Ginkgo leaf-shaped antimony sulfide micron dendritic crystal photoelectric detection material and preparation method and application thereof

Abstract

The invention relates to a ginkgo leaf-shaped antimony sulfide micron dendritic crystal photoelectric detection material and a preparation method and application thereof.The preparation method comprises the steps that an antimony source precursor and a morphology modifier are taken and added into water, the mixture is stirred to be uniform, then a sulfur source precursor is added, the mixture continues to be stirred to be uniform, the obtained mixed solution is transferred into a hydrothermal reaction kettle to be subjected to a hydrothermal reaction for 10-24 h at the temperature of 120-200 DEG C, and the ginkgo leaf-shaped antimony sulfide micron dendritic crystal photoelectric detection material is obtained; and cooling, centrifugally washing, and carrying out vacuum drying on the precipitate, thereby obtaining the product. According to the prepared ginkgo leaf-shaped antimony sulfide micron dendritic crystal, nanowires or nanorods serve as basic structural units, the bionic micron dendritic crystal with the complex grading order is constructed through the directional attachment and self-assembly process, rich surface states are introduced into the huge specific surface area of the bionic micron dendritic crystal, absorption of a material to visible-near infrared light can be promoted, and the bionic micron dendritic crystal has the good grading order. The characteristics of the bionic hierarchical structure and the intrinsic semiconductor are synergistic, the self-energized photoelectric detector has excellent self-energized photoelectric detection performance at 625 nm, 740 nm and 850 nm, and photoelectric detection from visible to near-infrared bands is realized without external pressure.

Description

Technical Field

[0001] This invention belongs to the field of photoelectric detection material preparation technology, specifically relating to a ginkgo leaf-shaped antimony sulfide micron dendrite photoelectric detection material, its preparation method, and its application. Background Technology

[0002] Antimony sulfide belongs to the V-VI group of semiconductor materials, possessing a direct band gap of approximately 1.4-1.7 eV, a high light absorption coefficient, and a tunable two-dimensional layered structure, demonstrating significant technological value in industrial applications. Antimony sulfide exhibits excellent light-harvesting and carrier separation capabilities in the visible to infrared spectral region, making it suitable for industrial applications such as photocatalytic reactions and energy conversion devices.

[0003] In photovoltaic devices, antimony sulfide is considered a viable alternative to cadmium-containing buffer layer materials due to its environmental friendliness and chemical stability. Studies have confirmed that antimony sulfide can form good bandgap matching with light-absorbing layers such as copper indium gallium selenide (CIGS) or perovskite, which helps in the effective separation and transport of photogenerated carriers, thereby improving the overall efficiency of photovoltaic devices. Furthermore, the material's low toxicity and good biocompatibility also offer potential applications in biosensing and medical detection. Compared to traditional semiconductors containing heavy metals such as cadmium and lead, antimony sulfide is more in line with the environmental and safety standards of green electronics.

[0004] As a common semiconductor material, antimony sulfide has a tunable bandgap, enabling modulation of its light response across different spectral ranges (such as visible and near-infrared light). This characteristic gives it significant potential in infrared detection. In fields such as military reconnaissance, medical imaging, and industrial non-destructive testing, where high detector sensitivity and response speed are required, antimony sulfide-based photodetectors have the potential to become ideal infrared sensing and imaging devices.

[0005] Although antimony sulfide shows promising applications in optoelectronic devices, its existing synthesis processes still face challenges such as high complexity and stringent conditions. For example, one existing technology (CN 110776006 A) reports a scheme for preparing multilayer two-dimensional antimony sulfide nanosheets via chemical exfoliation. This process involves a solvothermal reaction and the introduction of lithium reagents. After lithium-ion intercalation, nanosheets of different thicknesses are obtained through ultrasonication, washing, and centrifugation. However, the nanosheets prepared by this method exhibit poor uniformity in size, thickness, and morphology, and structural control is relatively difficult. Another existing technology (CN103274466 A) proposes a hydrothermal synthesis method for antimony sulfide micro / nanosheet arrays with tunable thickness. This method uses antimony salts as the antimony source, mercapto compounds as the sulfur source, water as the solvent, and sodium citrate dihydrate and ethylenediamine as morphology modifiers to achieve array growth on a tungsten substrate. However, the ethylenediamine used in this process is a highly irritating, corrosive, and sensitizing toxic chemical substance, classified as a Class 6 hazardous material, posing a threat to human health and the environment, and is inconsistent with the modern concept of green synthesis. These problems severely restrict the practical application of antimony sulfide nanomaterials. Therefore, developing a simple, easy-to-implement, and highly controllable preparation process to produce high-purity, high-stability antimony sulfide nanomaterials is particularly important for the industrial application of antimony sulfide. Summary of the Invention

[0006] The purpose of this invention is to provide a ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material, its preparation method, and its application. Ginkgo leaf-shaped antimony sulfide micron dendrites are prepared by a simple one-step hydrothermal synthesis method. The micron dendrites use nanowires or nanorods as basic structural units and are constructed into biomimetic micron dendrites with complex hierarchical order through directional attachment and self-assembly processes. They have regular morphology, stable structure, and unique physicochemical properties, showing potential application prospects in photodetectors, sensor devices, and functional surfaces.

[0007] This invention is specifically achieved through the following technical solution: a ginkgo leaf-shaped antimony sulfide micron-shaped photoelectric detection material proposed according to this invention includes the following steps: (1) Take the antimony source precursor and morphology modifier and add them to deionized water. Stir magnetically at room temperature until the mixture is homogeneous. Then, add the sulfur source precursor to the mixture and continue stirring at room temperature to obtain a mixed solution. (2) Transfer the mixed solution obtained in step (1) to a reaction vessel lined with polytetrafluoroethylene, and then place the reaction vessel in an oven and set the temperature to 120-200 ℃. React at this temperature for 10-24 h, and then allow it to cool naturally to room temperature after completion. (3) The mixture obtained after the hydrothermal reaction in step (2) is first washed by centrifugation with double-distilled water. After centrifugation, the supernatant is discarded and the precipitate is retained. The precipitate is then washed repeatedly with deionized water 3-5 times, and then washed with anhydrous ethanol 3-5 times in the same way. Finally, the precipitate is dried in a vacuum drying oven to obtain the ginkgo leaf-shaped antimony sulfide micron dendrite photoelectric detection material.

[0008] The aforementioned method for preparing the Ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material, in step (1), the antimony source precursor is selected from one or more of antimony acetate, antimony chloride, and antimony oxide; the morphology modifier is selected from one or more of 1-hexadecyl-3-methylimidazole chloride, 1-hexadecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole chloride, 1-tetradecyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole chloride, 1-dodecyl-3-methylimidazole bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride; the sulfur source is selected from one or more of sodium thiosulfate, thiourea, urea, and sodium sulfide.

[0009] The aforementioned method for preparing ginkgo leaf-shaped antimony sulfide micron dendritic photodetector material includes step (1) where the molar ratio of antimony atoms to sulfur atoms is less than 1:2; and the molar ratio of morphology modifier to antimony atoms is 1:(2-4).

[0010] In the aforementioned method for preparing ginkgo leaf-shaped antimony sulfide micron dendritic photodetector material, the amount of deionized water added in step (1) must ensure that the filling degree of the polytetrafluoroethylene liner in step (2) is 40~80%.

[0011] The aforementioned method for preparing ginkgo leaf-shaped antimony sulfide micron dendritic photoelectric detector material includes a heating rate of 5-10 ℃ / min in the oven in step (2) and a drying temperature of 40-80 ℃ and a drying time of 8-24 h in the vacuum drying oven in step (3).

[0012] The aforementioned method for preparing ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material yields ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material with a dendrite length of 10-15 m. These dendrites are folded and assembled from nanowires or nanorods with a width of 100-500 nm, exhibiting a distinct biomimetic texture structure.

[0013] The present invention also provides a ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material prepared according to the aforementioned preparation method and its application in photodetectors.

[0014] This invention also provides a photodetector comprising ginkgo leaf-shaped antimony sulfide micron-dendritic photodetector material prepared according to the aforementioned method. For example, the photodetector includes fluorine-doped indium tin oxide (FTO) glass, with an antimony sulfide thin film coated on one side of the FTO glass, and a Pt metal electrode deposited on the antimony sulfide thin film. This photodetector exhibits good self-powered photodetector response under irradiation at 625 nm, 740 nm, and 850 nm light sources, demonstrating stable switching irradiation cycles and strong light sensing sensitivity. This demonstrates that the ginkgo leaf-shaped antimony sulfide micron-dendritic material prepared by this invention has great application potential in the fields of visible and near-infrared light detection.

[0015] Compared with existing technologies, this invention has significant advantages and beneficial effects. Through the above technical solution, this invention achieves considerable technological advancement and practicality, and has broad application value, possessing at least the following advantages: (1) This invention has a relatively wide range of raw material selection. Specifically, antimony acetate, antimony oxide, and antimony chloride are selected as antimony sources, sodium thiosulfate, thiourea, urea, or sodium sulfide are selected as sulfur sources, and 1-hexadecyl-3-methylimidazole chloride, 1-hexadecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole chloride, 1-tetradecyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole chloride, 1-dodecyl-3-methylimidazole bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride are selected as morphology modifiers. Deionized water is used as the solvent, and the product is synthesized by hydrothermal method. The critical environment of high temperature and high pressure is used as the reaction micro-region, and the required high pressure environment is created by controlling the filling degree of the reaction vessel. The process route is simple, the reaction conditions are mild, and the ginkgo leaf-shaped antimony sulfide micron dendrites can be obtained through subsequent centrifugation, washing, and drying. The entire method uses inexpensive and readily available raw materials, is safe and reliable, and is environmentally friendly.

[0016] (2) The present invention is essentially a hierarchical assembly process driven by the synergistic effect of sulfur source decomposition kinetics, anisotropic crystal growth, and morphology modifier guidance. The specific mechanism is as follows: Slow release of sulfur source and formation of one-dimensional crystal nuclei: Sulfur source decomposes under hydrothermal high pressure environment, which can steadily release S 2- This relatively moderate sulfur source supply kinetics avoids instantaneous supersaturation of the reaction system, which is conducive to the formation of uniformly sized antimony sulfide crystal nuclei. Under the combined effect of the intrinsic growth habit of the crystals and the selective adsorption of morphology modifiers, these crystal nuclei preferentially grow along the one-dimensional direction, forming nanowires or nanorods as basic structural units.

[0017] Morphology guidance and assembly drive of morphology modifiers: Taking 1-hexadecyl-3-methylimidazolium chloride ionic liquid as an example, its hydrophilic imidazole cation head can be adsorbed onto specific crystal faces of newly formed antimony sulfide crystals through electrostatic interactions, effectively regulating the surface energy of different crystal faces, inhibiting radial growth, and thus strengthening the one-dimensional structure. At the same time, its hydrophobic long alkyl chain generates a steric hindrance effect in solution, and can guide and drive the orientation and self-assembly of the aforementioned one-dimensional nanowires and nanorods through non-covalent forces such as hydrophobic interactions.

[0018] Assembly of Ginkgo Leaf-like Hierarchical Dendrites: Under the influence of morphology modifiers, the initially formed one-dimensional structural units do not aggregate randomly, but rather assemble according to the principle of minimum energy through directional attachment and Ostwald ripening mechanism. They branch and connect at specific angles, mimicking the vein structure of natural ginkgo leaves, ultimately constructing ginkgo leaf-like micron dendrites with complex hierarchical order. This process successfully achieved the controllable construction from one-dimensional nanowires / nanorobars to two-dimensional biomimetic hierarchical structures.

[0019] (3) The ginkgo leaf-shaped antimony sulfide micron dendrite structure synthesized in this invention is at the mesoscale. This structure is constructed from nanoscale nanowires or nanorods as basic structural units, forming a dense, biomimetic micron dendrite with a complex hierarchical order through directional attachment and self-assembly processes. Therefore, the ginkgo leaf-shaped antimony sulfide micron dendrite is a biomimetic hierarchical mesoscale structure assembled from one-dimensional nanounits, exhibiting a regular morphology, good structural stability, and unique physicochemical properties, showing potential application prospects in fields such as photoelectric detection, sensor devices, and functional surfaces. Attached Figure Description

[0020] Figure 1 This is a SEM image of the leaf-shaped antimony sulfide micron dendrites synthesized in Example 1.

[0021] Figure 2 This is the XRD pattern of the ginkgo leaf-shaped antimony sulfide micron dendrites synthesized in Example 1.

[0022] Figure 3 The current-time (It) curves of the photodetector made from the micron-sized antimony sulfide dendrites of Ginkgo biloba synthesized in Example 1 under irradiation by light sources of different wavelengths are shown.

[0023] Figure 4 This is a SEM image of the ginkgo leaf-shaped antimony sulfide micron dendrites synthesized in Example 2.

[0024] Figure 5 This is a SEM image of the leaf-shaped antimony sulfide micron dendrites synthesized in Example 3. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] The present invention will be described in detail below with reference to specific embodiments. Unless otherwise specified, all conditions in the embodiments are performed under conventional conditions or conditions recommended by the manufacturer. Raw materials and reagents whose manufacturers are not specified are all commercially available products.

[0027] Example 1: (1) Weigh 0.39 mmol of antimony acetate and 0.1 mmol of 1-hexadecyl-3-methylimidazole chloride into a 50 mL beaker, add 15 mL of deionized water as a solvent, and stir magnetically for 30 min at room temperature to make the mixture homogeneous. Then, add 0.9 mmol of sodium thiosulfate to the mixture and continue stirring for 30 min at room temperature to obtain a mixed solution; (2) Transfer the mixed solution obtained in step (1) into a 25 mL polytetrafluoroethylene liner, and then put it into a stainless steel hydrothermal reactor, controlling the filling degree of the reactor liner to be 70%; then place the reactor in an oven, set the temperature to 150 ℃, and raise the oven to 150 ℃ at a heating rate of 5 ℃ / min. Keep the reaction at this temperature for 24 h, and then let it cool naturally to room temperature after completion. (3) The mixture obtained after the hydrothermal reaction in step (2) is centrifuged and washed. Specifically, the mixture is placed in a 50 mL centrifuge tube, 10 mL of double-distilled water is added, and after centrifugation, the supernatant is discarded and the precipitate is retained. The precipitate is then washed three times with deionized water and then washed three times with anhydrous ethanol. Finally, the centrifuge tube containing the precipitate is placed in a vacuum drying oven at 40 °C and dried for 12 h. The final antimony sulfide sample is then collected.

[0028] Figure 1 These are SEM images of the obtained antimony sulfide samples, from... Figure 1 It can be observed that the antimony sulfide sample consists of ginkgo leaf-shaped micron dendrites, with a length of approximately 10 μm. The main structure of the micron dendrites is composed of folded and assembled nanowires or nanorods with a width of approximately 100-500 nm, exhibiting a distinct biomimetic texture structure.

[0029] Figure 2 This is the XRD pattern of the obtained antimony sulfide sample, from... Figure 2It can be seen that the main diffraction peaks of the sample are very obvious and correspond to the diffraction peaks of the antimony sulfide standard card (JCPDS 42-1393). The main diffraction peaks of the sample correspond to the (020), (120), (130), (211), (221), (240), (151) and (132) crystal planes of antimony sulfide, respectively, and there are no other impurity peaks, which proves that the synthesized sample is antimony sulfide.

[0030] Preparation of antimony sulfide micron dendrite photodetector: 10 mg of the antimony sulfide micron dendrite sample prepared in step (3) of Example 1 was weighed and ultrasonically dispersed in 2 mL of anhydrous ethanol for 30 s. Then, an antimony sulfide film was spin-coated on one side of fluorine-doped indium tin oxide glass (FTO) using a spin-coating method (rotation speed of 800-3000 rpm). The thickness of the film was controlled at 300-1000 μm and allowed to air dry naturally. Subsequently, a Pt metal electrode was deposited on the side of the fluorine-doped indium tin oxide glass containing the antimony sulfide film using magnetron sputtering deposition to prepare an antimony sulfide micron dendrite photodetector. Process conditions for magnetron sputtering deposition of Pt metal electrode: sputtering power 30 W, start-up pressure parameter set to 1 Pa, sputtering deposition time 180 s, pre-sputtering time 30 s, argon flow rate 40 sccm.

[0031] The photoelectric performance of the prepared antimony sulfide micron-dendritic photodetector was tested using a Keithley 2400 digital source meter. The Pt metal electrode of the antimony sulfide micron-dendritic photodetector was brought into contact with the Keithley 2400 digital source meter. The timing shutter switch was turned on for 1 second and off for 1 second, with each cycle lasting 2 seconds. Six cycles were tested for each irradiation wavelength. This antimony sulfide micron-dendritic photodetector is a self-powered photodetector, requiring no external voltage during photoelectric performance testing. During testing, the illumination state is switched by controlling the opening and closing of the shutter: when the shutter is open, the antimony sulfide micron-dendritic material is irradiated, causing electrons to transition from the ground state to the excited state, generating photogenerated carriers. This photocurrent is led out through the Pt electrode and acquired by the digital source measurement unit, and the photocurrent signal can be observed to be rapidly generated and reach its peak instantaneously. When the shutter is closed, the illumination stops, the excited electrons in the material return to the ground state, and the photocurrent disappears. Due to structural defects and thermal effects inherent in the ginkgo leaf-shaped antimony sulfide micron dendrite material, the device exhibits only a low dark current under no-light conditions.

[0032] The photoelectric performance of the antimony sulfide micron-dendritic photodetector was tested using the above method, and the current-time (It) curves of the antimony sulfide micron-dendritic photodetector under irradiation with different wavelength light sources were obtained, as shown below. Figure 3 As shown. From Figure 3It can be observed that the prepared antimony sulfide micron-dendritic photodetector exhibits good self-powered photodetector response under visible light irradiation at 625 nm and 740 nm, demonstrating stable switching irradiation cycling. The maximum and minimum values ​​of the current represent the photocurrent and dark current of the photodetector, respectively. Figure 3 The results show that the photocurrent and dark current responses are very timely with almost no delay, indicating that the antimony sulfide micron-dendritic photodetector has strong light-sensing sensitivity. Subsequently, the current-time (It) curve of the antimony sulfide micron-dendritic photodetector under 850 nm near-infrared irradiation was tested, revealing that it still exhibits relatively stable photoresponse behavior under 850 nm light source irradiation, demonstrating strong light-sensing sensitivity. These findings indicate that the ginkgo leaf-shaped antimony sulfide micron-dendritic particles prepared in this invention have great application potential in the fields of visible and near-infrared light detection.

[0033] Ginkgo leaf-shaped antimony sulfide micron-dendritic structures exhibit excellent self-powered photodetector performance at wavelengths of 625 nm, 740 nm, and 850 nm, which may be attributed to the synergistic effect between their unique biomimetic hierarchical structure and intrinsic material properties. These micron-dendritic structures are composed of folded nanowires or nanorods with widths of approximately 100-500 nm, forming distinct vein-like patterns. This structure possesses a large specific surface area, introducing abundant surface states that facilitate the utilization of low-energy near-infrared light (e.g., at 850 nm) through multi-step absorption, thereby broadening the spectral response range. Simultaneously, it can effectively capture charge carriers excited by visible light (e.g., at 625 nm and 740 nm). Furthermore, the biomimetic patterns of the micron-dendritic structures form a highly efficient light-trapping network. Their fractal geometry and rough surfaces significantly increase the light propagation path within the material through multiple reflections and scatterings, enhancing the device's light absorption capability. At the numerous interfaces formed by the overlapping and folding of nanowires / nanorobars, local built-in electric fields are formed due to lattice mismatch and energy state differences. These electric fields can efficiently drive the separation of photogenerated electrons and holes, generating a photovoltaic effect, and ultimately realizing self-powered photoelectric detection in the visible to near-infrared bands.

[0034] Example 2: (1) Weigh 0.39 mmol of antimony chloride and 0.1 mmol of hexadecyltrimethylammonium bromide into a 50 mL beaker, add 15 mL of deionized water as a solvent, and stir magnetically for 30 min at room temperature to make the mixture homogeneous. Then, add 0.9 mmol of sodium thiosulfate to the mixture and continue stirring at room temperature for 30 min to obtain a mixed solution; (2) Transfer the mixed solution obtained in step (1) into a 25 mL polytetrafluoroethylene liner, and then put it into a stainless steel hydrothermal reactor, controlling the filling degree of the reactor to be 80%. Then place the hydrothermal reactor in an oven, set the temperature to 160 ℃, and raise the temperature to 160 ℃ at a rate of 5 ℃ / min. Maintain the temperature at this temperature for 18 h, and then allow it to cool naturally to room temperature after completion. (3) The mixture obtained after the hydrothermal reaction in step (2) is centrifuged and washed. Specifically, the mixture is placed in a 50 mL centrifuge tube, 10 mL of double-distilled water is added, and after centrifugation, the supernatant is discarded and the precipitate is retained. The precipitate is then washed three times with deionized water and then washed three times with anhydrous ethanol. Finally, the centrifuge tube containing the precipitate is placed in a vacuum drying oven at 50 °C and dried for 10 h. The final antimony sulfide sample is then collected.

[0035] Figure 4 This is a SEM image of the antimony sulfide sample prepared in Example 2. From the image, it can be observed that when hexadecyltrimethylammonium bromide is used as a morphology modifier and antimony chloride is used as the metallic antimony source, the morphology of the antimony sulfide sample obtained by hydrothermal synthesis is basically consistent with that of the antimony sulfide sample obtained in Example 1, also exhibiting ginkgo leaf-like micron dendrites. Figure 4 It can be observed that the length of the leaf-shaped antimony sulfide micron-dendritic crystals in Ginkgo biloba is approximately 15 μm. The main structure of the micron-dendritic crystals is composed of folded and assembled nanowires or nanorods, exhibiting a distinct biomimetic texture structure. Figure 1 compared to, Figure 4 The biomimetic texture is denser. The width of the nanowires or nanorods is approximately 100-500 nm, indicating that the process for preparing ginkgo leaf-shaped antimony sulfide micron dendrites in this invention has a certain degree of repeatability.

[0036] Example 3: (1) Weigh 0.2 mmol of antimony oxide and 0.1 mmol of 1-tetradecyl-3-methylimidazole chloride into a 50 mL beaker, add 15 mL of deionized water as a solvent, and stir magnetically for 30 min at room temperature to make the mixture homogeneous. Then, add 0.75 mmol of thiourea to the mixture and continue stirring at room temperature for 30 min to obtain the final mixed solution; (2) Transfer the mixed solution obtained in step (1) into a 25 mL polytetrafluoroethylene liner, and then put it into a stainless steel hydrothermal reactor, controlling the filling degree of the hydrothermal reactor to be 80%. Then place the hydrothermal reactor in an oven, set the temperature to 180 ℃, and raise the temperature to 180 ℃ at a heating rate of 5 ℃ / min. Maintain the temperature at this temperature for 12 h, and then allow it to cool naturally to room temperature after completion. (3) The mixture obtained after the hydrothermal reaction in step (2) is centrifuged and washed. Specifically, the mixture is placed in a 50 mL centrifuge tube, 10 mL of double-distilled water is added, and after centrifugation, the supernatant is discarded and the precipitate is retained. The precipitate is then washed three times with deionized water and then washed three times with anhydrous ethanol. Finally, the centrifuge tube containing the precipitate is placed in a vacuum drying oven at 50 °C and dried for 10 h. The final antimony sulfide sample is then collected.

[0037] Figure 5 This is a SEM image of the antimony sulfide sample prepared in Example 3. From the image, it can be observed that when 1-tetradecyl-3-methylimidazole chloride is used as a morphology modifier, antimony oxide as the antimony source, and thiourea as the sulfur source, the morphology of the antimony sulfide sample prepared by hydrothermal synthesis is basically consistent with that obtained in Examples 1 and 2, also exhibiting ginkgo leaf-like micron dendrites. Figure 5 It can be observed that the length of the Ginkgo leaf-shaped antimony sulfide micron dendrites is about 15 μm, and the main structure is composed of folded nanowires or nanorods with obvious biomimetic texture structure. The width of the nanowires or nanorods is about 100-500 nm.

[0038] The above description is merely an embodiment of the present invention and is not intended to limit the present invention in any way. The present invention can also have other embodiments based on the above structure and function, which will not be listed hereafter. Therefore, any simple modifications, equivalent changes, and alterations made by those skilled in the art to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing a ginkgo leaf-shaped antimony sulfide micron-sized photoelectric detection material, characterized in that, Includes the following steps: (1) Take the antimony source precursor and morphology modifier and add them to deionized water. Stir at room temperature until the mixture is homogeneous. Then, add the sulfur source precursor to the mixture and continue stirring at room temperature to obtain a mixed solution. (2) Transfer the mixed solution obtained in step (1) to a reaction vessel lined with polytetrafluoroethylene, place the reaction vessel in an oven, set the temperature to 120-200 ℃, and react at this temperature for 10-24 h. After completion, allow it to cool naturally to room temperature. (3) The mixture obtained after the hydrothermal reaction in step (2) is first washed by centrifugation with double-distilled water. After centrifugation, the supernatant is discarded and the precipitate is retained. The precipitate is then washed repeatedly with deionized water 3-5 times, and then washed with anhydrous ethanol 3-5 times in the same way. Finally, the precipitate is dried in a vacuum drying oven to obtain the ginkgo leaf-shaped antimony sulfide micron dendrite photoelectric detection material.

2. The preparation method of the ginkgo leaf-shaped antimony sulfide micron-shaped photoelectric detector material as described in claim 1, characterized in that, The antimony source precursor in step (1) is selected from one or more of antimony acetate, antimony chloride, and antimony oxide; the morphology modifier is selected from one or more of 1-hexadecyl-3-methylimidazole chloride, 1-hexadecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole chloride, 1-tetradecyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole chloride, 1-dodecyl-3-methylimidazole bromide, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride; the sulfur source is selected from one or more of sodium thiosulfate, thiourea, urea, and sodium sulfide.

3. The preparation method of the ginkgo leaf-shaped antimony sulfide micron-shaped photoelectric detector material as described in claim 1, characterized in that, Step (1) The molar ratio of antimony atoms to sulfur atoms is less than 1:2; the molar ratio of morphology modifier to antimony atoms is 1:(2-4).

4. The preparation method of the ginkgo leaf-shaped antimony sulfide micron-shaped photoelectric detector material as described in claim 1, characterized in that, The amount of deionized water added in step (1) must ensure that the filling degree of the polytetrafluoroethylene liner in step (2) is 40~80%.

5. The preparation method of the ginkgo leaf-shaped antimony sulfide micron-shaped photoelectric detector material as described in claim 1, characterized in that, The heating rate of the oven in step (2) is 5-10 ℃ / min, and the drying temperature of the vacuum drying oven in step (3) is 40-80℃, and the drying time is 8-24 h.

6. The method for preparing the ginkgo leaf-shaped antimony sulfide micron-dendritic photoelectric detection material as described in any one of claims 1-5, characterized in that, The obtained ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material has a dendrite length of 10-15 μm. The micron dendrite is assembled by folding nanowires or nanorods with a width of 100-500 nm and has an obvious biomimetic texture structure.

7. Ginkgo leaf-shaped antimony sulfide micron dendrite photoelectric detection material obtained by any of the preparation methods described in claims 1-5.

8. The application of the ginkgo leaf-shaped antimony sulfide micron dendrite photodetector material obtained by any of the preparation methods according to claims 1-5 in photodetectors.

9. A photodetector, characterized in that, The photodetector material includes the ginkgo leaf-shaped antimony sulfide micron dendrites prepared by any of the preparation methods described in claims 1-5.

Images