13 The transfer characteristics and light-dark response curves of organic phototransistors made from the polymer semiconductor material P3 prepared in Example 3 are shown. Detailed Implementation
[0062] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments.
[0063] In the following examples, every effort has been made to ensure the accuracy of the figures used (including quantities, temperatures, reaction times, etc.), but some experimental errors and biases should be taken into account. The pressures used in the following examples are atmospheric or near atmospheric pressure. All solvents used were purchased as HPLC grade, and all reactions were carried out under a high-purity nitrogen inert atmosphere. Unless otherwise stated, all reagents and raw materials were commercially available.
[0064] The following reagents are from the following sources:
[0065] 2FIID-C4C 10 C 10-2Br: Purchased from Shanghai Bid Pharmaceutical.
[0066] P(o-OMePh)3: Purchased from Sigma Aldrich.
[0067] PivOH: Purchased from Tokyo Chemical Industry Co., Ltd. (TCI).
[0068] Example 1: Preparation of n-type polymer semiconductor material P1 (see the synthesis route diagram below)
[0069]
[0070] The synthesis steps are as follows:
[0071] 1) Weigh 600 mg of 3,6-dibromothiophene[3,2-B]thiophene and 540 mg of CuCN into a single-necked flask, add 10 mL of DMF, dissolve completely, heat the reaction system to 140 °C, and stir overnight.
[0072] 2) After the reaction was complete, 100 mL of water was added to quench the reaction. After stirring for a period of time, the precipitate was filtered. The crude product was washed with water, then extracted with a dichloromethane / water system to separate the organic phase. The organic phase was dried with magnesium sulfate, filtered, and then evaporated to dryness before column chromatography. The eluent ratio was n-hexane:dichloromethane = 1:1, yielding 140 mg of a pale yellow solid (i.e., monomer 1,2CNTT), with a yield of 36.5%.
[0073] 3) Place 2FIID-C4C 10 C 10 -2Br (200.0 mg, 177.10 μmol), 2CNTT (33.69 mg, 177.10 μmol), Pd2(dba)3 (3.24 mg, 3.54 μmol), CuI (6.75 mg, 35.42 μmol), P(o-OMePh)3 (4.99 mg, 14.17 μmol), PivOH (5.43 mg, 53.13 μmol), Cs2CO3 (173.10 mg, 531.29 μmol), and ultra-dry toluene (4 mL) were added to a dry reaction flask, and the reaction mixture was stirred at 120 °C for 30 hours.
[0074] 4) Cool the mixture to room temperature and slowly precipitate it into methanol (100 mL). The precipitated solid polymer is eluted in a Soxhlet extractor with methanol, acetone, n-hexane, ethyl acetate, chloroform, and chlorobenzene in sequence. Finally, the components dissolved in chloroform and chlorobenzene are precipitated into methanol, filtered, and vacuum dried for 1 day to obtain fibrous polymer (i.e., polymer semiconductor material P1). The total amount of chloroform and chlorobenzene components is 170.5 mg, and the yield is 83%.
[0075] The structural characterization of monomer 1 prepared in Example 1 is as follows: Figure 1 , Figure 2 , Figure 3 As shown.
[0076] Example 2: Preparation of n-type polymer semiconductor material P2 (see the synthesis route diagram below)
[0077]
[0078] The synthesis steps are as follows:
[0079] 1) Same as step 1 in Example 1.
[0080] 2) Same as step 2 in Example 1.
[0081] 3) DPP-C5C 10 C 12 -2Br (100.0 mg, 82.26 μmol), 2CNTT (15.65 mg, 82.26 μmol), Pd2(dba)3 (1.51 mg, 1.65 μmol), CuI (3.13 mg, 16.45 μmol), P(o-OMePh)3 (2.32 mg, 6.58 μmol), PivOH (2.52 mg, 24.68 μmol), Cs2CO3 (80.41 mg, 246.79 μmol), and ultra-dry toluene (2 mL) were added to a dry reaction flask. The reaction mixture was stirred at 120 °C for 6 hours.
[0082] 4) Cool the mixture to room temperature and slowly precipitate it into methanol (100 mL). The precipitated solid polymer is eluted sequentially in a Soxhlet extractor with methanol, acetone, n-hexane, ethyl acetate, chloroform, and chlorobenzene. Finally, the fraction dissolved in chloroform and chlorobenzene is precipitated into methanol, filtered, and vacuum dried for one day to obtain a fibrous polymer (i.e., polymer semiconductor material P2). The total amount of chloroform and chlorobenzene components is 85.5 mg, with a yield of 83.4%.
[0083] Example 3: Preparation of n-type polymer semiconductor material P3 (see the synthesis route diagram below)
[0084]
[0085] 1) Same as step 1 in Example 1.
[0086] 2) Same as step 2 in Example 1.
[0087] 3) NDI-C8C 10-2Br (100.0 mg, 101.51 μmol), 2CNTT (19.31 mg, 101.51 μmol), Pd2(dba)3 (1.86 mg, 2.03 μmol), CuI (3.87 mg, 20.30 μmol), P(o-OMePh)3 (2.86 mg, 8.12 μmol), PivOH (3.11 mg, 30.45 μmol), Cs2CO3 (99.23 mg, 304.54 μmol), and ultra-dry toluene (2 mL) were added to a dry reaction flask. The reaction mixture was stirred at 120 °C for 72 hours.
[0088] 4) Cool the mixture to room temperature and slowly precipitate it into methanol (100 mL). The precipitated solid polymer was eluted sequentially in a Soxhlet extractor with methanol, acetone, n-hexane, ethyl acetate, and chloroform. Finally, the chloroform fraction was precipitated into methanol, filtered, and vacuum dried for one day to obtain a fibrous polymer (i.e., polymer semiconductor material P3). The total chloroform fraction was 59.5 mg, with a yield of 57.7%.
[0089] Test Example 1: Testing the basic physicochemical properties of polymer semiconductor materials
[0090] 1. High-temperature gel permeation chromatography
[0091] like Figure 5 , Figure 8 , Figure 11 As shown, the molecular weight distribution of the polymers was analyzed by high-temperature gel permeation chromatography. It can be seen that polymers P1, P2, and P3 were obtained in high yield according to Examples 1-3, and their molecular weights and molecular weight distributions are as follows. The molecular weights are 43.2 kDa / 2.6, 27.4 kDa / 1.7, and 35.6 kDa / 2.2, respectively. The high molecular weight polymers demonstrate the high reactivity of the 2CNTT structure in direct arylation reactions.
[0092] 2. UV-Vis absorption spectra measured in chloroform solution and on thin films
[0093] like Figure 6 , Figure 9 , Figure 12 As shown, P1-P3 exhibit obvious donor-acceptor polymer absorption characteristics in the visible light range, and all show dual-band absorption. They also show obvious fine structure near the maximum absorption peak, indicating typical intramolecular charge transfer behavior.
[0094] 3. Optical band gap of molecules
[0095] The optical band gap of a molecule can be determined by the empirical formula (E). g =1240 / λ edge The calculations are shown in Table 1.
[0096] Table 1 Optical absorption data of thin films in polymer semiconductor materials
[0097] molecular <![CDATA[λ max (nm)]]> <![CDATA[λ edge (nm)]]> <![CDATA[E g opt (eV)]]> P1 483 708 1.75 P2 843 977 1.27 P3 476 698 1.78
[0098] As shown in Table 1, the polymer thin film based on 2CNTT obtained by the above steps has a suitable absorption spectrum and a relatively narrow band gap in the visible light band, and can be used to prepare the active layer material of organic phototransistor devices.
[0099] Example 4: Organic phototransistor device with bottom-gate bottom-electrode (BGBC) structure
[0100] Device structure such as Figure 4 As shown, from bottom to top, it includes: gate, 300nm SiO2 dielectric layer (~11.5nF / cm). 2 A single-component active layer (made from the above-mentioned polymer semiconductor material) is provided with a source and a drain at both ends of the active layer.
[0101] The specific preparation method is as follows:
[0102] (1) An n-type heavily doped Si wafer was selected as the substrate, including a 300 nm SiO2 dielectric layer (~11.5 nF / cm). 2 ) and bottom gate electrode;
[0103] (2) A 30nm thick gold source and drain bottom electrode was patterned on the silicon dioxide surface using photolithography (with 3nm Ti as the adhesion layer, W / L = 1400μm / 50μm).
[0104] (3) The patterned Au gold substrate was first immersed in Piranha solution (H2SO4 and H2O2 volume ratio of 2:1) for 40 minutes. After cooling to room temperature, the substrate was further cleaned with deionized water, acetone and isopropanol in sequence, each solution for more than 15 minutes.
[0105] (4) Then, the substrate was dried with N2 and baked in a vacuum drying oven at 80°C for 1 hour. After being treated with O2 plasma for 10 minutes, the substrate was placed in a culture dish, and one drop of octadecyltrichlorosilane (OTS) was dropped in the center of the dish. The substrate was placed at 120°C for 3 hours, and after being vacuum cooled to room temperature, it was cleaned with chloroform, hexane, and isopropanol in sequence, and then dried with N2.
[0106] (5) The polymer semiconductor material P1 obtained in Example 1 was dissolved in chlorobenzene at a concentration of 5 mg / mL, heated to 90°C, and stirred for 10 hours. Before spin coating, the solution should be preheated at 90°C for at least 3 minutes. The solution was spin-coated onto an OTS-treated Si / SiO2 substrate at 4000 rpm for 1 minute, and then annealed at 150°C for 30 minutes to prepare a thin film (i.e., the active layer). After cleaning and drying the substrate, the remaining preparations were completed in a glove box.
[0107] Test Example 2: Testing the carrier transport properties and photoresponse characteristics of an organic phototransistor with a bottom-gate bottom electrode (BGBC) structure.
[0108] Following the method in Example 4, polymer semiconductor materials P2 and P3 were used to fabricate organic phototransistor devices, which were then tested.
[0109] like Figure 7 , Figure 10 , Figure 13 As shown, the electrical performance results of the device are summarized below.
[0110] Table 2 Summary of Device Test Carrier Transport Properties and Photoresponse Characteristics
[0111]
[0112] As shown in Table 2, the polymer materials based on the 2CNTT structure all exhibit both electron mobility and photoresponse characteristics. This indicates that the multiple cyano groups introduced at the β-position regulate the charge density of the polymer and promote the generation and utilization of photogenerated carriers.
[0113] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.
Claims
1. An n-type conjugated polymer containing a dicyanothiophene structure, the structure of which is shown in Formula II: In Formula II: A is an electron acceptor group, which has one of the following structures: in: X1 represents a substituent group consisting of H, F, or Cl atoms; X2 represents a heteroatom-conjugated aromatic ring, a fused ring formed by heteroatoms, a thiophene group, a selenophene group, a pyridine group, a furan group, a thiazole group, or a thiophene group; the heteroatoms are O, S, or Se; R represents a straight-chain or branched alkyl, alkoxy, alkylthio, or silyl group having 1-28 carbon atoms; n represents the degree of aggregation, and is a natural number ranging from 10 to 40.
2. The polymer according to claim 1, characterized in that, Selected from one or more of the following structures:
3. A method for preparing the n-type conjugated polymer containing a dicyanothiophene structure as described in claim 1 or 2, comprising the following steps: S1,3,6-dibromothiophene[3,2-B]thiophene reacts with CuCN to give a cyano-substituted intermediate; S2, the cyano-substituted intermediate and monomer A undergo arylation polycondensation reaction in a Pd2(dba)3 / CuI catalytic system; S3. The reaction solution obtained in step S2 is subjected to gradient purification to obtain an n-type conjugated polymer containing a dicyanothiophene structure.
4. The preparation method according to claim 3, characterized in that, In step S1, the reaction conditions are: temperature 135-145℃ and time 11-13h.
5. The preparation method according to claim 3 or 4, characterized in that, In step S2, the Pd2(dba)3 / CuI catalytic system comprises: 0.02 equivalents of Pd2(dba)3, 0.2 equivalents of CuI, 0.08 equivalents of P(o-OMePh)3, 0.3 equivalents of PivOH, and 3 equivalents of Cs2CO3. The reaction conditions are: temperature 90-140℃, time 6-72h.
6. The preparation method according to any one of claims 3-5, characterized in that, In step S3, the gradient purification is a Soxhlet extraction using methanol, acetone, n-hexane, ethyl acetate, and chloroform in sequence.
7. An organic phototransistor device comprising a single-component active layer; said single-component active layer being formed from one or more of the polymers of claim 1 or 2.
8. The organic phototransistor device according to claim 7, characterized in that, include: Gate: Formed from an n-type doped Si wafer; Dielectric layer: formed of SiO2 and surface modified with octadecyltrichlorosilane; Source and drain electrodes: formed of Au, with a Ti thin film adhered to the surface; Single-component active layer: formed from the polymer described in claim 1 or 2.
9. A photodetector comprising the polymer of claim 1 or 2.
10. A neuromorphic device comprising the polymer of claim 1 or 2.