A class of chiral organic photosensitive semiconductors, their preparation methods and applications

Abstract

The present invention belongs to the field of organic optoelectronic technology, and discloses a class of chiral organic photosensitive semiconductors and a preparation method and application thereof. The structure of the class of chiral organic photosensitive semiconductors is shown below. The organic photosensitive semiconductor of the present invention has strong chemical stability and chemical modifiability based on the quinoxaline unit; the electronegativity of its nitrogen atom is greater than that of the carbon atom, and the electron cloud density of the conjugated orbit of the heterocyclic ring is reduced by replacing the C atom with an N atom in the six-membered heterocyclic ring, that is, the electron deficiency of the heterocyclic ring is increased, which is beneficial to reduce the LUMO energy level of the compound, thereby adjusting the optical and carrier transport properties of the semiconductor compound, and can be used to prepare a circularly polarized light detector.

Description

Technical Field

[0001] The present invention belongs to the field of organic optoelectronic technology, and in particular relates to a chiral organic photosensitive semiconductor and a preparation method and application thereof. Background Art

[0002] Photodetectors (photodiodes, PDs) are the eyes of smart devices and an indispensable component of intelligent portable electronic devices. With the popularization of smart electronic devices, the market demand for high-performance, low-cost infrared photodetectors is increasing, providing important opportunities for the transformation and upgrading of industries such as automation, human-computer interaction, and artificial intelligence. In addition to photodetectors working in the visible light band (0.3-0.8 microns), photodetectors and image arrays with infrared bands (0.8-1.8 microns) have broad application prospects in portable electronic products, driverless cars, residential security systems, human-computer interaction, identity recognition required for Internet payment, and artificial intelligence.

[0003] The preparation of organic photodetectors based on organic photosensitive materials can not only realize small-size, high-pixel-density photodetector imaging arrays, but also does not require patterning of the photosensitive layer film, greatly reducing the preparation cost of the device. In addition, since organic semiconductor materials are mainly based on intermolecular van der Waals forces, photodetector devices covering a wide band can be directly obtained by blending multiple components with complementary absorption spectra, achieving a wider light response range and a more comprehensive working band.

[0004] In addition, organic semiconductor molecules with chiral structures have unparalleled advantages over inorganic semiconductors in the detection of circularly polarized light. The information contained in the optical signal is not only the intensity and wavelength, but also the polarization. The polarization direction of natural light changes randomly and irregularly, while the polarization direction of circularly polarized light changes according to a certain rule. The light whose light vector endpoints trace out a circular trajectory over time is called circularly polarized light; according to the direction of the light, the light vector rotates clockwise or counterclockwise over time, and the circularly polarized light is subdivided into "right-handed circularly polarized light" and "left-handed circularly polarized light". Since the atoms or ions in inorganic semiconductor crystals grow in three dimensions and are completely symmetrical, there is no chirality, while organic conjugated molecules can introduce chiral carbon atoms or chiral configurations. The electric field vectors of left and right circularly polarized light act on chiral molecules with different components, so circularly polarized light can be detected by the degree of photoelectric change of chiral molecules. Circularly polarized light has important applications in many photonic technologies. Ellipsometry can calculate or fit the properties of sample materials by measuring and analyzing the changes in the polarization state (amplitude, phase) of reflected light after the interaction between circularly polarized light and matter. This technology is widely used in semiconductor physics research, microelectronics and biology. In recent years, its application in the field of biomedical diagnosis has attracted the interest of many researchers. In optical communications, full-power communication can be achieved by modulating the polarization state of light. Since the proportion of circular polarization states of light in nature is very low, the use of circularly polarized light to modulate signals in the transmission channel can effectively reduce the interference of background light. Compared with other polarized light, circularly polarized light can also be used to transmit rotation information. In addition, circularly polarized light also has great application potential in quantum-based optical computing and information processing. Summary of the invention

[0005] In order to solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a class of chiral organic photosensitive semiconductors, wherein the quinoxaline unit connected to the chiral unit has a strong electron-absorbing property and can effectively adjust the molecular circular dichroism absorption characteristics and molecular orbital energy levels.

[0006] Another object of the present invention is to provide the above-mentioned polymer photosensitive semiconductor with chirality.

[0007] Another object of the present invention is to provide applications of the above-mentioned chiral organic photosensitive semiconductor and polymer semiconductor in the field of semiconductor devices.

[0008] To achieve the above object, the present invention adopts the following technical solution:

[0009] A chiral organic photosensitive semiconductor containing one of the following chemical structural formula units:

[0010]

[0011] The following applies to the symbols that appear:

[0012] X is independently selected from N, CR each time it appears 1 One of;

[0013] Each occurrence of Y is independently selected from: C(R 1 )2. NR 1 、Si(R 1 )2、Ge(R 1 2. R 1 C=CR 1 , C(R 1 )2C(R 1 )2, at least one of C=O, O, S, Se, Te, S(=O) and SO2;

[0014] Each occurrence of the group Ar is independently selected from R 1 , can be one or more R 1 A group of an aromatic ring system having 5 to 300 atoms substituted by a group, which may be substituted by one or more R 1 One of the groups of a group-substituted heteroaromatic ring system having 3 to 300 atoms;

[0015] Where R 1 Each occurrence is independently selected from H, D, F, Cl, Br, I, CN, C(=O)R 2 ,Si(R 2 )3,N(R 2 )2,OR 2 ,SR 2 ,S(=O)R 2 ,S(=O)2R 2 , CH=C(CN)2, group A, one or more -CH2- groups in group A are replaced by -R 3 C=CR 3 -,-C≡C-,Si(R 3 )2,C=O,C=NR 3 ,-C(=O)O-,-C(=O)NR 3 -,NR 3 , O, S, S(=O) or SO2 substituted, wherein the group A is a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms, or a heteroaromatic organic group having 3 to 60 carbon atoms; two or more groups R 1 Can be linked to each other and can form a loop;

[0016] R 2 , R 3 Each occurrence is independently selected from a linear alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms, and a heteroaromatic organic group having 3 to 60 carbon atoms; two or more groups R 2 , R 3 Can be linked to each other and can form a loop.

[0017] Preferably, in the chiral organic photosensitive semiconductor, the Ar unit preferably has the following structure and is surrounded by at least one R 1 At least one of the following structures substituted with a group:

[0018]

[0019] Among them, X, Y, R 1 , R 2 , R 3 The definition of X, Y, R is the same as that of 1 , R 2 , R 3 The definition is the same.

[0020] More preferably, the chiral organic photosensitive semiconductor has a structure of one of the following structures:

[0021]

[0022] A class of chiral polymer semiconductors with the following chemical structure:

[0023]

[0024]

[0025] n is the number of repeating units, n = 2-1000;

[0026] The definitions of X, Y and Ar are the same as those in the above description.

[0027] Preferably, the chiral polymer semiconductor has a chemical structure as shown below:

[0028]

[0029] n is the number of repeating units, n=2-1000.

[0030] A method for preparing the above-mentioned chiral organic photosensitive semiconductor comprises the following key steps:

[0031] (a) and Response

[0032] (b) Reduction to diamine

[0033] (c) With diketone functional groups A cyclization reaction occurs to obtain

[0034] (d) The formaldehyde group is introduced through the Vilsmeier-Haack-Arnold reaction, and finally condensed with the corresponding end group molecule under the catalysis of an organic base to obtain a chiral organic photosensitive semiconductor;

[0035] The reaction in step (a) refers to a reaction at 60°C-153°C for 24 hours under the catalysis of an organic solvent and a base, wherein the organic solvent is preferably N,N-dimethylformamide (DMF), and the base is preferably one of potassium carbonate, sodium carbonate, and cesium carbonate.

[0036] The reduction described in step (b) refers to the addition of iron for reduction, and the reduction conditions are 25° C.-120° C. for 1-24 hours.

[0037] The reaction shown in step (c) refers to the reaction at 60°C-120°C for 8h in a solvent, wherein the solvent is preferably acetic acid;

[0038] The introduction of formaldehyde group in step (d) refers to first adding n-butyl lithium to extract hydrogen, and then adding DMF to introduce formaldehyde group.

[0039] Preferably, the step (d) of first adding n-butyl lithium to extract hydrogen refers to stirring and reacting at -100°C to -78°C for 1.5h to 2.0h under nitrogen protection; and the step of then adding DMF to introduce formaldehyde groups refers to reacting at room temperature for 4-8h in the dark.

[0040] The organic base described in step (d) is one of sodium acetate and pyridine; the condensation refers to stirring the reaction at room temperature to 75°C for 40min-16h.

[0041] A method for preparing the above-mentioned chiral polymer semiconductor comprises the following key steps: Will The polymer semiconductor is obtained by double bromination with a brominating agent, and then polymerization with a monomer having a double functional group (such as Sn(CH3)3-Ar-Sn(CH3)3) is carried out using a coupling reaction such as Stille coupling or Suzuki coupling.

[0042] The brominating agent is preferably liquid bromine or N-bromosuccinimide; the dibromination is carried out at 50°C for 24 hours;

[0043] The polymerization refers to a reaction at 70°C to 140°C for 1 to 48 hours under the action of a catalyst, wherein the catalyst is preferably at least one of tetrakistriphenylphosphine palladium, bistriphenylphosphine palladium dichloride, palladium acetate, and Pd2(dba)3.

[0044] The application of the chiral organic photosensitive semiconductors and polymer semiconductors in the field of semiconductor devices has great development potential and prospects in the field of circularly polarized light detection because of their good energy level structure, circular dichroism absorption characteristics, thermal stability, and solution processing characteristics, which are conducive to realizing the needs of efficient and stable organic light-to-electric conversion.

[0045] A preparation comprising at least one compound of the above formula (I) or polymer of (II) and at least one solvent, preferably chloroform, chlorobenzene, methyltetrahydrofuran, methoxytetrahydrofuran, o-dichlorobenzene, toluene.

[0046] An electronic device selected from: an organic thin film transistor (OFET), an organic solar cell (OSC), an organic photodiode (OPD), an organic phototransistor (OPT), and an organic light emitting diode (OLED); the electronic device comprises at least one compound of the above formula (I) or a polymer of (II).

[0047] An array of the above devices.

[0048] Compared with the existing technology, the present invention has the following advantages:

[0049] (1) The quinoxaline unit based on the present invention has good push-pull electron properties;

[0050] (2) The quinoxaline unit based on the present invention is directly connected to the chiral group, which is conducive to achieving high circular dichroism absorption characteristics;

[0051] (3) The quinoxaline unit based on the present invention has good chemical stability and strong modifiability;

[0052] (4) The organic photosensitive semiconductor of the present invention is based on the quinoxaline unit, which has strong chemical stability and chemical modifiability; the electronegativity of its nitrogen atom is greater than that of the carbon atom. Replacing the C atom with a N atom in the six-membered heterocyclic ring can reduce the electron cloud density of the heterocyclic conjugated orbital, that is, increase the electron deficiency of the heterocyclic ring, which is beneficial to reduce the LUMO energy level of the compound, thereby adjusting the optical and carrier transport properties of the semiconductor compound, and can be used to prepare circularly polarized light detectors. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 Circular dichroism characteristics of the polymer P(R)-M4 film in Example 6.

[0054] Figure 2 This is the external quantum efficiency-wavelength characteristic curve of the device in Example 8. DETAILED DESCRIPTION

[0055] The present invention is further described in detail below in conjunction with the examples and drawings, but the embodiments of the present invention are not limited thereto. If specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0056] Unless otherwise specified, the reagents used in the examples can be purchased from the market.

[0057] Example 1 Synthesis of Compound (R)-M1

[0058]

[0059] Synthesis of compound (R)-1: Under nitrogen protection, 10.00 g (49.00 mmol) of 1,2-difluoro-4.5-dinitrobenzene, 12.75 g (44.54 mmol) of (R)-1,1'-bi-2-naphthol, and 15.39 g (111.36 mmol) of potassium carbonate were dissolved in 100 ml of anhydrous N,N-dimethylformamide (DMF), stirred for 15 minutes, and then heated to 70 degrees Celsius and reacted at constant temperature for 24 hours. After the reaction was completed, the temperature was restored to room temperature, the mixed solution was introduced into 250 ml of deionized water, and extracted with dichloromethane three times. The organic phase was dried, filtered, concentrated, and separated by column chromatography. A mixed solution of petroleum ether: dichloromethane with a volume ratio of 2:1 was used as an eluent. Recrystallization was carried out twice with a mixed solvent of dichloromethane and methanol, and the solid was filtered and dried in a vacuum drying oven for 24 hours. Finally, 11.93 g of solid was obtained with a yield of 59.5%.

[0060] The chemical reaction equation is as follows:

[0061]

[0062] Synthesis of compound (R)-2: Under nitrogen protection, add 10.00 g (22.20 mmol) of compound (R)-1 and 24.80 g (444.00 mmol) of iron powder to 200 ml of acetic acid. After stirring for 15 minutes, heat to 60 degrees Celsius and react for 2 hours. Monitor the reaction by TLC. After the reaction is completed, use a magnet to suck out the remaining iron powder in the solution, then filter it with diatomaceous earth while hot, wash the filter cake twice with an appropriate amount of hot water, and then wash it twice with a small amount of anhydrous methanol. Cool the filtrate to -20 degrees Celsius, precipitate the solid, filter it with suction, wash the filter residue 3 times with methanol, and dry it in vacuum for 2 hours. Obtain 7.42 g of solid compound (R)-2 with a yield of 85.6%.

[0063] Synthesis of compound (R)-3: 7.00 g (17.93 mmol) of compound (R)-2 and 5.92 g (26.89 mmol) of benzo[1,2-B:6,5-B′]dithiophene-4,5-dione were dissolved in 100 ml of acetic acid, stirred for 15 minutes, heated to 60 degrees Celsius, and reacted for 8 hours. After the reaction was completed, the temperature was restored to room temperature, and the acetic acid was dried by rotary evaporation. The remaining crude product was extracted with dichloromethane and deionized water three times, and the organic phase was dried, filtered, concentrated, and separated by column chromatography in turn, and a mixed solution of petroleum ether: dichloromethane with a volume ratio of 1.5:1 was used as an eluent. The obtained solid was recrystallized once with dichloromethane and anhydrous methanol, filtered, and the filter residue was placed in a vacuum drying oven for drying, and finally 6.03 g of solid compound (R)-3 was obtained, with a yield of 58.5%.

[0064] The chemical reaction equation is as follows:

[0065]

[0066] Synthesis of compound (R)-4: Under nitrogen protection, 6.00 (10.44 mmol) of compound (R)-3 was dissolved in 60 ml of anhydrous tetrahydrofuran, and the solution was placed in a 250 ml three-necked flask and stirred at -78 degrees Celsius for 15 minutes. 26.1 ml of 1.0 mol / L n-butyl lithium in n-hexane solution reagent (26.10 mmol) was added dropwise and stirred at -78 degrees Celsius for 1.5 hours. Then 4.0 ml (52.2 mmol) of anhydrous DMF was added dropwise to the reaction solution, and the temperature was naturally raised to room temperature and reacted at room temperature for 4 hours. After the reaction was completed, the solvent was spun off, and the remaining crude product was extracted 3 times with deionized water and dichloromethane, and the organic phase was dried, filtered, concentrated, and separated by column chromatography. A mixed solution with a volume ratio of petroleum ether: dichloromethane of 1.5:1 was used as an eluent. The obtained solid was recrystallized with dichloromethane and anhydrous methanol, the solid-liquid mixture was filtered, and the solid was placed in a vacuum drying oven and dried for 24 hours to obtain 4.79 grams of solid compound (R)-4, with a yield of 72.7%.

[0067] Synthesis of compound (R)-M1: 1.00 g (1.59 mmol) of compound (R)-4, 1.26 g (19.03 mmol) of malononitrile, and 1.04 g (12.68 mmol) of sodium acetate were dissolved in 20 ml of anhydrous ethanol and stirred at room temperature for 40 minutes. A 2.0 M dilute hydrochloric acid aqueous solution was then added dropwise to the reaction solution until the pH of the reaction solution was within the range of 1-2, and stirred at room temperature for 20 minutes. Filter, wash the filter residue with deionized water to obtain a crude product, recrystallize the crude product twice with acetic acid, filter the solid-liquid mixture by suction, and dry the filter residue in a vacuum drying oven for 24 hours. Compound (R)-M1 was obtained, 0.97 g of solid powder, and a yield of 84.2%.

[0068] The chemical reaction equation is as follows:

[0069]

[0070] Example 2 Synthesis of Compound (S)-M1

[0071]

[0072] Synthesis of compound (S)-1: Under nitrogen protection, 10.00 g (49.00 mmol) of 1,2-difluoro-4.5-dinitrobenzene, 12.75 g (44.54 mmol) of (S)-1,1'-bi-2-naphthol, and 15.39 g (111.36 mmol) of potassium carbonate were dissolved in 100 ml of anhydrous N,N-dimethylformamide (DMF), stirred for 15 minutes, and then heated to 70 degrees Celsius and reacted at constant temperature for 24 hours. After the reaction was completed, the mixture was returned to room temperature, introduced into 250 ml of deionized water, and extracted with dichloromethane three times. The organic phase was dried, filtered, concentrated, and separated by column chromatography. A mixed solution of petroleum ether: dichloromethane with a volume ratio of 2:1 was used as an eluent. Recrystallization was performed twice with a mixed solvent of dichloromethane and methanol, and the solid was filtered and dried in a vacuum drying oven for 24 hours. Finally, 12.41 g of solid was obtained, with a yield of 61.9%.

[0073] The chemical reaction equation is as follows:

[0074]

[0075] Synthesis of compound (S)-2: Under nitrogen protection, add 10.00 g (22.20 mmol) of compound (S)-1 and 24.80 g (444.00 mmol) of iron powder to 200 ml of acetic acid. After stirring for 15 minutes, heat to 60 degrees Celsius and react for 2 hours. Monitor the reaction by TLC. After the reaction is completed, use a magnet to suck out the remaining iron powder in the solution, then filter it with diatomaceous earth while hot, wash the filter cake with an appropriate amount of hot water twice, and then wash it with a small amount of anhydrous methanol twice. Cool the filtrate to -20 degrees Celsius, precipitate the solid, filter it with suction, wash the filter residue with methanol 3 times, and vacuum dry it for 2 hours. Obtain 7.63 g of solid compound (S)-2 with a yield of 88.0%.

[0076] Synthesis of compound (S)-3: 7.00 g (17.93 mmol) of compound (S)-2 and 5.92 g (26.89 mmol) of benzo[1,2-B:6,5-B′]dithiophene-4,5-dione were dissolved in 100 ml of acetic acid, stirred for 15 minutes, heated to 60 degrees Celsius, and reacted for 8 hours. After the reaction was completed, the temperature was restored to room temperature, and the acetic acid was dried by rotary evaporation. The remaining crude product was extracted with dichloromethane and deionized water three times, and the organic phase was dried, filtered, concentrated, and separated by column chromatography in turn, and a mixed solution of petroleum ether: dichloromethane with a volume ratio of 1.5:1 was used as an eluent. The obtained solid was recrystallized once with dichloromethane and anhydrous methanol, filtered, and the filter residue was placed in a vacuum drying oven for drying, and finally 6.94 g of solid compound (S)-3 was obtained, with a yield of 67.4%.

[0077] The chemical reaction equation is as follows:

[0078]

[0079] Synthesis of compound (S)-4: Under nitrogen protection, 6.00 (10.44 mmol) of compound (S)-3 was dissolved in 60 ml of anhydrous tetrahydrofuran, and the solution was placed in a 250 ml three-necked flask and stirred at -78 degrees Celsius for 15 minutes. 26.1 ml of 1.0M n-butyl lithium in n-hexane solution reagent (26.10 mmol) was added dropwise and stirred at -78 degrees Celsius for 1.5 hours. Then 4.0 ml (52.2 mmol) of anhydrous DMF was added dropwise to the reaction solution, and the temperature was naturally raised to room temperature and reacted at room temperature for 4 hours. After the reaction was completed, the solvent was spun off, and the remaining crude product was extracted 3 times with deionized water and dichloromethane, and the organic phase was dried, filtered, concentrated, and separated by column chromatography. A mixed solution of petroleum ether: dichloromethane with a volume ratio of 1.5:1 was used as an eluent. The obtained solid was recrystallized with dichloromethane and anhydrous methanol, the solid-liquid mixture was filtered, and the solid was placed in a vacuum drying oven for 24 hours to obtain 5.02 grams of solid compound (S)-4, with a yield of 76.2%.

[0080] Synthesis of compound (S)-M1: 1.00 g (1.59 mmol) of compound (S)-4, 1.26 g (19.03 mmol) of malononitrile, and 1.04 g (12.68 mmol) of sodium acetate were dissolved in 20 ml of anhydrous ethanol and stirred at room temperature for 40 minutes. A 2.0 M dilute hydrochloric acid aqueous solution was then added dropwise to the reaction solution until the pH of the reaction solution was within the range of 1-2, and stirred at room temperature for 20 minutes. Filter, wash the filter residue with deionized water to obtain a crude product, recrystallize the crude product twice with acetic acid, filter the solid-liquid mixture by suction, and dry the filter residue in a vacuum drying oven for 24 hours. Compound (S)-M1 was obtained, 934 mg of solid powder, and a yield of 81.1%.

[0081] The chemical reaction equation is as follows:

[0082]

[0083] Example 3 Synthesis of Compound (R)-M2

[0084] Under nitrogen protection, 1.00 g (1.59 mmol) of compound (R)-4 and 1.85 g (9.51 mmol) of 2-(3-oxo-2,3-dihydro-1H-inden-1-yl) propanedinitrile were dissolved in 30 ml of chloroform and stirred in the dark for 10 minutes. Then 0.5 ml of pyridine was added dropwise to the solution, stirred in the dark for 8 hours at room temperature (25 degrees Celsius), and the temperature was raised to 35 degrees Celsius for another 8 hours. The reaction was stopped, and the reaction solution was dropped into 500 ml of anhydrous methanol. Solids precipitated, and the solid-liquid mixture was placed in a 0 degree Celsius environment for 1 hour. Filtered by suction, the obtained filter residue was recrystallized twice with chloroform and anhydrous methanol. Filtered by suction, the obtained filter residue was dried in a vacuum drying oven for 24 hours. Finally, 837 mg of dark blue crystals of compound (R)-M2 were obtained with a yield of 53.7%.

[0085] The chemical reaction equation is as follows:

[0086]

[0087] Example 4 Synthesis of Compound (S)-M2

[0088] Under nitrogen protection, 1.00 g (1.59 mmol) of compound (S)-4 and 1.85 g (9.51 mmol) of 2-(3-oxo-2,3-dihydro-1H-inden-1-yl) propanedinitrile were dissolved in 30 ml of chloroform and stirred in the dark for 10 minutes. 0.5 ml of pyridine was then added dropwise to the solution, stirred in the dark for 8 hours at room temperature (25 degrees Celsius), and then heated to 35 degrees Celsius for another 8 hours. The reaction was stopped, and the reaction solution was dropped into 500 ml of anhydrous methanol. Solids precipitated, and the solid-liquid mixture was placed in a 0 degree Celsius environment for 1 hour. Filtered by suction, the obtained filter residue was recrystallized twice with chloroform and anhydrous methanol. Filtered by suction, the obtained filter residue was dried in a vacuum drying oven for 24 hours. Finally, 865 mg of dark blue crystals of compound (S)-M2 were obtained with a yield of 55.5%.

[0089] The chemical reaction equation is as follows:

[0090]

[0091] Example 5 Synthesis of Compound (R)-M3

[0092] Synthesis of compound (R)-5: Under nitrogen protection, 3.00 g (7.68 mmol) of compound (R)-2 and 2.54 g (11.53 mmol) of benzo[1,2-B:4,3-B′]dithiophene-4,5-dione were dissolved in 30 ml of acetic acid, stirred for 15 minutes, heated to 60 degrees Celsius, and reacted for 8 hours. After the reaction was completed, the temperature was restored to room temperature, and the acetic acid was dried by rotary evaporation. The remaining crude product was extracted with dichloromethane and deionized water three times, and the organic phase was dried, filtered, concentrated, and separated by column chromatography in turn, and a mixed solution of petroleum ether: dichloromethane with a volume ratio of 1.5:1 was used as an eluent. The obtained solid was recrystallized once with dichloromethane and anhydrous methanol, filtered, and the filter residue was placed in a vacuum drying oven for drying, and finally 3.03 g of solid compound (R)-5 was obtained, with a yield of 68.6%.

[0093] The chemical reaction equation is as follows:

[0094]

[0095] Synthesis of compound (R)-6: Under nitrogen protection, 3.00 (5.22 mmol) of compound (R)-5 was dissolved in 30 ml of anhydrous tetrahydrofuran, and the solution was placed in a 250 ml three-necked flask and stirred at -78 degrees Celsius for 15 minutes. 13.1 ml of 1.0M n-butyl lithium in n-hexane solution reagent (13.1 mmol) was added dropwise and stirred at -78 degrees Celsius for 1.5 hours. 2.0 ml (16.1 mmol) of anhydrous DMF was then added dropwise to the reaction solution, and the temperature was naturally raised to room temperature and reacted at room temperature for 4 hours. After the reaction was completed, the solvent was spun off, and the remaining crude product was extracted 3 times with deionized water and dichloromethane, and the organic phase was dried, filtered, concentrated, and separated by column chromatography. A mixed solution of petroleum ether: dichloromethane with a volume ratio of 1.5:1 was used as an eluent. The obtained solid was recrystallized with dichloromethane and anhydrous methanol, the solid-liquid mixture was filtered, and the solid was placed in a vacuum drying oven for 24 hours to obtain 2.44 grams of solid compound (R)-6, with a yield of 74.1%.

[0096] Synthesis of compound (R)-M3: 1.00 g (1.59 mmol) of compound (R)-6, 1.26 g (19.03 mmol) of malononitrile, and 1.04 g (12.68 mmol) of sodium acetate were dissolved in 20 ml of anhydrous ethanol and stirred at room temperature for 40 minutes. A 2.0 M dilute hydrochloric acid aqueous solution was then added dropwise to the reaction solution until the pH of the reaction solution was within the range of 1-2, and stirred at room temperature for 20 minutes. Filter, wash the filter residue with deionized water to obtain a crude product, recrystallize the crude product twice with acetic acid, filter the solid-liquid mixture by suction, and dry the filter residue in a vacuum drying oven for 24 hours. Compound (R)-M3 was obtained, 869 mg of solid powder, and a yield of 75.4%.

[0097] The chemical reaction equation is as follows:

[0098]

[0099] Example 6 Synthesis of polymer P(R)-M4

[0100] Synthesis of compound (R)-M4: Under nitrogen protection, 9.00 g (1.74 mmol) of compound (R)-3 and 650.4 mg (3.65 mmol) of N-bromosuccinimide (NBS) were dissolved in 20 ml of chloroform solvent, stirred for 15 minutes in a dark environment, and then 0.5 ml of N,N-dimethylformamide (DMF) was added dropwise to the reaction solution. The temperature was raised to 50 degrees Celsius and the reaction was carried out for 24 hours. After the reaction was completed, the temperature was restored to room temperature and extracted with dichloromethane and deionized water three times. The organic phase was dried, filtered, concentrated, and separated by column chromatography in sequence, and petroleum ether: dichloromethane was used as an eluent in a volume ratio of 3:1. The obtained product was further purified by recrystallization with anhydrous methanol and dichloromethane, filtered, and the solid was placed in a vacuum drying oven for drying. Finally, 930 mg was obtained with a yield of 73.0%.

[0101]

[0102] Synthesis of polymer P(R)-M4: Under argon protection, 366.2 mg (0.50 mmol) of compound (R)-M4 and 452.3 mg (0.50 mmol) of compound 7 were dissolved in 5 ml of anhydrous chlorobenzene, stirred thoroughly, and then 29.0 mg (0.025 mmol) of tetrakistriphenylphosphine palladium catalyst was added, the pressure tube was sealed, the temperature was slowly raised to 140 degrees Celsius, and the reaction was carried out at a constant temperature for 48 hours. After the reaction was completed, it was returned to room temperature. The reaction solution was dripped into 500 ml of anhydrous methanol, the polymer was precipitated, filtered, and the filter residue was extracted with acetone, n-hexane, and chloroform in a Soxhlet extractor in turn. The chloroform component obtained was concentrated to 5-10 ml, and the concentrated solution was dripped into 400 ml of anhydrous methanol for precipitation, filtered, and the obtained solid was dried in a vacuum drying oven. Finally, 448 mg of solid was obtained with a yield of 76.0%.

[0103]

[0104] The polymer P(R)-M4 can be dissolved in organic solvents such as toluene, xylene, chlorobenzene, dichlorobenzene, chloroform, methyltetrahydrofuran, cyclopentyl methyl ether, etc. The circular dichroism characteristics of the dried film are as follows: Figure 1 As shown in the figure, it can be seen that the film has different absorption characteristics for different circularly polarized light.

[0105] Example 7 Synthesis of Polymer P(R)-M5

[0106]

[0107] Synthesis of compound (R)-11: Under nitrogen protection, 3.00 g (14.70 mmol) of 1,2-difluoro-4.5-dinitrobenzene, 3.93 g (13.36 mmol) of (R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol, and 4.62 g (33.41 mmol) of potassium carbonate were dissolved in 30 ml of anhydrous N,N-dimethylformamide (DMF), stirred for 15 minutes, and then heated to 70 degrees Celsius and reacted at constant temperature for 24 hours. After the reaction was completed, the temperature was restored to room temperature, the mixed solution was introduced into 250 ml of deionized water, and extracted with dichloromethane three times. The organic phase was dried, filtered, concentrated, and separated by column chromatography. A mixed solution with a volume ratio of petroleum ether: dichloromethane of 4:1 was used as an eluent. The product was recrystallized twice with a mixed solvent of dichloromethane and methanol, filtered, and the solid was dried in a vacuum drying oven for 24 hours. Finally, 4.07 g of solid was obtained with a yield of 66.4%.

[0108] The chemical reaction equation is as follows:

[0109]

[0110] Synthesis of compound (R)-12: Under nitrogen protection, add 4.00 g (8.72 mmol) of compound (R)-11 and 9.74 g (174.49 mmol) of iron powder to 40 ml of acetic acid. After stirring for 15 minutes, heat to 60 degrees Celsius and react for 2 hours. Monitor the reaction by TLC. After the reaction is completed, use a magnet to suck out the remaining iron powder in the solution, then filter it with diatomaceous earth while hot. Wash the filter cake twice with an appropriate amount of hot water, and then wash it twice with a small amount of anhydrous methanol. Cool the filtrate to -20 degrees Celsius, precipitate the solid, filter it with suction, wash the filter residue 3 times with methanol, and dry it in vacuum for 2 hours. Obtain 2.89 g of solid compound (R)-12 with a yield of 83.1%.

[0111] Synthesis of compound (R)-13: 2.70 g (6.78 mmol) of compound (R)-12 and 2.24 g (10.16 mmol) of benzo[1,2-B:6,5-B′]dithiophene-4,5-dione were dissolved in 30 ml of acetic acid, stirred for 15 minutes, heated to 60 degrees Celsius, and reacted for 8 hours. After the reaction was completed, the temperature was restored to room temperature, and the acetic acid was dried by rotary evaporation. The remaining crude product was extracted with dichloromethane and deionized water three times, and the organic phase was dried, filtered, concentrated, and separated by column chromatography in turn, and a mixed solution of petroleum ether: dichloromethane with a volume ratio of 1.5:1 was used as an eluent. The obtained solid was recrystallized once with dichloromethane and anhydrous methanol, filtered, and the filter residue was placed in a vacuum drying oven for drying, and finally 1.97 g of solid compound (R)-13 was obtained, with a yield of 49.9%.

[0112] The chemical reaction equation is as follows:

[0113]

[0114] Synthesis of compound (R)-M5: Under nitrogen protection, 1.50 g (2.57 mmol) of compound (R)-13 and 962.1 mg (5.41 mmol) of N-bromosuccinimide (NBS) were dissolved in 20 ml of chloroform solvent, stirred for 15 minutes in a dark environment, and then 0.5 ml of N,N-dimethylformamide (DMF) was added dropwise to the reaction solution. The temperature was raised to 50 degrees Celsius and the reaction was carried out for 24 hours. After the reaction was completed, the temperature was restored to room temperature and extracted with dichloromethane and deionized water three times. The organic phase was dried, filtered, concentrated, and separated by column chromatography in sequence, and petroleum ether: dichloromethane was used as an eluent in a volume ratio of 5:1. The obtained product was further purified by recrystallization with anhydrous methanol and dichloromethane, filtered, and the solid was placed in a vacuum drying oven for drying. Finally, 1.36 g was obtained with a yield of 71.4%.

[0115] Synthesis of polymer P(R)-M5: Under argon protection, 740.5 mg (1.00 mmol) of compound (R)-M5 and 409.8 mg (1.00 mmol) of bis(trimethyltinyl)thiophene were dissolved in 8 ml of anhydrous chlorobenzene, stirred thoroughly, and then 30.0 mg of tetrakistriphenylphosphine palladium catalyst was added. The pressure tube was sealed, and the temperature was slowly raised to 140 degrees Celsius. The reaction was kept at a constant temperature for 48 hours. After the reaction was completed, it was returned to room temperature. The reaction solution was dripped into 500 ml of anhydrous methanol, the polymer was precipitated, filtered, and the filter residue was extracted with acetone, n-hexane, and chloroform in a Soxhlet extractor in turn. The chloroform component obtained was concentrated to 10-15 ml, and the concentrated solution was dripped into 400 ml of anhydrous methanol for precipitation, filtered, and the obtained solid was dried in a vacuum drying oven. Finally, 462 mg of solid was obtained with a yield of 66.7%.

[0116]

[0117] Example 8 Preparation of organic photodiode

[0118] (1) Cleaning of ITO conductive glass. Place the ITO glass substrate on a washing rack and use an ultrasonic device to clean it. The order of cleaning liquids used is acetone, isopropyl alcohol, detergent, deionized water and isopropyl alcohol, and then dry it in a vacuum oven;

[0119] (2) placing the ITO in an oxygen plasma etcher and bombarding it with oxygen plasma (O2Plasma) for 2 minutes to completely remove any residual organic matter on the surface of the ITO glass substrate;

[0120] (3) A 50 nm thick hole injection layer of PEDOT:PSS (Heraeus P VP AI 4083) was spin-coated on the ITO and then dried in a vacuum oven at 80 °C for 12 h;

[0121] (4) In a glove box with nitrogen atmosphere, a layer of polymer P(R)-M4 and Y6 (Shulun Organic Photoelectric Technology (Beijing) Co., Ltd.) was spin-coated on the PEDOT:PSS layer. A chlorobenzene solution with a mass ratio of 1:1 was then heated and annealed on a heating table at 110°C for 20 minutes to remove residual solvent and improve the morphology of the light-emitting layer film;

[0122] (5) In the vacuum deposition chamber, the -4 A 1nm thick layer of lithium fluoride (LiF) is evaporated on the organic film under a vacuum degree of Pa to facilitate electron injection. Then a 110nm thick aluminum cathode (Al) is evaporated on the LiF, where the LiF and aluminum layers are vacuum deposited through a mask plate, and the thickness is monitored by a quartz crystal. After the device is prepared, it is polarly cured and encapsulated in ultraviolet light with epoxy resin and a thin layer of glass. The single-layer device structure is (ITO / PEDOT:PSS(50nm) / P(R)-M4:Y6=1:1wt(100nm) / LiF(1nm) / Al(110nm).

[0123] The photoelectric performance of the obtained devices was tested respectively, and the test results are as follows: Figure 2 As shown in the figure, it can be seen that the P(R)-M4 device has different responses to different circular polarizations.

[0124] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A class of chiral polymer semiconductors characterized by It has the following chemical structure: n is the number of repeating units, n=2-1000.

2. A method for preparing a chiral polymer semiconductor according to claim 1, characterized in that The following steps are involved: (a) and Response (b) Reduction to diamine (c) With diketone functional group A cyclization reaction occurs to obtain (d) preparing the The double bromination is carried out with a brominating agent, and then reacted with a monomer having a bifunctional group The polymer semiconductor is obtained by coupling polymerization.

3. Use of the chiral polymer semiconductor according to claim 1 in the field of semiconductor devices.

4. Application of the chiral polymer semiconductor according to claim 1 in the field of circularly polarized light detection.

5. An electronic device, characterized in that The electronic device comprises the chiral polymer according to claim 1; the electronic device is selected from the group consisting of an organic thin film transistor, an organic solar cell, an organic photodiode, an organic phototransistor, and an organic light emitting diode.

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