Receptor material, near-infrared organic photoelectric detector containing receptor material, and preparation method and application of receptor material

Abstract

The invention relates to the technical field of organic photoelectric materials, and discloses an acceptor material, a near-infrared organic photoelectric detector containing the acceptor material, and a preparation method and application of the near-infrared organic photoelectric detector. The acceptor material is marked as ZCH-12, and the chemical structure of the acceptor material is as shown in formula (1): (1) the acceptor material ZCH-12 molecule is designed by introducing a quinone pi bridge between an electron-rich central unit and an electron-deficient terminal group in a manner of asymmetrically introducing one end; the optical energy gap of the ZCH-12 is remarkably reduced by asymmetrically introducing the quinone pi bridge, electron polarization is induced, and electrostatic interaction sites are formed. By introducing a quinoline ring quinone type pi-bridge structure for increasing the length of a connecting chain, aggregation can be enhanced, a stronger intramolecular charge transfer effect can be promoted, and a good stacking characteristic is achieved. The asymmetric acceptor molecule ZCH-12 provided by the invention has excellent absorption characteristic at 1002nm, and when the asymmetric acceptor molecule ZCH-12 is matched with a PBDB-T donor molecule with a proper energy level to serve as an active layer of an organic photoelectric device, the asymmetric acceptor molecule ZCH-12 shows extremely low dark current noise and high specific detection rate, and shows good film thickness insensitivity.

Description

Technical Field

[0001] This application relates to the field of organic optoelectronic materials technology, specifically to a receptor material, a near-infrared organic photodetector containing the same, its preparation method, and its application. Background Technology

[0003] Currently, common methods for detecting microplastics in drinking water include visual microscopy, fluorescence spectroscopy, and pyrolysis-gas chromatography / mass spectrometry (Py-Gs / Ms). These methods are limited to time-consuming, expensive, and cumbersome laboratory equipment, requiring specialized technicians and are not suitable for real-time on-site testing in daily life.

[0004] Organic photodetectors (OPD devices) offer advantages such as tunable molecular bandgap, good biocompatibility, high sensitivity, and fast response. They can reflect changes in pollutant concentration through variations in photoelectric signals and can even achieve specific detection of different water pollutants by changing the wavelength of the irradiated laser. This allows for rapid on-site monitoring of pollutants such as microplastics in bottled drinking water without the need for water sample pretreatment. However, considering the extremely low levels of microplastics in bottled drinking water, especially the presence of nanoscale microplastics, the OPD devices used require excellent detection performance, such as low noise interference and high specificity detection rate. However, currently reported OPD devices are limited by high dark current and insufficient response due to the organic photoelectric materials, posing a challenge for microplastic detection in drinking water. Summary of the Invention

[0005] This application provides a receptor material, a near-infrared organic photodetector containing the same, a method for preparing the same, and its application, aiming to solve the technical problems of high dark current and insufficient response in existing organic photodetectors due to limitations of organic photoelectric materials.

[0006] To achieve the above objectives, the present application adopts the following technical solution.

[0007] A first aspect of this application provides a receptor material, denoted as ZCH-12, whose chemical structure is shown in formula (1): (1).

[0008] A second aspect of this application provides a method for preparing the above-mentioned receptor material, the synthetic route of which is as follows: .

[0009] Preferably, the method for preparing the receptor material includes: S1, compound CHDBr, hexamethyldistin, and tetraphenylphosphine palladium were dissolved in toluene and heated under reflux under argon protection; then, after removing toluene and performing chromatography, compound 1 was obtained; The chemical structure of the compound CHDBr is shown below:

[0010] S2, compound 1, 4,6-dibromo-3-fluorothiopheno[3,4-b]thiophene-2-carboxylic acid octyl ester, tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphine were dissolved in toluene and heated under argon protection and refluxed; then, after removing toluene and performing chromatography, compound 2 was obtained; S3, under argon protection, compound 2, phosphoryl chloride and DMF were added to 1,2-dichloroethane and stirred at room temperature; water was slowly added and the mixture was extracted with ethyl acetate; the extract was washed, dried and the solvent was removed to obtain the crude product; the crude product was purified to obtain compound 3; S4, under argon protection, compound 3, 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile was dissolved in chloroform, pyridine was slowly added, and the mixture was heated and stirred to carry out the reaction; the reaction product was precipitated with methanol, and the precipitate was purified to obtain the acceptor material ZCH-12.

[0011] Preferably, in steps S1 and S2, The molar ratio of compound CHDBr, hexamethyldistin, and tetra-triphenylphosphine palladium is 1:(5~10):(0.04~0.1); The molar ratio of compound 1, octyl 4,6-dibromo-3-fluorothiopheno[3,4-b]thiophene-2-carboxylate, tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphine is 1:(1.2~2):(0.06~0.1):(0.24~0.4); The heating reflux temperature is 110-125℃, and the time is 8-12h.

[0012] Preferably, in step S3, the molar ratio of compound 2, phosphoryl chloride, and DMF is 1:(2~10):(10~50).

[0013] Preferably, in step S4, the molar ratio of compound 3, 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile and pyridine is 1:(3~6):(0.01~0.02); The reaction temperature is 60~65℃ and the time is 8~12h.

[0014] A third aspect of this application provides a near-infrared organic photodetector, which includes a transparent substrate, a bottom electrode, an electron transport layer, an active layer, a hole transport layer, and a metal electrode. The active layer comprises PBDB-T and the receptor material ZCH-12 as described in claim 1.

[0015] Preferably, the transparent substrate includes either a rigid substrate or a flexible substrate; When the transparent substrate is a rigid substrate, the electron transport layer includes 2PACz, the hole transport layer includes PDINO, and the metal electrode is Ag; When the transparent substrate is a flexible substrate, the electron transport layer includes PEDOT:PSS, the hole transport layer includes PDINO, and the metal electrode is Ag.

[0016] In a fourth aspect of this application, the above-mentioned near-infrared organic photodetector is provided for the detection of microplastic contaminants in sewage or drinking water.

[0017] Preferably, the detection method is as follows: The near-infrared organic photodetector is encapsulated and placed in a water sample or attached to the bottle wall in a watertight manner. It responds to the refraction and reflection of light by microplastic pollutants in water / absorption of specific spectral bands after dyeing. The concentration of microplastics is determined by real-time monitoring of the photocurrent changes of the near-infrared organic photodetector using a laser beam.

[0018] Compared with the prior art, the beneficial effects of this application are as follows: This application designs the acceptor material ZCH-12 molecule by introducing a quinone-type π-bridge asymmetrically at one end between the electron-rich central unit and the electron-deficient terminal group. The asymmetric introduction of the quinone-type π-bridge significantly reduces the optical bandgap of ZCH-12, induces electronic polarization, and forms electrostatic interaction sites. The introduction of the quinoline ring quinone-type π-bridge structure, which increases the length of the connecting chain, enhances aggregation and promotes a stronger intramolecular charge transfer effect, exhibiting excellent stacking properties. The asymmetric acceptor molecule ZCH-12 of this application exhibits excellent absorption characteristics at 1002 nm. When paired with a PBDB-T donor molecule of suitable energy level as the active layer of an organic optoelectronic device, it displays extremely low dark current noise and high specific detectivity, and exhibits good film thickness insensitivity.

[0019] The near-infrared organic photodetector of this application exhibits excellent detection sensitivity, displaying a broader and optimized responsivity in the 300–1000 nm wavelength range, peaking at 908 nm; it can cover almost all absorption bands of different types of water pollutants, making it better suited for the detection of trace microplastics. It also exhibits good underwater photostability at 7.5 μW·cm⁻¹.-2 After 5000 seconds of laser irradiation with high optical power, only less than 0.1% degradation was observed, demonstrating high reliability in sustainable water quality monitoring applications. Furthermore, its insensitivity to membrane thickness makes it easier to handle large areas and allows for flexible fabrication. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments recorded in this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 The UV-Vis spectra of ZCH-12 in chloroform solution and solid films are shown. Figure 2 The results of thermogravimetric analysis of ZCH-12 are shown in the figure. Figure 3 The graph shows the test results of the responsivity test of the rigid near-infrared organic photodetector in Example 2. Figure 4 The graph shows the dark current density-voltage test results of the rigid near-infrared organic photodetector in Example 2. Figure 5 The graph shows the specific detectivity test results of the rigid near-infrared organic photodetector in Example 2. Figure 6 A schematic diagram of a testing device for detecting microplastics in bottled drinking water; Figure 7 This is a graph showing the test results for microplastics in bottled drinking water. Detailed Implementation

[0022] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0023] In the following description of this embodiment, the terms "including", "comprising", "having", and "containing" are all open-ended terms, meaning that they include but are not limited to.

[0024] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0025] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0026] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0027] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0028] Those skilled in the art will understand that the numerical ranges in the embodiments of this application should be understood as each intermediate value between the upper and lower limits of the specifically disclosed range. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this application. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0029] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0030] In a first aspect, this application provides a receptor material, denoted as ZCH-12, whose chemical structure is shown in formula (1): (1).

[0031] The synthetic route of the receptor material ZCH-12 in this application is as follows: .

[0032] Its preparation methods include: S1, compound CHDBr, hexamethyldistin, and tetraphenylphosphine palladium were dissolved in toluene and heated under reflux under argon protection; then, after removing toluene and performing chromatography, compound 1 was obtained; The chemical structure of the compound CHDBr is shown below:

[0033] The molar ratio of compound CHDBr, hexamethyldistin, and tetraphenylphosphine palladium is 1:(5~10):(0.04~0.1). The heating reflux temperature is 110~125℃, and the time is 8~12h.

[0034] In this application, after the reaction, the solvent toluene is removed by vacuum distillation, and then compound 1 is obtained by column chromatography of basic aluminum oxide.

[0035] S2, compound 1, octyl 4,6-dibromo-3-fluorothiopheno[3,4-b]thiophene-2-carboxylate, tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphine were dissolved in toluene and heated under argon protection and refluxed; then the solvent was removed and chromatography was performed to obtain compound 2; The molar ratio of compound 1, 4,6-dibromo-3-fluorothiopheno[3,4-b]thiophene-2-carboxylic acid octyl ester, tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphine is 1:(1.2~2):(0.06~0.1):(0.24~0.4). The heating reflux temperature is 110~125℃, and the time is 8~12h.

[0036] In this application, after the reaction, the solvent toluene is removed by vacuum distillation, and then compound 2 is obtained by column chromatography of basic aluminum oxide.

[0037] S3, under argon protection, compound 2, phosphoryl chloride and DMF were added to 1,2-dichloroethane and stirred at room temperature; water was slowly added and extracted with ethyl acetate; the extract was washed, dried and the solvent was removed to obtain a crude product; the crude product was purified to obtain compound 3; wherein the molar ratio of compound 2, phosphoryl chloride and DMF was 1:(2~10):(10~50).

[0038] In this application, the extract was washed with saturated brine, and the organic layer after washing was dried with anhydrous Na2SO4 for 1 hour; then the solvent was removed under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography with hexane as the eluent to obtain compound 2 as a purple-red solid.

[0039] S4, under argon protection, compound 3, 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile was dissolved in chloroform, pyridine was slowly added, and the mixture was heated and stirred to carry out the reaction; the reaction product was precipitated with methanol, and the precipitate was purified to obtain the acceptor material ZCH-12.

[0040] The molar ratio of compound 3, 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile and pyridine is 1:(3~6):(0.01~0.02); The reaction temperature is 60~65℃ and the time is 8~12h.

[0041] In this application, the precipitate was purified by silica gel column chromatography using petroleum ether / chloroform (volume ratio 4 / 5) as the eluent to obtain the black acceptor material ZCH-12.

[0042] This application also provides a near-infrared organic photodetector, which includes a transparent substrate, a bottom electrode, an electron transport layer, an active layer, a hole transport layer, and a metal electrode; wherein, the active layer includes PBDB-T and the acceptor material ZCH-12 as described in claim 1, preferably with a mass ratio of PBDB-T to ZCH-12 of 1:1.2.

[0043] In this application, the transparent substrate includes either a rigid substrate or a flexible substrate; the rigid substrate may be glass, and the flexible substrate may be PET. By selecting either a rigid or flexible transparent substrate, rigid near-infrared organic photodetectors or flexible near-infrared organic photodetectors can be fabricated.

[0044] In this application, when a rigid substrate such as glass is selected as the transparent base, a rigid near-infrared organic photodetector is obtained. The electron transport layer of the rigid near-infrared organic photodetector includes 2PACz, the hole transport layer includes PDINO, and the metal electrode is Ag. Its structure is ITO / 2PACz / PBDB-T:ZCH-12 / PDINO / Ag.

[0045] When a flexible substrate such as PET is used as the transparent base, a flexible near-infrared organic photodetector is obtained. The electron transport layer of the flexible near-infrared organic photodetector includes PEDOT:PSS, the hole transport layer includes PDINO, and the metal electrode is Ag. Its structure is PET / ITO / PEDOT:PSS / PBDB-T:ZCH-12 / PDINO / Ag.

[0046] The near-infrared organic photodetector of this application can be used to detect pollutants in water, such as microplastics, heavy metals and dyes, and is especially suitable for detecting microplastic pollutants in sewage or drinking water.

[0047] During detection, the near-infrared organic photodetector is encapsulated and placed in the water sample or attached to the bottle wall in a watertight manner. It responds to the refraction and reflection of light by microplastic pollutants in the water / absorption of specific spectral bands after staining. The photocurrent change of the near-infrared organic photodetector is monitored in real time by a laser beam to determine the concentration of microplastics.

[0048] The present application will be further illustrated by the following examples.

[0049] Example 1 This embodiment provides a receptor material ZCH-12, the synthetic route of which is as follows:

[0050] Preparation methods include: S1, 0.2 g of CHDBr, 0.22 g of hexamethyldistin, 0.07 g of tetraphenylphosphine palladium and 15 ml of dry chromatographically pure toluene were added to a two-necked round-bottom flask. The mixture was heated under argon protection at 120 °C for 12 h under reflux. After cooling to room temperature, the solvent toluene was removed by vacuum distillation. The mixture was then subjected to alkaline alumina column chromatography to obtain 0.18 g of compound 1. S2, 0.18 g of compound 1, 0.07 g of 4,6-dibromo-3-fluorothiopheno[3,4-b]thiophene-2-carboxylic acid octyl ester, 0.007 g of tris(dibenzylideneacetone)palladium (Pd2(dba)3), 0.01 g of tris(o-methylphenyl)phosphine (P(o-tol)3), and 20 ml of dry chromatographically pure toluene were added to a two-necked round-bottom flask. The mixture was heated under argon protection and refluxed at 120 °C for 12 h. After cooling to room temperature, the solvent toluene was removed by vacuum distillation, and 0.12 g of compound 2 was obtained by column chromatography.

[0051] In step S3, under argon protection, 80 mg of compound 2, 0.3 mL of phosphoric acid chloride, and 2 mL of DMF were added to 20 mL of 1,2-dichloroethane (20 mL), and the mixture was stirred at room temperature for 12 h. Subsequently, 60 mL of water was slowly added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, the organic layer was collected, dried over anhydrous Na₂SO₄ for 1 h, and then the solvent was removed under vacuum to obtain the crude product. The crude product was purified by silica gel column chromatography using hexane as the eluent to give 53 mg of a purple-red solid, which was compound 3.

[0052] The NMR data for compound 3 are as follows: ¹H NMR (400 MHz, CDCl₃) ¹H NMR (400 MHz, chloroform-d) δ 10.16 (s, ¹H), 9.96 (s, ¹H), 8.19 (q, J = 8.9 Hz, 2H), 4.67 (t, J = 7.7 Hz, 4H), 4.35 (t, J = 6.6 Hz, 2H), 3.25 (t, J = 7.8 Hz, 2H), 3.09 (t, J = 7.9 Hz, 2H), 2.14 (h, J = 6.5 Hz, 3H), 1.95 (dt, J = 17.7, 8.1 Hz, 5H), 1.77 (p, J = 6.8 Hz, 3H), 1.48 (dp, J = 35.1, 6.5 Hz, 13H), 1.27 (s, 26H), 1.18 – 0.64 (m, 105H).

[0053] In step S4, under argon protection, 53 mg of compound 3, 42 mg of 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile, and 20 mL of dry chloroform were added to a two-necked round-bottom flask, followed by the slow addition of 0.2 mL of pyridine. The mixture was stirred at 65 °C for 12 h. After cooling to room temperature, 70 mL of methanol was added to precipitate the reaction mixture. The precipitate was purified by silica gel column chromatography using petroleum ether / chloroform (4 / 5 v / v) as the eluent to give 26 mg of the black compound ZCH-12.

[0054] NMR data from ZCH-12: ¹H NMR (400 MHz, CDCl₃) ¹H NMR (400 MHz, chloroform-d) δ 9.06 (s, ¹H), 8.78 (s, ¹H), 8.48 (q, J = 8.2 Hz, 2H), 8.00 (dt, J = 19.1, 9.1 Hz, 2H), 7.67 (dt, J = 16.2, 7.4 Hz, 2H), 4.77 (d, J = 7.7 Hz, 4H), 4.36 (t, J = 6.9 Hz, 2H), 3.23 (dt, J = 14.3, 7.6 Hz, 4H), 2.29 (s, 2H), 2.01 (p, J = 7.9 Hz, 2H), 1.84 (dt, J = 28.3, 7.6Hz, 4H), 1.58 (dt, J = 25.9, 7.5 Hz, 5H), 1.19 – 0.97 (m, 52H), 0.82 (ddt, J = 47.9, 19.3, 6.6 Hz, 28H).

[0055] Example 2 This embodiment provides a rigid near-infrared organic photodetector, the preparation method of which includes: The ITO-coated glass substrate (17 × 17 mm) was cleaned in an ultrasonic bath with detergent water, deionized water, acetone and isopropanol for 15 min respectively, and dried by nitrogen purging; then it was subjected to ultraviolet irradiation treatment in an ultraviolet ozone chamber for 15 min. An ethanol solution of [2-(9h-carbazole-9-yl)ethyl]phosphonic acid (2PACz) with a concentration of 0.3 mg / mL was applied to an ITO / glass substrate using a pipette. The substrate was then spin-coated at 3000 rpm for 20 s using a spin coater, baked at 100°C for 15 min, and the ethanol solvent was evaporated to obtain the 2PACz layer. PBDB-T and ZCH-12 were dissolved in chlorobenzene at a mass ratio of 1:1.2 to obtain a mixed solution with a PBDB-T concentration of 8 mg / mL; the mixed solution was spin-coated onto a 2PACz layer to form an active layer with a thickness of 120 nm. PDINO was dissolved in methanol to obtain a concentration of 1.0 mg / mL. -1 The solution was spin-coated onto the top of the active layer at a speed of 3000 rpm for 20 seconds to obtain the PDINO layer; Subsequently, at a pressure of 2 × 10 -5 Rigid near-infrared organic photodetectors, denoted as rigid OPDs, are obtained by depositing a 100 nm thick Ag layer on a PDINO layer through thermal evaporation under a vacuum of Pa. Their effective area is 2 × 2 mm. 2.

[0056] Example 3 This embodiment provides a flexible near-infrared organic photodetector, the preparation method of which includes: The ITO-coated PET flexible substrate (17 × 17 mm) was cleaned in an ultrasonic bath with detergent water, deionized water, acetone and isopropanol for 15 min respectively, dried by nitrogen purging, and then attached to a glass substrate and subjected to ultraviolet irradiation treatment in an ultraviolet ozone chamber for 5 min. An ethanol solution of [2-(9h-carbazole-9-yl)ethyl]phosphonic acid (2PACz) with a concentration of 0.3 mg / mL was applied to an ITO / glass substrate using a pipette. The substrate was then spin-coated at 3000 rpm for 20 s using a spin coater, baked at 100°C for 15 min, and the ethanol solvent was evaporated to obtain the 2PACz layer. PBDB-T and ZCH-12 were dissolved in chlorobenzene at a mass ratio of 1:1.2 to obtain a mixed solution with a PBDB-T concentration of 8 mg / mL; the mixed solution was spin-coated onto a 2PACz layer to form an active layer with a thickness of 120 nm. PDINO was dissolved in methanol to obtain a concentration of 1.0 mg / mL. -1 The solution was spin-coated onto the top of the active layer at a speed of 3000 rpm for 20 seconds to obtain the PDINO layer; Subsequently, at a pressure of 2 × 10 -5 Under a vacuum of Pa, a 100 nm thick Ag layer was deposited on the PDINO layer by thermal evaporation. After peeling off the glass substrate, a flexible near-infrared organic photodetector, denoted as flexible OPDs, was obtained, with an effective area of ​​2 × 2 mm. 2 .

[0057] Part 1: The performance molecular characterization and analysis of the receptor material ZCH-12 prepared in Example 1.

[0058] 1. UV absorption performance test of ZCH-12 ZCH-12 single component and a mixed component of PBDB-T:ZCH-12 with a mass ratio of 1:1.2 were dissolved separately in chloroform, with the concentration of the ZCH-12 single component solution being 10 mg / ml and the concentration of the PBDB-T:ZCH-12 mixed component solution being 8 mg / ml. Both solutions were then spin-coated onto a 1.7 x 1.7 cm quartz plate at 2000 rpm to obtain solid films. Simultaneously, ZCH-12 single component was dissolved in chloroform in a volumetric flask to prepare a 10% concentration solution. -6 A dilute solution of mol / L.

[0059] The above-mentioned solid film and dilute solution were subjected to ultraviolet absorption tests. The ultraviolet-visible spectra were measured using a Cary 5000 ultraviolet-visible spectrophotometer. The starting scan position was 1100 nm, and the ending scan position was 300 nm. The grating switching position was 900 nm.

[0060] The UV-Vis spectra of ZCH-12 in chloroform solution and solid films are as follows: Figure 1 As shown. From Figure 1 It can be seen that ZCH-12 exhibits a maximum absorption peak at 758 nm in diluted chloroform solution. The maximum absorption peak in the thin film was 883 nm, a 125 nm redshift compared to the solution. This indicates that introducing a quinoline cycloquinone π-bridge structure that increases the linker chain length enhances aggregation and promotes a stronger intramolecular charge transfer (ICT) effect.

[0061] 2. Thermogravimetric analysis test Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were performed on ZCH-12 at a heating rate of 10 °C / min. -1 Using a nitrogen atmosphere, the test results are as follows: Figure 2 As shown.

[0062] Depend on Figure 2 It can be seen that ZCH-12 has a decomposition temperature of 314℃ and exhibits good thermal stability.

[0063] The second part evaluates the photoelectric performance of the rigid near-infrared organic photodetector prepared in Example 2, as detailed below: 1. Response Test The responsivity of the device was tested using an Enlitech QE-R EQE system equipped with a standard silicon diode in the wavelength range of 300-1100 nm. The test results are as follows: Figure 3 As shown. From Figure 3 It can be seen that a value of 0.51 A / W is achieved at a wavelength of 908 nm in the near-infrared region, which is the best value reported to date for near-infrared photodetectors.

[0064] 2. Dark current density-voltage test The dark current density-voltage curve was recorded using a semiconductor device analyzer (Keysight Technologies, B1500A). The test results are as follows: Figure 4 As shown. From Figure 4 It can be seen that the ZCH-12 OPD device exhibits an extremely low dark current density (4.6 × 10⁻⁶) at -1V. -9 Acm -2 ), which is 2.5 × 10 at 0V. -12 A cm -2This demonstrates that the low noise, charge recombination process, and few defect states of the ZCH-12 OPD device are conducive to achieving a better signal-to-noise ratio and excellent optoelectronic performance.

[0065] 3. Detectability test Specific detectivity of rigid near-infrared organic photodetectors This quantifies its ability to detect weak light signals. Specific detectivity (SDR) ) is defined as:

[0066] , Where A is 0.2 cm × 0.2 cm, B is the bandwidth (1 Hz), and in is the noise current in area A.

[0067] Test results are as follows Figure 5 As shown. From Figure 5 It can be seen that it has a wavelength greater than 10 in the entire 300-1000nm spectral range. 13 Jones ratio detectivity demonstrates excellent high-specificity optical detection capability.

[0068] Part Three: Detection of Microplastics in Bottled Drinking Water A commercially available 550 nm laser source was used as the optical signal generator to generate a pre-prepared polypropylene microplastic solution (concentration 4 mg / mL). -1 Dilute to a specific concentration gradient (e.g., 2 mg / L) -1 1 mg L -1 0.5 mg L -1 0.2 mg L -1 The flexible near-infrared organic photodetector of Example 3 was used for real-time photocurrent detection, and the test device was inserted into the device. Figure 6 As shown in the figure. Current values ​​corresponding to concentration changes were recorded using a semiconductor device analyzer (KEYSIGHT B1500A). The current-concentration linear detection range was then fitted to determine the minimum detection limit. The test results are as follows: Figure 7 As shown.

[0069] from Figure 7 It is known that the limit of detection (LOD) of the flexible near-infrared organic photodetector in this application for detecting trace polypropylene microplastics in bottled drinking water is 0.5 mg / L and no additional fluorescent staining is required; the detection limit of polypropylene microplastics is further increased to 0.2 mg / L through staining treatment, which significantly improves the detection sensitivity; the detection limit is lower than the national safety emission standard and is comparable to the detection capability of ultraviolet-visible light.

[0070] The OPD in-situ detection of trace microplastics in water using the method described in this application can save costs, time, energy consumption and human resources, and is more relevant to daily life; it is of great significance for protecting human health and promoting sustainable environmental development.

[0071] Although this application has been described in detail in this specification with general descriptions and specific embodiments, some modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, such modifications or improvements made without departing from the spirit of this application are all within the scope of protection claimed in this application.

Claims

1. A material for a receptor, characterized by, The acceptor material is denoted as ZCH-12, and the chemical structure is shown as formula (1): (1)。 2. The method of producing a receptor material according to claim 1, characterized by, The synthesis route is as follows: 。 3. The method of claim 2, wherein the acceptor material is prepared by a process comprising: It comprises: S1, compound CHDBr, hexamethyl ditin and tetraphenylphosphonium palladium are dissolved in toluene, heated to reflux under argon protection, then toluene is removed, and chromatography is processed to obtain compound 1; The chemical structure of the compound CHDBr is as follows: ； S2, compound 1, 4, 6-dibromo-3-fluoro thieno [3, 4-b] thien-2-carboxylic acid octyl ester, tris (dibenzalacetone) palladium and tris (o-methyl phenyl) phosphorus are dissolved in toluene, heated to reflux under argon protection, then toluene is removed, and chromatography is processed to obtain compound 2; S3, under argon protection, compound 2, phosphorus oxychloride and DMF are added to 1, 2-dichloroethane, stirred at room temperature, water is slowly added, and extracted with ethyl acetate, then the extract is washed, dried and the solvent is removed to obtain the crude product, and the crude product is purified to obtain compound 3; S4, under argon protection, compound 3 and 2-(5, 6-difluoro-3-oxo-2, 3-dihydro-1H-inden-1-yl) malononitrile are dissolved in chloroform, pyridine is slowly added, heated and stirred to react, the reaction product is precipitated with methanol, and the precipitate is purified to obtain the acceptor material ZCH-12.

4. The production method according to claim 3, characterized by, In steps S1 and S2, The molar ratio of compound CHDBr, hexamethyl ditin and tetraphenylphosphonium palladium is 1: (5-10) : (0.04-0.1) ; The molar ratio of compound 1, 4, 6-dibromo-3-fluoro thieno [3, 4-b] thien-2-carboxylic acid octyl ester, tris (dibenzalacetone) palladium and tris (o-methyl phenyl) phosphorus is 1: (1.2-2) : (0.06-0.1) : (0.24-0.4) ; The temperature of the heating reflux is 110-125℃, and the time is 8-12h.

5. The preparation method according to claim 3, characterized in that, In the step S3, the molar ratio of compound 2, phosphorus oxychloride and DMF is 1: (2-10) : (10-50).

6. The preparation method according to claim 3, characterized in that, In the step S4, the molar ratio of compound 3, 2-(5, 6-difluoro-3-oxo-2, 3-dihydro-1H-inden-1-yl) malononitrile and pyridine is 1: (3-6) : (0.01-0.02) ; The temperature of the reaction is 60-65℃, and the time is 8-12h.

7. A near-infrared organic photodetector, characterized by, It comprises a transparent substrate, a bottom electrode, an electron transport layer, an active layer, a hole transport layer and a metal electrode; The active layer comprises PBDB-T and the acceptor material ZCH-12 of claim 1.

8. The near-infrared organic photodetector of claim 7, wherein, The transparent substrate comprises any one of rigid substrate or flexible substrate; When the transparent substrate is a rigid substrate, the bottom electrode is ITO, the electron transport layer comprises 2PACz, the hole transport layer comprises PDINO, and the metal electrode is Ag; When the transparent substrate is a flexible substrate, the bottom electrode is ITO, the electron transport layer comprises PEDOT:PSS, the hole transport layer comprises PDINO, and the metal electrode is Ag.

9. Use of the near-infrared organic photodetector of claim 7 for detecting microplastic pollutants in sewage or drinking water.

10. Use according to claim 9, characterized in that, The method for detecting is: The near-infrared organic photodetector is sealed in the water sample or attached to the bottle wall, which responds to the specific spectral band generated by the microplastic pollutants in the water after refraction and reflection of light / dyeing; The photogenerated current change of the near-infrared organic photodetector is monitored in real time by a laser beam, thereby determining the concentration of microplastics.

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