Polymer based on diketopyrrolopyrrole, preparation method of polymer, organic polymer optical detector and application of organic polymer optical detector

Abstract

The invention provides a diketopyrrolopyrrole-based polymer and a preparation method thereof, and an organic polymer optical detector and application thereof, and belongs to the technical field of organic functional materials and organic electronics. The diketopyrrolopyrrole-based polymer provided by the invention has a structural general formula as shown in a formula I which is described in the specification. The diketopyrrolopyrrole-based polymer provided by the invention is used as a donor material to prepare an active layer of an organic polymer photodetector with fullerene, a condensed ring or a polymer acceptor material, so that the organic polymer photodetector has relatively high EQE and responsivity.

Description

Technical Field

[0001] This invention belongs to the field of organic functional materials and organic electronics technology, specifically relating to a polymer based on pyrrolopyrroledione and its preparation method, and an organic polymer photodetector and its application. Background Technology

[0002] Photodetectors, as devices that convert light signals into electrical signals, have greatly promoted the development of fields such as optical communication, optoelectronic imaging, environmental monitoring, machine vision, and healthcare. Compared to visible light, short-wave infrared (SWIR, 1000~2700nm) light has higher transmittance in the atmosphere and biological tissues, is less harmful to the human eye, and is less affected by environmental interference. Therefore, short-wave infrared photodetectors have important applications in biomedicine, optical communication, autonomous driving, and night vision surveillance. However, the most commonly used silicon photodetectors have limited detectivity beyond ~1000nm. The light response rate drops rapidly, reaching almost zero at ~1100nm. Currently, SWIR photodetectors are mainly inorganic photodetectors (IPDs), such as germanium (Ge) and indium gallium arsenide (InGaAs). However, the production of inorganic semiconductor single crystals requires a strict crystal growth environment and a lattice-matched substrate, making the production cost of these inorganic photodetectors high. In addition, these photodetectors typically need to operate at low temperatures to suppress dark current and achieve high specific detectivity. ).

[0003] Compared to inorganic semiconductor materials, organic semiconductor materials offer advantages such as solution-processability, tunable optical bandgap, high extinction coefficient, and the ability to be fabricated into flexible devices. Based on device structure and working principle, organic photodetectors can be categorized into diode-type (with two electrodes), photoconductive-type, and phototransistor-type (with three electrodes). Among these, diode-type organic photodetectors (OPDs) utilize the photovoltaic effect to convert light signals into electrical signals. Their device structure is similar to that of organic solar cells, enabling self-driven light detection without an external power source, making them particularly suitable for wearable devices and thus attracting widespread attention. Through the development of SWIR-absorbing organic semiconductor materials and device fabrication processes, the detection range of diode-type organic photodetectors has now been extended to 1800 nm, achieving a wavelength range of 1000–1140 nm. 12 Specific detectivity ( Despite significant progress in SWIR organic photodetectors in recent years, the variety of short-wave infrared absorbing polymer materials remains limited, and they suffer from low EQE and responsivity. Currently, materials with short-wave infrared absorption are mainly divided into two categories: small molecule acceptors based on the Y-series and polymer donors based on benzodiazepines and quinoxalines. The former offers higher responsivity but suffers from complex synthesis steps, high cost, and limitations in large-scale production. The latter typically exhibits lower packing order, making it difficult to achieve high EQE and responsivity. Therefore, developing a short-wave infrared absorbing material that is easy to synthesize and possesses high EQE and high sensitivity is of great importance in the field of SWIR photodetectors. Summary of the Invention

[0004] The purpose of this invention is to provide a polymer based on pyrrolopyrroledione and its preparation method, as well as an organic polymer photodetector and its application. The organic polymer photodetector prepared based on the polymer provided by this invention exhibits a wide spectral response range, high photodetection capability, and strong thermal stability.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a polymer based on pyrrolopyrroledione, having the general structural formula shown in Formula I: Formula I, In Formula I, n is a natural number between 5 and 1000; R is C1~C 40 Straight-chain or branched alkyl groups, C1~C 40 Straight-chain or branched haloalkyl groups, C1~C 40 alkenyl, C1~C 40 The alkynyl group has the general formula -(CH2CH2O). p CH3 or -(CH2CH2O) p The oligoether chain of H has the general formula -(CH2). y Si[(CH2) k CH3]3 or -(CH2) y Si[(CH2) k The silicon chain of CH3]2CH3 has the general formula -(CH2). x Si[(OCH2) m CH3]3 or -(CH2) x One of the silicon-oxygen chains of Si[OSi(CH3)3]2CH3, wherein p is a natural number from 1 to 40, y is a natural number from 1 to 10, k is a natural number from 1 to 40, x is a natural number from 1 to 40, and m is a natural number from 0 to 20. X1 is either O or S; Ar1 is one of II-1, II-2, II-3, II-4, and II-5; Ar2 is one of II-1, II-2, II-3, II-4, II-5, II-6, II-7, III-1, III-2, III-3, III-4, III-5, IV-1, IV-2, IV-3, IV-4, and IV-5, where X2 is one of O, S, Se, and Te, Y1 is one of F, Cl, and Br, and R1 is C1~C1. 40 Straight-chain or branched alkyl groups, C1~C 40 Halogenated alkyl groups, C1~C 40 alkenyl and C1~C 40 One of the alkynyl groups; , , , , , , , , , , , , , , , , .

[0006] The present invention also provides a method for preparing the polymer based on pyrrolopyrroledione described in the above technical solution, comprising the following steps: (1) After reacting tert-amyl alcohol and sodium, add Ar1-containing nitrile compounds and diisopropyl succinate to carry out the first substitution reaction to obtain the first intermediate product; (2) The first intermediate obtained in step (1) is mixed with cesium carbonate and a first organic solvent to carry out a nucleophilic substitution reaction, and then a compound containing R is added and mixed to carry out a second substitution reaction to obtain a second intermediate. (3) The second intermediate obtained in step (2) is mixed with the second organic solvent and the halogenated reagent to carry out the third substitution reaction to obtain the third intermediate; (4) The third intermediate product obtained in step (3) is mixed with Ar2-containing compound, catalyst, ligand and third organic solvent to carry out polymerization reaction to obtain a polymer based on pyrrolopyrroledione.

[0007] Preferably, in step (1), the molar ratio of the Ar1-containing nitrile compound to diisopropyl succinate is (20~22):10.03; the temperature of the first substitution reaction is 110~120℃, and the time of the first substitution reaction is 10~15h.

[0008] Preferably, in step (2), the molar ratio of the first intermediate product to the R-containing compound is (5~8):13.87; the temperature of the second substitution reaction is 90~130℃, and the time of the second substitution reaction is 10~15h.

[0009] Preferably, in step (3), the molar ratio of the second intermediate product to the halogenated reagent is (1~1.5):2.77; the temperature of the third substitution reaction is -5~5℃, and the time of the third substitution reaction is 5~15min.

[0010] Preferably, in step (4), the molar ratio of the third intermediate product to the Ar2-containing compound is (0.9~1.1):1; the polymerization temperature is 110~120℃, and the polymerization time is 3~5h.

[0011] The present invention also provides an organic polymer photodetector, comprising an anode, a hole transport layer, an active layer, an electron transport layer and a cathode arranged sequentially; the active layer is prepared by a polymer based on pyrrolopyrroledione as described in the above technical solution or a polymer based on pyrrolopyrroledione prepared by the preparation method described in the above technical solution and a acceptor material.

[0012] Preferably, the receptor material includes one of fullerene receptor materials, fused ring receptor materials, and polymer receptor materials.

[0013] Preferably, the thickness of the active layer is 50~1000nm.

[0014] This invention also provides applications of the organic polymer photodetector described above in the fields of health monitoring, shortwave infrared imaging, optical communication, lidar, and environmental remote sensing.

[0015] This invention provides a polymer based on pyrrolopyrroledione, having the general structural formula shown in Formula I. Using the pyrrolopyrroledione-based polymer provided by this invention as a donor material, and with fullerenes, fused rings, or polymer acceptor materials, the active layer of an organic polymer photodetector is prepared, resulting in an organic polymer photodetector with high EQE and responsivity. Attached Figure Description

[0016] Figure 1 This is a schematic diagram of the upright structure of the organic polymer photodetector provided by the present invention; Figure 2 A schematic diagram of the inverted structure of the organic polymer photodetector provided by the present invention; Figure 3 This is a flowchart illustrating the preparation process of the polymer based on pyrrolopyrroledione in Example 1; Figure 4 The NMR spectrum of compound 3 obtained in step (2) of Example 1; Figure 5 The NMR spectrum of compound 4 obtained in step (3) of Example 1; Figure 6 The NMR spectrum of compound 5 obtained in step (4) of Example 1; Figure 7 The NMR spectrum of compound 6 prepared in step (5) of Example 1; Figure 8 The NMR spectrum of compound 7 obtained in step (6) of Example 1; Figure 9 The infrared spectrum of the polymer based on pyrrolopyrroledione prepared in Example 1; Figure 10 GPC curves based on pyrrolopyrroledione prepared in Example 1; Figure 11 The infrared spectrum of the polymer based on pyrrolopyrroledione prepared in Example 2; Figure 12 GPC curves of pyrrolopyrroledione prepared in Example 2; Figure 13 The GPC curve of pyrrolopyrroledione prepared in Example 3; Figure 14 The EQE curve of the organic polymer photodetector in Application Example 1; Figure 15 The EQE curve of the organic polymer photodetector in Application Example 2; Figure 16 The EQE curve of the organic polymer photodetector in Application Example 3; Figure 17 The EQE curve of the organic polymer photodetector in Application Example 4 is shown. Detailed Implementation

[0017] This invention provides a polymer based on pyrrolopyrroledione, having the general structural formula shown in Formula I: Formula I.

[0018] In this invention, n in Formula I is a natural number between 5 and 1000.

[0019] In this invention, in formula I, R is C1~C40 Straight-chain or branched alkyl groups, C1~C 40 Straight-chain or branched haloalkyl groups, C1~C 40 alkenyl, C1~C 40 The alkynyl group has the general formula -(CH2CH2O). p CH3 or -(CH2CH2O) p The oligoether chain of H has the general formula -(CH2). y Si[(CH2) k CH3]3 or -(CH2) y Si[(CH2) k The silicon chain of CH3]2CH3 has the general formula -(CH2). x Si[(OCH2) m CH3]3 or -(CH2) x One of the silicon-oxygen chains of Si[OSi(CH3)3]2CH3, wherein p is a natural number from 1 to 40, y is a natural number from 1 to 10, k is a natural number from 1 to 40, x is a natural number from 1 to 40, and m is a natural number from 0 to 20.

[0020] In this invention, X1 in Formula I is O or S.

[0021] In this invention, in Formula I, Ar1 is one of II-1, II-2, II-3, II-4, and II-5; Ar2 is one of II-1, II-2, II-3, II-4, II-5, II-6, II-7, III-1, III-2, III-3, III-4, III-5, IV-1, IV-2, IV-3, IV-4, and IV-5; X2 is one of O, S, Se, and Te; Y1 is one of F, Cl, and Br; and R1 is C1~C1. 40 Straight-chain or branched alkyl groups, C1~C 40 Halogenated alkyl groups, C1~C 40 alkenyl and C1~C 40 One of the alkynyl groups; , , , , , , , , , , , , , , , , .

[0022] Using the pyrrolopyrrole dione-based polymer provided by this invention as a donor material, the active layer of an organic polymer photodetector is prepared with fullerene, fused ring, or polymer acceptor materials, resulting in an organic polymer photodetector with high EQE and responsivity.

[0023] The present invention also provides a method for preparing the polymer based on pyrrolopyrroledione described in the above technical solution, comprising the following steps: (1) After reacting tert-amyl alcohol and sodium, add Ar1-containing nitrile compounds and diisopropyl succinate to carry out the first substitution reaction to obtain the first intermediate product; (2) The first intermediate obtained in step (1) is mixed with cesium carbonate and a first organic solvent to carry out a nucleophilic substitution reaction, and then a compound containing R is added and mixed to carry out a second substitution reaction to obtain a second intermediate. (3) The second intermediate obtained in step (2) is mixed with the second organic solvent and the halogenated reagent to carry out the third substitution reaction to obtain the third intermediate; (4) The third intermediate product obtained in step (3) is mixed with Ar2-containing compound, catalyst, ligand and third organic solvent to carry out polymerization reaction to obtain a polymer based on pyrrolopyrroledione.

[0024] Unless otherwise specified, the present invention does not impose any special restrictions on the source of the raw materials, and commercially available products well known to those skilled in the art can be used.

[0025] In this invention, tert-amyl alcohol and sodium are mixed and reacted, and then an Ar1-containing nitrile compound and diisopropyl succinate are added to carry out a first substitution reaction to obtain a first intermediate product.

[0026] In this invention, the volume ratio of tert-amyl alcohol to the molar ratio of sodium is preferably 180 mL:(25~35) mmol, more preferably 180 mL:30 mmol. In this invention, tert-amyl alcohol is also used as a solvent.

[0027] In this invention, the reaction temperature is preferably 110~120℃, more preferably 115℃; the reaction time is preferably 2~4h, more preferably 3h; and the reaction is preferably carried out under reflux conditions.

[0028] After the reaction is complete, the product is preferably cooled to 75-85°C, and then mixed with an Ar1-containing nitrile compound and diisopropyl succinate.

[0029] The present invention does not impose any special limitations on the cooling operation; any technical solution known to those skilled in the art can be used to cool the temperature to 75~85℃.

[0030] As one embodiment, the Ar1-containing nitrile compound may specifically be 4-methoxy-2-thiophenone nitrile, with the structural formula as follows: It can also be specifically 2-thiophenone.

[0031] As one embodiment, the preparation method of the 4-methoxy-2-thiophenone nitrile is as follows: 4-bromothiophene-2-thiophene carboxaldehyde (104.69 mmol), ethylene glycol (125.63 mmol), and p-toluenesulfonic acid (1.05 mmol) are dissolved in 209.38 mL of toluene, and the mixture is stirred and refluxed for an aldol condensation reaction for 12 h. After the reaction is completed, the mixture is washed successively with sodium bicarbonate solution, dried with magnesium sulfate, filtered, and distilled under reduced pressure to obtain the first intermediate; the first intermediate (85.07 mmol) is dissolved in 110 mL of potassium iodide (25.5 mmol) and cuprous iodide (85.07 mmol). In 1,4-dioxane, sodium methoxide solution (55.2 mL, 5.4 mol / L) was added, and the reaction was carried out at 110 °C for 5 h. After the reaction was completed, the reaction solution was filtered through diatomaceous earth to obtain the filtrate. 4 mol / L hydrochloric acid (85.07 mL) was added to the filtrate, and the reaction was carried out under an inert atmosphere for 2 h. The reaction was quenched by adding saturated sodium bicarbonate aqueous solution. The mixture was then subjected to water washing, drying with anhydrous magnesium sulfate, vacuum distillation, and silica gel column separation (eluent: petroleum ether and dichloromethane in a 1:1 volume ratio) to obtain... The second intermediate (35.17 mmol) was dissolved in 70 mL of tetrahydrofuran with 28 wt% ammonia solution (70 mL). Elemental iodine (total 42.20 mmol) was added in three batches at 5 min intervals. The reaction was carried out at room temperature for 5 h. The reaction was quenched by adding sodium thiosulfate aqueous solution. The reaction was then subjected to ethyl acetate extraction, drying with anhydrous magnesium sulfate, vacuum distillation, and silica gel column separation (eluent was petroleum ether and dichloromethane in a volume ratio of 2:1) to obtain 4-methoxy-2-thiophenone nitrile.

[0032] In this invention, the volume ratio of the tert-amyl alcohol to the molar amount of the Ar1-containing nitrile compound is preferably 180 mL: (20~22) mmol, more preferably 180 mL: 21.56 mmol.

[0033] In this invention, the molar ratio of the Ar1-containing nitrile compound to diisopropyl succinate is preferably (20~22):10.03, more preferably 21.56:10.03.

[0034] In this invention, the preferred method for mixing the Ar1-containing nitrile compound and diisopropyl succinate is to first add the Ar1-containing nitrile compound, followed by the dropwise addition of diisopropyl succinate. This invention does not impose any particular limitation on the dropping rate of the diisopropyl succinate; any dropping technique well-known to those skilled in the art can be used.

[0035] In this invention, the temperature of the first substitution reaction is preferably 110~120℃, more preferably 115℃; the time of the first substitution reaction is preferably 10~15h, more preferably 12h.

[0036] After the first substitution reaction is completed, the product of the first substitution reaction is preferably cooled to 60-70°C, then acetic acid is added dropwise, the mixture is filtered, and then washed with methanol and water in sequence to obtain the first intermediate product.

[0037] In this invention, the preferred mass concentration of the acetic acid is 17.4 mol / L; the preferred volume ratio of the tert-amyl alcohol to the acetic acid is (35~37):1, more preferably 36:1. This invention does not impose any particular limitation on the dropping rate of the acetic acid; any dropping technique well-known to those skilled in the art can be used.

[0038] The present invention does not impose any special limitations on the operation of the filtration, methanol and water washing, and any technical solution known to those skilled in the art can be used.

[0039] After obtaining the first intermediate product, the present invention mixes the first intermediate product with cesium carbonate and a first organic solvent to carry out a nucleophilic substitution reaction, and then adds a compound containing R to mix and carry out a second substitution reaction to obtain the second intermediate product.

[0040] In this invention, the molar ratio of the first intermediate product to cesium carbonate is preferably 5.55:(15~18), more preferably 5.55:16.65.

[0041] In this invention, the first organic solvent is preferably N,N-dimethylformamide.

[0042] In this invention, the preferred molar ratio of the first intermediate product to the volume ratio of the first organic solvent is 5.55 mmol: (50~70) mL, more preferably 5.55 mmol: 60 mL.

[0043] In this invention, the temperature of the nucleophilic substitution reaction is preferably 90~110℃, more preferably 100℃; the time of the nucleophilic substitution reaction is preferably 10~15h, more preferably 12h.

[0044] In one embodiment, the R-containing compound may specifically be 7-(3-bromopropyl)pentadecane.

[0045] In this invention, the molar ratio of the first intermediate product to the R-containing compound is preferably (5~8):13.87, more preferably 5.55:13.87.

[0046] In this invention, the R-containing compound is preferably added by dropwise addition. This invention does not impose any particular limitation on the dropwise addition rate; any dropwise addition technique well-known to those skilled in the art can be used.

[0047] In this invention, the temperature of the second substitution reaction is preferably 90~130℃, more preferably 120℃; the time of the second substitution reaction is preferably 10~15h, more preferably 12h.

[0048] After the second substitution reaction is completed, the product of the second substitution reaction is preferably subjected to water washing, dichloromethane extraction, drying with anhydrous magnesium sulfate, vacuum distillation, and silica gel column separation in sequence.

[0049] The present invention does not impose any special limitations on the operation of water washing, dichloromethane extraction, anhydrous magnesium sulfate drying and vacuum distillation, and any technical solutions known to those skilled in the art can be used.

[0050] As one implementation, the eluent for silica gel column separation may specifically be petroleum ether and dichloromethane in a volume ratio of 1:1.

[0051] After obtaining the second intermediate product, the present invention mixes the second intermediate product with a second organic solvent and a halogenated reagent to carry out a third substitution reaction to obtain a third intermediate product.

[0052] In this invention, the second organic solvent is preferably trichloromethane.

[0053] In this invention, the preferred molar ratio of the second intermediate product to the volume ratio of the second organic solvent is 1.16 mmol: (30~50) mL, more preferably 1.16 mmol: 40 mL.

[0054] In this invention, the halogenated reagent is preferably N-bromosuccinimide.

[0055] In this invention, the molar ratio of the second intermediate product to the halogenated reagent is preferably (1~1.5):2.77, more preferably 1.16:2.77.

[0056] In this invention, the mixing of the second intermediate product with the second organic solvent and the halogenated reagent is preferably carried out by mixing the second intermediate product with the second organic solvent and adding the halogenated reagent in batches under light-protected conditions at -5~5°C.

[0057] In this invention, the halogenated reagent is preferably added in 3 to 5 batches; the amount added in each batch is preferably the same, that is, the halogenated reagent is added in 3 to 5 batches on average; the interval between each batch is preferably 5 minutes.

[0058] In this invention, the temperature of the third substitution reaction is preferably -5 to 5°C, more preferably 0°C; the time of the third substitution reaction is preferably 5 to 15 min, more preferably 10 min; and the third substitution reaction is carried out under light-protected conditions.

[0059] After the third substitution reaction is completed, the present invention preferably mixes the product of the third substitution reaction with methanol, precipitates it, and filters it to obtain the third intermediate product.

[0060] In this invention, the preferred molar ratio of the second intermediate product to the volume of methanol is 1 mmol: 100 mL; the preferred precipitation temperature is 25°C; and the preferred precipitation time is 10 min.

[0061] The present invention does not impose any special limitations on the filtering operation; any technical solution known to those skilled in the art can be used.

[0062] After obtaining the third intermediate product, the present invention mixes the third intermediate product with an Ar2-containing compound, a catalyst, a ligand and a third organic solvent to carry out a polymerization reaction to obtain a polymer based on pyrrolopyrroledione.

[0063] As one embodiment, the Ar2-containing compound may specifically be 2,5-bis(trimethyltin)-tellurol, with the structural formula [insert structural formula here]. It can also be specifically 2,5-bis(trimethyltin)-selenophenol.

[0064] In this invention, the molar ratio of the third intermediate product to the Ar2-containing compound is preferably (0.9~1.1):1, more preferably 0.98:1.

[0065] In this invention, the catalyst is preferably Pd2(dba)3.

[0066] In this invention, the molar ratio of the third intermediate product to the catalyst is preferably (190~200):5.87, more preferably 196:5.87.

[0067] In this invention, the ligand is preferably PPh3.

[0068] In this invention, the molar ratio of the third intermediate product to the ligand is preferably (190~200):23.47, more preferably 196:23.47.

[0069] In this invention, the third organic solvent is preferably toluene and N,N-dimethylformamide; the volume ratio of toluene and N,N-dimethylformamide is preferably (9~11):1, more preferably 10:1.

[0070] In this invention, the preferred molar ratio of the third intermediate product to the volume ratio of the third organic solvent is 0.196 mmol: (8~10) mL, more preferably 0.196 mmol: 9.68 mL.

[0071] In this invention, the mixing of the third intermediate product with the Ar2-containing compound, catalyst, ligand and third organic solvent is preferably carried out by mixing the third intermediate product with the Ar2-containing compound, catalyst and ligand, and adding the third organic solvent under an inert atmosphere.

[0072] In this invention, the inert atmosphere is preferably nitrogen or argon.

[0073] In this invention, the polymerization temperature is preferably 110~120℃, more preferably 115℃; the polymerization time is preferably 3~5h, more preferably 4h; and the polymerization reaction is preferably carried out under stirring conditions. This invention does not impose any special limitations on the stirring method and rate; any technical solution well-known to those skilled in the art can be used.

[0074] After the polymerization reaction is completed, the product of the polymerization reaction is preferably cooled, then methanol is added to precipitate it, and then the product is successively filtered, washed with ethanol, washed with acetone and washed with n-hexane to obtain a polymer based on pyrrolopyrroledione.

[0075] The present invention does not impose any special limitations on the cooling technology solution; any technology well known to those skilled in the art can be used to cool to room temperature.

[0076] In this invention, the preferred molar ratio of the third intermediate product to the volume of methanol is 0.196 mmol: 196 mL.

[0077] The present invention does not have a specific time limit for the precipitation, as long as the precipitation is complete.

[0078] The present invention does not impose any special limitations on the filtration operation; any technical solution known to those skilled in the art can be used to obtain the solid.

[0079] In one implementation, the ethanol washing, acetone washing, and n-hexane washing can be performed in a Soxhlet extractor. The present invention does not impose any particular limitation on the specific operation of the extraction and washing; any technical solution well-known to those skilled in the art can be used.

[0080] The preparation method provided by this invention is simple and can further improve the purity and yield of the product by controlling parameters such as the amount of each raw material, reaction temperature and time.

[0081] The present invention also provides an organic polymer photodetector, comprising an anode, a hole transport layer, an active layer, an electron transport layer and a cathode arranged sequentially; the active layer is prepared by a polymer based on pyrrolopyrroledione as described in the above technical solution or a polymer based on pyrrolopyrroledione prepared by the preparation method described in the above technical solution and a acceptor material.

[0082] In this invention, the organic polymer photodetector preferably also includes a substrate.

[0083] In one embodiment, the structure of the organic polymer photodetector may include a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode arranged sequentially (upright structure), or it may include a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode arranged sequentially (inverted structure). A schematic diagram of the upright organic polymer photodetector provided by this invention is shown below. Figure 1 As shown in the diagram, the structure of the inverted organic polymer photodetector is as follows: Figure 2 As shown.

[0084] In one embodiment, the substrate may be made of glass; the cathode may be made of ITO; the electron transport layer may be made of PNDIT-F3N-Br film, ZnO / PFNBr film or PEDOT layer; the hole transport layer may be made of molybdenum trioxide film or PNDIT-F3N-Br film; and the anode may be made of silver.

[0085] In one embodiment, the present invention mixes a polymer based on pyrrolopyrroledione with an acceptor material and a solvent to obtain a slurry, spin-coates the slurry onto the surface of a hole transport layer or an electron transport layer, and then performs thermal annealing to obtain an active layer.

[0086] In this invention, the receptor material preferably includes one of fullerene receptor materials, fused ring receptor materials, and polymer receptor materials.

[0087] In this invention, the preferred structural formula of the fullerene receptor material is shown in Formula V-1: Formula V-1.

[0088] In this invention, the preferred structural formula of the fused-ring receptor material is shown in Formula V-2: Formula V-2; in Formula V-2, Y2 is one of F, Cl, Br and H, and R2 and R3 are independently C1~C 40 Straight-chain or branched alkyl groups, C1~C 40 Halogenated alkyl groups, C1~C 40 alkenyl and C1~C 40 One of the alkynyl groups.

[0089] In this invention, the preferred structural formula of the polymer receptor material is shown in Formula V-3: Equation V-3; in Equation V-3, R4 is C1~C 40 Straight-chain or branched alkyl groups, C1~C 40 Halogenated alkyl groups, C1~C 40 alkenyl and C1~C 40 It is one of the alkynyl groups; n1 is a natural number between 5 and 4000.

[0090] In this invention, the mass ratio of the polymer based on pyrrolopyrroledione to the receptor material is preferably 1:(0.2~5).

[0091] In this invention, the solvent is preferably one of chloroform, chlorobenzene, and o-dichlorobenzene.

[0092] In this invention, the total concentration of the pyrrolopyrrole dione-based polymer and the acceptor material in the slurry is preferably 5-15 mg / mL.

[0093] In this invention, the spin coating rate is preferably 500~5000 rpm, more preferably 4000 rpm; the spin coating time is preferably 20~60 s.

[0094] In this invention, the temperature of the heat annealing is preferably 100~200℃; the heat annealing time is preferably 10~30min.

[0095] In this invention, the thickness of the active layer is preferably 50~1000 nm.

[0096] The present invention does not impose any special limitations on the preparation method of the other layers; any preparation method well known to those skilled in the art can be used.

[0097] In one embodiment, the area of ​​the organic polymer photodetector may specifically be 3.8 mm². 2 .

[0098] Using the pyrrolopyrrole dione-based polymer provided by this invention as a donor material, the active layer of an organic polymer photodetector is prepared with fullerene, fused ring, or polymer acceptor materials, resulting in an organic polymer photodetector with high EQE and responsivity.

[0099] This invention also provides applications of the organic polymer photodetector described above in the fields of health monitoring, shortwave infrared imaging, optical communication, lidar, and environmental remote sensing.

[0100] The organic polymer photodetector provided by this invention has high EQE and responsivity, and therefore can be used in the above-mentioned fields.

[0101] The present invention does not impose any special limitations on the operation of the application, and any technical solution known to those skilled in the art can be used.

[0102] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0103] Example 1 A polymer based on pyrrolopyrroledione, with the structural formula as follows: , where n is 26; The preparation method of the polymer based on pyrrolopyrroledione is as follows: (1) 4-bromothiophene-2-thiophenecarboxaldehyde (104.69 mmol, compound 1), ethylene glycol (125.63 mmol) and p-toluenesulfonic acid (1.05 mmol) are dissolved in 209.38 mL of toluene, stirred and refluxed for aldol condensation reaction for 12 h. After the reaction is completed, the product is washed with sodium bicarbonate solution, dried with anhydrous magnesium sulfate, filtered and distilled under reduced pressure to obtain the first intermediate (white liquid, 21.16 g, yield 86%), which is denoted as compound 2. (2) The first intermediate (85.07 mmol) was dissolved in 110 mL of 1,4-dioxane with potassium iodide (25.5 mmol) and cuprous iodide (85.07 mmol). Sodium methoxide solution (55.2 mL, concentration 5.4 mol / L) was added and the reaction was carried out at 110 °C for 5 h. After the reaction was completed, the reaction solution was filtered with diatomaceous earth to obtain the filtrate. 4 mol / L hydrochloric acid (85.07 mL) was added to the filtrate and the reaction was carried out under nitrogen atmosphere for 2 h. The reaction was quenched by adding saturated sodium bicarbonate aqueous solution. The reaction was then washed with water, dried with anhydrous magnesium sulfate, distilled under reduced pressure and separated by silica gel column (eluent was petroleum ether and dichloromethane in a volume ratio of 1:1) to obtain the second intermediate (white solid, 9.44 g, yield 76%), which was designated as compound 3. (3) The second intermediate (35.17 mmol) and 28 wt% ammonia (70 mL) were dissolved in 70 mL of tetrahydrofuran. Elemental iodine (total amount of elemental iodine was 42.20 mmol) was added in three equal batches at 5 min intervals. The reaction was carried out at room temperature for 5 h. The reaction was quenched by adding sodium thiosulfate aqueous solution. The reaction was then carried out by ethyl acetate extraction, drying with anhydrous magnesium sulfate, vacuum distillation, and silica gel column separation (eluent was petroleum ether and dichloromethane in a volume ratio of 2:1) to obtain 4-methoxy-2-thiophenone (white solid, 3.92 g, yield 80%), which was designated as compound 4. (4) Sodium (30 mmol) was added to 180 mL of tert-amyl alcohol and refluxed at 115 °C for 3 h. The temperature was lowered to 80 °C and 4-methoxy-2-thiophenone nitrile (21.56 mmol) was added. Then diisopropyl succinate (10.03 mmol) was added dropwise and the reaction was carried out at 115 °C for 12 h. After the reaction was completed, the temperature was lowered to 65 °C and 5 mL of acetic acid (concentration of 17.4 mol / L) was added dropwise. The mixture was filtered while hot and washed with methanol and water in sequence to obtain the first intermediate product (dark red solid, 2.71 g, yield 75%), which was designated as compound 5. (5) The first intermediate (5.55 mmol) and cesium carbonate (16.65 mmol) were dissolved in 60 mL of N,N-dimethylformamide and reacted at 100 °C for 12 h. Then, 7-(3-bromopropyl)pentadecane (13.87 mmol) was added dropwise and the temperature was raised to 120 °C for 12 h. After the reaction was completed, the product was washed with water and extracted with dichloromethane, dried with anhydrous magnesium sulfate, separated by vacuum distillation and silica gel column (eluent was petroleum ether and dichloromethane in a volume ratio of 1:1) to obtain the second intermediate (red solid, 3.60 g, yield 75%), which was designated as compound 6. (6) The second intermediate (1.16 mmol) was dissolved in 40 mL of chloroform. N-bromosuccinimide (total amount 2.77 mmol) was added in three equal portions at 0 °C in the dark, with an interval of 5 min between each addition. The reaction was carried out at 0 °C in the dark for 10 min. Methanol was added to precipitate the product. The third intermediate (purple solid, 0.97 g, yield 82%) was obtained by filtration and designated as compound 7. (7) The third intermediate (0.196 mmol), 2,5-di(trimethyltin)-tellurol (0.199 mmol), catalyst Pd2(dba)3 (5.87 μmol) and ligand PPh3 (23.47 μmol) were mixed, and 8.8 mL of toluene and 0.88 mL of N,N-dimethylformamide were added under a nitrogen atmosphere. The mixture was stirred at 115 °C for 4 h. After the reaction was completed, the mixture was cooled to room temperature, and methanol was added to precipitate the product. The mixture was filtered, and then extracted and washed in a Soxhlet extractor with ethanol, acetone and n-hexane in sequence. After drying, a polymer based on pyrrolopyrroledione (black solid, 194 mg, yield 95%) was obtained, denoted as PTODPP-Te-HDO.

[0104] The preparation flow chart of the polymer based on pyrrolopyrroledione in Example 1 is shown below. Figure 3 As shown.

[0105] The NMR data of compound 2 obtained in step (1) of Example 1 are as follows: 1H NMR (400MHz, CDCl3) δ7.21 (d, J=1.5Hz, 1H), 7.07 (dd, J=1.5, 0.6Hz, 1H), 4.14-4.05 (m, 2H), 4.05-3.97 (m, 2H).

[0106] The NMR spectrum of compound 3 obtained in step (2) of Example 1 is as follows: Figure 4 As shown, the NMR data are: 1 H NMR (400MHz, CDCl3) δ 9.82 (d, J=1.1, 1H), 7.40 (d, 1.9, 1H), 6.75 (dd, J=1.7-1.1, 1H), 3.85 (s, 3H).

[0107] The NMR spectrum of compound 4 obtained in step (3) of Example 1 is as follows: Figure 5 As shown, the NMR data are: 1 H NMR (400MHz, CDCl3) δ 7.23 (d, J=1.7Hz, 1H), 6.53 (d, J=1.7Hz, 1H), 3.83 (d, J=1.5Hz, 3H).

[0108] The NMR spectrum of compound 5 obtained in step (4) of Example 1 is as follows: Figure 6 As shown, the NMR data are: 1 H NMR (400MHz, CDCl3) δ 11.16 (s, 2H), 7.82 (s, 2H), 7.07 (s, 2H), 3.80 (s, 6H).

[0109] The NMR spectrum of compound 6 obtained in step (5) of Example 1 is as follows. Figure 7 As shown, the NMR data are: 1 H NMR (400MHz, CDCl3) δ 8.60 (s, 2H), 6.62 (s, 2H), 6.62 (t, J =8.0Hz, 4H), 3.90 (s, 6H), 1.70 (m, 4H), 1.25 (m, 60H), 0.87 (t, J=6.9Hz, 12H).

[0110] The NMR spectrum of compound 7 obtained in step (6) of Example 1 is as follows: Figure 8 As shown, the NMR data are: 1H NMR (400MHz, CDCl3) δ 8.85 (s, 2H), 4.05 (s, 6H), 3.92 (d, J=7.7Hz, 4H), 1.39 (p, J=6.6Hz, 2H), 1.44-1.10 (m, 54H), 0.85 (q, J=6.2Hz, 12H).

[0111] The infrared spectrum of the polymer based on pyrrolopyrroledione prepared in Example 1 is shown below. Figure 9 As shown, the GPC curve is as follows Figure 10 As shown. From Figure 9 It can be seen that the molecules are in the range of 1000~1500 cm. -1 The presence of a distinct CO single bond vibration absorption peak indicates that methoxy groups have been successfully introduced into the polymer. From Figure 10 As can be seen from the data, the polymer based on pyrrolopyrroledione has Mp of 65369, Mn of 27071, Mv of 66370, Mw of 75861, Mz of 145605, Mz+1 of 214508, and PD of 2.8023.

[0112] Example 2 A polymer based on pyrrolopyrroledione, with the structural formula as follows: , where n is 27; The preparation method of the polymer based on pyrrolopyrroledione differs from that in Example 1 only in that 2,5-bis(trimethyltin)-tellurol in step (7) of Example 1 is replaced with 2,5-bis(trimethyltin)-selenophenol, denoted as PTODPP-Se-HDO.

[0113] The infrared spectrum of the polymer based on pyrrolopyrroledione prepared in Example 2 is shown below. Figure 11 As shown, the GPC curve is as follows Figure 12 As shown. From Figure 11 It can be seen that the molecules are in the range of 1000~1500 cm. -1 The presence of a distinct CO single bond vibration absorption peak indicates that methoxy groups have been successfully introduced into the polymer. From Figure 12 As can be seen from the data, the polymer based on pyrrolopyrroledione has Mp of 59223, Mn of 26401, Mv of 57338, Mw of 63697, Mz of 105631, Mz+1 of 143588, and PD of 2.4127.

[0114] Example 3 A polymer based on pyrrolopyrroledione, with the structural formula as follows: , where n is 50; The preparation method of the polymer based on pyrrolopyrroledione differs from that in Example 1 only in that 4-methoxy-2-thiophenonitrile in step (4) of Example 1 is replaced with 2-thiophenonitrile, denoted as PThDPP-Te-HDO.

[0115] The GPC curve of the polymer based on pyrrolopyrroledione prepared in Example 3 is shown below. Figure 13 As shown. From Figure 13 As can be seen from the data, the polymer based on pyrrolopyrroledione has Mp of 77725, Mn of 51138, Mv of 111304, Mw of 129436, Mz of 255206, Mz+1 of 388978, and PD of 2.5317.

[0116] Application Example 1 An organic polymer photodetector comprises a glass substrate / ITO / PEDOT / PTODPP-Te-HDO:PC arranged sequentially. 61 Composition: BM / PNDIT-F3N-Br / Ag; The organic polymer photodetector is prepared as follows: A glass substrate coated with ITO is cleaned; PEDOT:PSS is spin-coated onto the ITO surface at 5000 pm; the substrate is annealed at 200°C for 40 min; and then transferred to a glove box (water and oxygen both <0.01 ppm); the PEDOT:PSS prepared in Example 1 and the acceptor material PC are then... 61 BM was dissolved in chlorobenzene at a mass ratio of 1:2.5 to obtain a slurry with a concentration of 7 mg / mL. The slurry was then spin-coated onto the PEDOT surface at a speed of 4000 rpm for 40 s. After spin-coating, the surface was heat-annealed at 200℃ for 30 min. A methanol solution of PNDIT-F3N-Br (concentration 0.5 mg / mL) was then spin-coated onto PTODPP-Te-HDO:PC at a speed of 2000 rpm. 61 After drying the BM layer, silver electrodes are deposited by vapor deposition to obtain an organic polymer photodetector, wherein the PEDOT layer is 40 nm thick, and the PODOT layer is PTODPP-Te-HDO:PC. 61 The BM layer has a thickness of 128 nm, the PNDIT-F3N-Br layer has a thickness of 5 nm, and the Ag layer has a thickness of 80 nm.

[0117] PC 61 The structural formula of BM is: .

[0118] The external quantum efficiency curve of the organic polymer photodetector in Application Example 1 was tested in air using a quantum efficiency testing system, and the results are as follows: Figure 14 As shown, standard silicon and germanium cells were used for calibration before testing. Figure 14As can be seen, the photodetector in Application Example 1 exhibits a responsivity of 0.16 A / W at 1200 nm without an applied bias voltage. This demonstrates that the organic photodetector possesses a wide spectral response range and high photodetection capability.

[0119] Application Example 2 An organic polymer photodetector is composed of a glass substrate / ITO / ZnO / PFNBr / PTODPP-Te-HDO:Y7-BO / MoO3 / Ag arranged sequentially. The organic polymer photodetector is prepared as follows: A glass substrate coated with ITO is cleaned; 0.168 g of ethanolamine and 0.3 g of zinc acetate are dissolved in 5 mL of ethylene glycol methyl ether and spin-coated onto the ITO surface at 4000 rpm; the substrate is then annealed at 150°C for 40 min; after annealing, the substrate is transferred to a glove box (water and oxygen <0.01 ppm); a methanol solution of PFNBr (concentration 1 mg / mL) is spin-coated onto the ZnO layer; and the PTODPP-Te-HDO prepared in Example 1 and the acceptor material Y7-BO are mixed at a mass ratio of 1:1. 6. Dissolved in chloroform, a slurry with a concentration of 7 mg / mL was obtained. The slurry was then spin-coated onto the PFNBr surface at a speed of 4000 rpm for 40 s. After spin-coating, it was heat-annealed at 200℃ for 10 min. After depositing a MoO3 layer, a silver electrode was then deposited to obtain an organic polymer photodetector, wherein the ZnO layer thickness was 80 nm, the PFNBr layer thickness was 5 nm, the PTODPP-Te-HDO:Y7-BO layer thickness was 234 nm, the MoO3 layer thickness was 5.0 nm, and the Ag layer thickness was 80 nm.

[0120] The structural formula of Y7-BO is: .

[0121] The EQE curve of the organic polymer photodetector in Application Example 2 is as follows: Figure 15 As shown. From Figure 15 As can be seen, the device exhibits a responsivity of 0.33 A / W at 1200 nm without applied bias. This demonstrates that the organic photodetector possesses a wide spectral response range and high photodetection capability.

[0122] Application Example 3 An organic polymer photodetector is composed of a glass substrate / ITO / ZnO / PFNBr / PTODPP-Se-HDO:Y7-BO / MoO3 / Ag arranged sequentially. The difference between the preparation method of the organic polymer photodetector and application example 2 is that the PTODPP-Se-HDO prepared in example 2 is used instead of the PTODPP-Te-HDO prepared in example 1, and the thickness of the PTODPP-Se-HDO:Y7-BO layer is 226 nm.

[0123] The EQE curve of the organic polymer photodetector in Application Example 3 is as follows: Figure 16 As shown. From Figure 16 As can be seen, the device exhibits a responsivity of 0.56 A / W at 1100 nm without applied bias. This demonstrates that the organic photodetector possesses a wide spectral response range and high photodetection capability.

[0124] Application Example 4 An organic polymer photodetector is composed of a glass substrate / ITO / ZnO / PFNBr / PThDPP-Te-HDO:Y7-BO / MoO3 / Ag arranged sequentially. The difference between the preparation method of the organic polymer photodetector and application example 2 is that the PThDPP-Te-HDO prepared in example 3 is used instead of the PThDPP-Te-HDO prepared in example 1, and the thickness of the PThDPP-Te-HDO:Y7-BO layer is 225nm.

[0125] The EQE curve of the organic polymer photodetector in Application Example 4 is as follows: Figure 17 As shown. From Figure 17 As can be seen, the device exhibits a responsivity of 0.10 A / W at 900 nm without applied bias. This demonstrates that the organic photodetector possesses a wide spectral response range and high photodetection capability.

[0126] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A polymer based on pyrrolopyrroledione, having the general structural formula shown in Formula I: Formula I, In Formula I, n is a natural number between 5 and 1000; R is C1~C 40 Straight-chain or branched alkyl groups, C1~C 40 Straight-chain or branched haloalkyl groups, C1~C 40 alkenyl, C1~C 40 The alkynyl group has the general formula -(CH2CH2O). p CH3 or -(CH2CH2O) p The oligoether chain of H has the general formula -(CH2). y Si[(CH2) k CH3]3 or -(CH2) y Si[(CH2) k The silicon chain of CH3]2CH3 has the general formula -(CH2). x Si[(OCH2) m CH3]3 or -(CH2) x One of the silicon-oxygen chains in Si[OSi(CH3)3]2CH3, wherein, p is a natural number from 1 to 40, y is a natural number from 1 to 10, k is a natural number from 1 to 40, x is a natural number from 1 to 40, and m is a natural number from 0 to 20. X1 is either O or S; Ar1 is one of II-1, II-2, II-3, II-4, and II-5; Ar2 is one of II-1, II-2, II-3, II-4, II-5, II-6, II-7, III-1, III-2, III-3, III-4, III-5, IV-1, IV-2, IV-3, IV-4, and IV-5, where X2 is one of O, S, Se, and Te, Y1 is one of F, Cl, and Br, and R1 is C1~C1. 40 Straight-chain or branched alkyl groups, C1~C 40 Halogenated alkyl groups, C1~C 40 alkenyl and C1~C 40 One of the alkynyl groups; 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 2. The method for preparing the polymer based on pyrrolopyrroledione according to claim 1, comprising the following steps: (1) After reacting tert-amyl alcohol with sodium, add Ar1-containing nitrile compounds and diisopropyl succinate to carry out the first substitution reaction to obtain the first intermediate product; (2) The first intermediate obtained in step (1) is mixed with cesium carbonate and a first organic solvent to carry out a nucleophilic substitution reaction, and then a compound containing R is added and mixed to carry out a second substitution reaction to obtain a second intermediate. (3) The second intermediate obtained in step (2) is mixed with the second organic solvent and the halogenated reagent to carry out the third substitution reaction to obtain the third intermediate; (4) The third intermediate product obtained in step (3) is mixed with Ar2-containing compound, catalyst, ligand and third organic solvent to carry out polymerization reaction to obtain a polymer based on pyrrolopyrroledione.

3. The preparation method according to claim 2, characterized in that, In step (1), the molar ratio of the Ar1-containing nitrile compound to diisopropyl succinate is (20~22):10.03; the temperature of the first substitution reaction is 110~120℃, and the time of the first substitution reaction is 10~15h.

4. The preparation method according to claim 2, characterized in that, In step (2), the molar ratio of the first intermediate product to the R-containing compound is (5~8):13.87; the temperature of the second substitution reaction is 90~130℃, and the time of the second substitution reaction is 10~15h.

5. The preparation method according to claim 2, characterized in that, In step (3), the molar ratio of the second intermediate product to the halogenated reagent is (1~1.5):2.77; the temperature of the third substitution reaction is -5~5℃, and the time of the third substitution reaction is 5~15min.

6. The preparation method according to claim 2, characterized in that, In step (4), the molar ratio of the third intermediate product to the Ar2-containing compound is (0.9~1.1):1; the polymerization temperature is 110~120℃, and the polymerization time is 3~5h.

7. An organic polymer photodetector, comprising an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode arranged sequentially; wherein the active layer is prepared by a polymer based on pyrrolopyrroledione as described in claim 1 or a polymer based on pyrrolopyrroledione prepared by any one of claims 2 to 6 and a acceptor material.

8. The organic polymer photodetector according to claim 7, characterized in that, The receptor material includes one of fullerene receptor materials, fused ring receptor materials, and polymer receptor materials.

9. The organic polymer photodetector according to claim 7, characterized in that, The thickness of the active layer is 50~1000nm.

10. The application of the organic polymer photodetector according to any one of claims 7 to 9 in the fields of health monitoring, short-wave infrared imaging, optical communication, lidar and environmental remote sensing.

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