Three-dimensional insert type cage-shaped indium sulfide, preparation method thereof and indium sulfide photoelectric detector

Abstract

The invention belongs to the technical field of fine chemical engineering, and particularly relates to three-dimensional insertion piece type cage-shaped indium sulfide, a preparation method thereof and an indium sulfide photoelectric detector, the diameter of the three-dimensional insertion piece type cage-shaped indium sulfide is 10-15 microns, the main body structure of the cage-shaped indium sulfide is a micron flower ball formed by folding and assembling a plurality of ultrathin indium sulfide nanosheets, the diameter of the micron flower ball body is 10 microns, the thickness of the ultrathin indium sulfide nanosheets forming the micron flower ball is 50 nm, and a plurality of indium sulfide square sheets with the thickness of 100-200 nm and the side length of 1-3 microns are embedded in the micron flower ball. The prepared three-dimensional insertion sheet type cage-shaped indium sulfide is novel in structure, good in dispersity, high in stability and large in specific surface area, has a wider ultraviolet-visible light absorption range and higher absorption strength, is beneficial to effective separation and transmission of photon-generated carriers, shows huge performance improvement in ultraviolet-visible light detection application, and can be used for preparing the three-dimensional insertion sheet type cage-shaped indium sulfide. Wide application prospects are realized in the fields of photocatalysis, photoelectric devices, energy storage, environmental pollutant treatment and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of fine chemical industry, and particularly relates to a three-dimensional plug-in sheet type cage-like indium sulfide and a preparation method thereof and an indium sulfide photoelectric detector. BACKGROUND

[0002] Indium sulfide is rapidly becoming a focus material in multiple cutting-edge technology fields due to its unique wide band gap (~2.0-2.3 eV) semiconductor properties. The core attraction lies in its excellent light capture ability and efficient photoelectric conversion mechanism. This compound exhibits significant affinity for visible and near-infrared light, and can efficiently convert incident photons into excited-state carriers (electron-hole pairs), which makes it outstanding in photocatalytic applications, such as driving water decomposition to produce hydrogen or accelerating surface redox reactions in the degradation process of pollutants. In the field of photovoltaic technology, indium sulfide is being used as a key buffer layer material to replace traditional toxic cadmium sulfide due to its good biocompatibility. It can form an optimized energy band coordination with light-absorbing layers such as copper indium gallium selenide or perovskite, effectively promoting the separation and directional transport of photo-generated charges, thereby becoming an important driving force for improving the energy conversion efficiency and long-term operation stability of solar cells. Indium sulfide shows application potential in electrochemical energy storage systems, especially in lithium-ion batteries. Its unique crystal layer structure and suitable lithium ion insertion / extraction potential window make it a candidate for negative electrode materials, aiming to achieve higher energy storage density (specific capacity) and longer charge and discharge cycle life.

[0003] It is particularly worth noting that the penetration of indium sulfide in photoelectric sensing technology is accelerating. This is mainly due to the synergistic effect of three advantages: excellent light response and speed (rapid and sensitive response to weak light signals), efficient carrier transport capability (ensuring rapid migration of photo-generated charges within the material, low recombination loss, improving device response rate and signal-to-noise ratio), and inherent low biological toxicity (meeting the rigid demand for green and safe modern electronic devices). The integration of these characteristics makes indium sulfide an ideal semiconductor substrate for building high-performance optical detectors, imaging sensors, ambient light sensing elements, ultraviolet sensitive devices, and even emerging flexible wearable optoelectronic systems, providing indispensable material support for front-line applications such as Internet of Things sensing layer, machine vision, and biomedical monitoring, and serving as a reliable bridge for precise and efficient conversion of optical signals to electrical signals.

[0004] At present, the morphology of indium sulfide is mostly hexagonal sheet or nanoflower ball, and the morphology is relatively single. The preparation of indium sulfide nanomaterials with complex morphology needs to use ion liquid and polyvinylpyrrolidone as surfactants. However, after adding these morphology modifiers, the sample cleaning process is difficult to increase, and the production cost is increased. At the same time, since the morphology modifiers are difficult to completely remove, the comprehensive performance (such as surface activity) of the sample is also affected. The synthesis method is relatively complex, and the subsequent purification process is complicated. For example, the patent CN102335616A uses a wet chemical method to synthesize indium sulfide powder. The pH of the precursor solution is first controlled to 1-3 by using acetic acid. Finally, the nanoflower ball with uneven morphology is obtained, and the morphology control lacks stability.

[0005] The above problems seriously restrict the application of indium sulfide materials. Therefore, it is particularly important to develop a simple and easy-to-operate preparation process with strong controllability to produce an indium sulfide material with high purity, high stability and novel structure for the industrial application of indium sulfide in the field of photoelectric detection. SUMMARY

[0006] In view of the above problems, the present application provides a three-dimensional plug-in sheet type cage-like indium sulfide and a preparation method thereof and an indium sulfide photoelectric detector, so as to solve the problems of single morphology of indium sulfide prepared by the prior art, and the need for template agent for preparing indium sulfide materials with complex morphology, which causes complex subsequent treatment process and high cost. The three-dimensional plug-in sheet type cage-like indium sulfide prepared by the present application has novel structure, good dispersity, high stability, large specific surface area, wider ultraviolet-visible light absorption range and stronger absorption intensity, and has wide application prospect in the fields of photocatalysis, photoelectric devices, energy storage and environmental pollution control.

[0007] One of the purposes of the present application is to provide a three-dimensional plug-in sheet type cage-like indium sulfide. The diameter of the whole cage-like indium sulfide is 10-15 μm. The main structure of the cage-like indium sulfide is a micron flower ball assembled by folding a plurality of ultrathin indium sulfide nanosheets. The diameter of the micron flower ball is 10 μm. The thickness of the ultrathin indium sulfide nanosheet constituting the micron flower ball is 50 nm. A plurality of indium sulfide square sheets with a thickness of 100-200 nm and a side length of 1-3 μm are inlaid on the micron flower ball.

[0008] Another purpose of the present application is to provide a preparation method of the three-dimensional plug-in sheet type cage-like indium sulfide, which specifically comprises the following steps: (1) Take indium source precursor and sulfur source precursor into solvent, stir at room temperature to obtain precursor dispersion; wherein the molar ratio of indium atom and sulfur atom is <2:3, the solvent can be selected from one of ethanol, propanol, isopropanol, ethylene glycol, glycerol, or a mixed solvent of two or three of ethanol, propanol, isopropanol, ethylene glycol, glycerol; the amount of solvent used is 50-80% of the volume of the inner lining of the hydrothermal reactor in step (2); (2) Transfer the precursor dispersion obtained in step (1) to a hydrothermal reactor, and hydrothermal reaction at 120-200 ℃ for 10-24 h, and then naturally cool to room temperature after the reaction is completed; (3) Take out the product in the cooled reactor, centrifugal separation, and then wash the precipitate after centrifugation with distilled water for 3-5 times, and then wash with anhydrous ethanol for 3-5 times, and then place the centrifuge tube containing the precipitate sample in a vacuum drying oven to dry, to obtain a yellow powder product, which is a three-dimensional plug type cage-like indium sulfide.

[0009] The preparation method of the three-dimensional plug type cage-like indium sulfide, the indium source precursor can be selected from one of indium acetate, indium nitrate, and indium chloride, and the sulfur source precursor can be selected from one of thioacetamide, sodium thiosulfate, and thiourea.

[0010] The preparation method of the three-dimensional plug type cage-like indium sulfide, the filling degree of the hydrothermal reactor lining in step (2) is preferably 50-80%.

[0011] The preparation method of the three-dimensional plug type cage-like indium sulfide, the heating rate during hydrothermal reaction in step (2) is preferably 4-10 ℃ / min.

[0012] The preparation method of the three-dimensional plug type cage-like indium sulfide, the temperature of vacuum drying in step (3) is preferably 40-80 ℃, and the drying time is preferably 8-24 h.

[0013] Another object of the present application is to provide an indium sulfide photoelectric detector, wherein the indium sulfide in the indium sulfide photoelectric detector is a three-dimensional plug type cage-like indium sulfide obtained by the above preparation method. The indium sulfide photoelectric detector can be prepared according to the following method, but the amount of indium sulfide and anhydrous ethanol used in the following preparation method and other preparation parameters are not considered as limitations of the present application: Take 5 mg of the indium sulfide powder prepared according to the preparation method of the three-dimensional inserted sheet type cage-shaped indium sulfide described above, and use 2 mL of anhydrous ethanol for ultrasonic dispersion, for 1 min, to obtain a uniform and stable indium sulfide dispersion. A uniform film is deposited on the surface of a pre-cleaned and dried fluorine-doped tin oxide (FTO) conductive glass substrate (size: 1 0mm ×10 mm, square resistance: < 10Ω / sq) by using a spin coating method: drop a proper amount of the indium sulfide dispersion at the center of the FTO substrate, first spin at a speed of 500 rpm for 5 s to spread the solution, then quickly increase the speed to 4000 rpm and maintain for 30 s to form a uniform film, this process is repeated 1-3 times, and finally the thickness of the indium sulfide film is accurately controlled in the range of 300 ~ 1000 μm. The film after spin coating is naturally air-dried at room temperature. After the film is completely dried, a screen printing equipment is used to print an Ag strip electrode pattern on the surface of the indium sulfide film using a commercially available high-conductivity silver paste (model: RY-120 line silver paste), the width of each electrode is 2.0 mm, the length is 8.0 mm, and the spacing between the edges of adjacent electrodes is 4.0 mm, and after printing, it is cured at 60 ℃ for 60 min to form a firm Ag electrode, thereby preparing a photoelectric detector device based on the three-dimensional inserted sheet type cage-shaped indium sulfide.

[0014] The essence of preparing the three-dimensional inserted sheet type cage-shaped indium sulfide is the synergistic result of the decomposition kinetics of the sulfur source and the guiding effect of the alcohol solvent. Taking thiourea as an example, the specific step-by-step mechanism is as follows: (1) Progressive decomposition of thiourea and release of sulfur source: thiourea ((NH2)2C=S) slowly decomposes in alcohol solvent at high temperature (usually 120~200 ℃), releasing H2S and intermediate mercaptan species (such as NH2C≡S), avoiding local supersaturation leading to agglomeration, and creating conditions for ordered nucleation.

[0015] (2) Coordination and morphology guidance of alcohol solvent: alcohol solvent is not only a medium, but also a soft template and a coordination agent: its hydroxyl group forms [In(ROH) 3+ ] n 3+ complex with indium ions (In

[0016] (3) Assembly mechanism of inserted sheet structure: the initially formed indium sulfide nanosheets self-assemble through Ostwald ripening due to surface energy anisotropy. Alcohol molecules form a hydrogen-bonded network between the sheet layers, guiding the sheet layers to stack in a "edge-face" or "face-face" manner, and finally forming an inserted sheet type hierarchical structure.

[0017] ​The present application has obvious advantages and beneficial effects compared with the prior art. By the above technical scheme, the present application can achieve considerable technical progress and practicability, and has wide utilization value, and at least has the following advantages: (1) The present application uses a solvothermal method, and uses an alcohol solvent as a morphology control agent, to successfully prepare three-dimensional inserted sheet type cage-like indium sulfide with good dispersibility, high stability and high purity. The three-dimensional inserted sheet type cage-like indium sulfide mainly has alpha phase indium sulfide micron flower balls, and beta phase indium sulfide square sheets with a thickness of 100-200 nm are inlaid in the alpha phase indium sulfide micron flower balls. As can be seen from the scanning electron microscope (SEM) image, the insertion of the beta phase indium sulfide square sheets effectively prevents the agglomeration of the spherical matrix, so that the cage-like indium sulfide exhibits excellent dispersibility, and the sample morphology is complete and not broken, which confirms the good structural stability. Figure 5 Figure 2 The X-ray diffraction pattern shows that the indium sulfide has sharp diffraction peaks, and has characteristic peak types of alpha phase and beta phase, without other impurity peaks, which proves that the three-dimensional inserted sheet type cage-like indium sulfide has high purity. The BET adsorption method is used to measure that the specific surface area of the three-dimensional inserted sheet type cage-like indium sulfide is as high as 105 m 2 / g, which significantly improves the number of active sites of the material. The ultraviolet-visible absorption spectrum ranges from 350 nm to 800 nm, which is mainly due to the synergistic effect of the heterostructure formed by the alpha phase and the beta phase indium sulfide, which effectively widens and enhances the light absorption capacity. The wide and strong light absorption characteristics are particularly beneficial to promote the effective separation and transmission of photo-generated carriers, thereby significantly improving its performance in ultraviolet-visible light photodetectors, and showing broad application prospects in the fields of photocatalysis, photovoltaic devices, energy storage and environmental pollution control.

[0018] (2) The present application is relatively wide in raw material selection, and can use indium acetate, indium nitrate, indium chloride, etc. as the indium source, and thioacetamide, sodium thiosulfate, and thiourea as the sulfur source. The solvent can be selected from conventional solvents such as ethanol, propanol, isopropanol, ethylene glycol, and glycerol. The entire solvothermal process does not need to add any morphology modifier, template agent, such as polyvinylpyrrolidone, sodium dodecyl sulfate, cetyltrimethylammonium bromide, ionic liquid, etc., which conforms to the ecological concept of green environmental protection.

[0019] ​(3) The present application utilizes the critical environment of high temperature and high pressure as the reaction microzone, and creates the high pressure environment required for the reaction by controlling the filling degree of the reaction kettle. In the reaction process, the presence of the alcohol solvent not only slows down the rate of sulfur ion release from the sulfur source, making the supply of sulfur ions more stable and controllable, but also can be adsorbed on the specific crystal face of the generated indium sulfide nanocrystal, changing the surface energy of different crystal faces, thereby regulating the crystal growth rate and the final morphology, promoting the formation of sheet structure, sheet layer stacking or specific exposed crystal face. In addition, the surface tension of the alcohol solvent is usually lower than that of water, which is conducive to reducing the overall surface tension of the system, helping the reactants and intermediates to disperse better in the solvent, reducing agglomeration, and promoting the uniform deposition of the product on the substrate, thereby forming three-dimensional inserted sheet type cage-like indium sulfide with special morphology. The entire synthesis process is relatively simple, the reaction conditions are mild, the safety is good, the raw materials are cheap and easy to obtain, the production cost is reduced, the product post-processing process is simplified, and the impact on the environment is reduced.

[0020] (4) The three-dimensional inserted sheet type cage-like indium sulfide synthesized by the present application is a material with a unique hierarchical mesostructure, which spans the nanometer to micrometer scale. The three-dimensional inserted sheet type cage-like indium sulfide is composed of two parts: ① The core building unit is a nanoscale indium sulfide nanosheet. Through a precise assembly and folding process, these nanoscale indium sulfide nanosheets first construct a porous micrometer flower ball matrix. The micrometer flower ball matrix is not a dense solid, but has abundant mesopores (2-50 nm) and macropores (>50 nm) in the interior, forming a highly open three-dimensional network framework with good light trapping effect, which can significantly improve the photoelectric detection performance of the material. ② The micrometer level (usually 1-3 μm) indium sulfide square sheet is ingeniously embedded or "inserted" into the micrometer flower ball. These micrometer level indium sulfide square sheets have regular structures and form a strong structural coupling with the micrometer flower ball matrix, finally forming a "cage-like" overall structure. The internal core area of the three-dimensional inserted sheet type cage-like indium sulfide is usually hollow, and the multi-level pore wall wrapped or supported around the hollow core is composed of the micrometer flower ball matrix and the micrometer level indium sulfide square sheet embedded in the micrometer flower ball matrix. Thus, the three-dimensional inserted sheet type cage-like indium sulfide prepared by the present application perfectly combines the high specific surface area and porosity of the micrometer flower ball, the stability and structure of the micrometer level indium sulfide square sheet, and the unique spatial environment provided by the hollow cage cavity, and is a typical hierarchical mesostructure material with large specific surface area, high stability and good physical and chemical properties, which has broad application prospects in the fields of photocatalysis, optoelectronic devices, energy storage and environmental pollution control. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is the SEM image of the three-dimensional inserted sheet type cage-like indium sulfide prepared in Example 1.

[0022] Figure 2is an XRD pattern of the three-dimensional intercalated cage-like indium sulfide prepared in Example 1.

[0023] Figure 3 is an ultraviolet-visible absorption spectrum of the three-dimensional intercalated cage-like indium sulfide prepared in Example 1.

[0024] Figure 4 is a plot of the time-dependent current of the indium sulfide photodetector made of the three-dimensional intercalated cage-like indium sulfide prepared in Example 1 under illumination of different wavelengths of LED light.

[0025] Figure 5 is an SEM image of the three-dimensional intercalated cage-like indium sulfide prepared in Example 2.

[0026] Figure 6 is an SEM image of the three-dimensional intercalated cage-like indium sulfide prepared in Example 3. DETAILED DESCRIPTION

[0027] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the present application will be described below in connection with specific embodiments. Obviously, the described embodiments are only some of the embodiments of the present application but not all the embodiments. Based on the embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without creative effort belong to the scope of protection of the present application.

[0028] The present application will be described in detail below with specific embodiments. In the following embodiments, the specific conditions not mentioned are all carried out according to the conventional conditions or the conditions recommended by the manufacturers. The raw materials and reagents used are all conventional products that can be purchased on the market, and the manufacturers are not mentioned.

[0029] Example 1 (1) 0.2 mmol of indium acetate and 0.6 mmol of thioacetamide were weighed into a 50 mL beaker, 32 mL of isopropyl alcohol was added as a solvent, and the mixture was stirred magnetically at room temperature for 30 min to obtain a precursor dispersion; (2) The precursor dispersion prepared in step (1) was transferred into a 50 mL polytetrafluoroethylene liner, and then the liner was loaded into a simple hydrothermal reaction kettle made of stainless steel. The filling degree of the liner in the reaction kettle was controlled to be 64%. The hydrothermal reaction kettle was placed in an oven, the temperature was set to 160 ℃, and the temperature was raised to 160 ℃ at a rate of 5 ℃ / min. The reaction time was set to 12 h, and the reaction was cooled to room temperature naturally after completion. (3) The product in the reactor after cooling was taken out and centrifuged, the precipitate after centrifugation was washed with distilled water twice and centrifuged 3 times, then the centrifuge tube containing the precipitate sample was placed in a vacuum drying oven at 50 ℃ for 12 h, and the dried sample was collected, which was a yellow indium sulfide powder.

[0030] The obtained indium sulfide powder was characterized in terms of morphology, composition and phase, as shown in Figures 1-4 . Figure 1 is a SEM image of the indium sulfide powder obtained in Example 1, from which it can be observed that the indium sulfide has a cage-like structure feature, the diameter of the whole cage-like indium sulfide is 10-15 μm, the main structure of the cage-like indium sulfide is a micron flower ball assembled by folding a plurality of ultrathin indium sulfide nanosheets, the diameter of the micron flower ball is about 10 μm, the thickness of the ultrathin indium sulfide nanosheet constituting the micron flower ball is about 50 nm, a plurality of indium sulfide quadrilateral sheets with a thickness of 100-200 nm and an edge length of 1-3 μm are inserted into the micron flower ball, the indium sulfide quadrilateral sheets are stacked or crossed with each other, the internal core area of the three-dimensional inserted sheet type cage-like indium sulfide is a hollow structure, and the multi-level pore wall wrapped or supported around the hollow core is composed of the micron flower ball matrix and the indium sulfide quadrilateral sheets inserted into the micron flower ball matrix, thereby forming the three-dimensional inserted sheet type cage-like indium sulfide with a special morphology structure. The specific surface area of the three-dimensional inserted sheet type cage-like indium sulfide was measured by BET adsorption method to be 105 m² / g.

[0031] Figure 2 is an XRD pattern of the indium sulfide powder obtained in Example 1, which shows sharp indium sulfide diffraction peaks, proving that the synthesized is indium sulfide, the diffraction peaks have characteristic peak patterns of α phase and β phase, and there is no other impurity peak, proving that the three-dimensional inserted sheet type cage-like indium sulfide material synthesized has high purity. The α phase indium sulfide is the micron flower ball matrix, and the β phase indium sulfide is the indium sulfide quadrilateral sheet.

[0032] The indium sulfide powder obtained in Example 1 was dispersed by ultrasonic dispersion with ethanol solvent, and the obtained dispersion was tested by ultraviolet-visible spectrophotometer, and the results are shown in Figure 3 . It can be seen that the cage-like indium sulfide prepared has a wide spectrum absorption due to the significant hierarchical structure, and the absorption wavelength is 350-800 nm, and there is a more obvious absorption peak near 415 nm. This is mainly due to the synergistic effect of the heterostructure formed by the α phase indium sulfide micron flower ball and the β phase indium sulfide quadrilateral sheet, which effectively widens and enhances the light absorption capacity. The wide and strong light absorption characteristics are particularly beneficial to promote the effective separation and transmission of photo-generated carriers, thereby significantly improving its performance in ultraviolet-visible light photodetector.

[0033] Weigh 5.0 mg of the three-dimensional insert-type cage-like indium sulfide sample prepared in Example 1 and place it in 2.0 mL of anhydrous ethanol for ultrasonic dispersion. The dispersion time was strictly controlled within 1 min to obtain a uniform and stable indium sulfide dispersion. Subsequently, a thin film was deposited on a pre-cleaned and dried fluorine-doped tin oxide (FTO) conductive glass substrate (size: 10 mm × 10 mm, sheet resistance: < 10 Ω / sq) using a spin-coating method: an appropriate amount of indium sulfide dispersion was dropped onto the center of the FTO substrate, and the substrate was first rotated at 500 rpm for 5 s to achieve solution spreading. Then, the rotation speed was rapidly increased to 4000 rpm and held for 30 s to form a uniform film. This process was repeated 1-3 times, and the thickness of the indium sulfide film was finally precisely controlled within the range of 300-1000 μm. The spin-coated film was allowed to air dry at room temperature. After the film is completely dry, Ag strip electrode patterns are printed on the surface of the indium sulfide film using a screen printing machine with commercially available high-conductivity silver paste (model: RY-120 line silver paste). Each electrode is 2.0 mm wide and 8.0 mm long, and the spacing between the edges of adjacent electrodes is 4.0 mm. After printing, the electrode is cured at 60 °C for 60 minutes to form a solid Ag electrode, thereby obtaining a photodetector device based on three-dimensional intercalated cage-like indium sulfide.

[0034] To evaluate its photoelectric performance, the indium sulfide photodetector was placed in a completely dark room under zero bias (0V) conditions. A Keithley 2400 digital source meter was used as the current sensing device, connected to a computer data acquisition system. The device was illuminated with a standard LED light source (25 mW / cm²) covering the ultraviolet to visible light region (e.g., 365 nm, 465 nm, 530 nm, 625 nm). The chronocurrent (It) curve of the indium sulfide photodetector under periodic illumination (on / off cycle: 2 seconds) was recorded and plotted in real time. Figure 4 As shown in the figure. The test results confirm that the prepared photodetector based on three-dimensional insert-type cage-like indium sulfide exhibits significant and stable photocurrent response in the ultraviolet-visible wavelength range, demonstrating excellent self-powered photodetector performance.

[0035] Example 2: (1) Weigh 0.2 mmol indium chloride and 0.5 mmol thiourea into a 50 mL beaker, add 35 mL glycerol as solvent, and stir magnetically for 30 min at room temperature to obtain a precursor dispersion; (2) The precursor dispersion liquid prepared in step (1) is transferred into a 50 mL polytetrafluoroethylene liner, and then the liner is loaded into a simple hydrothermal reaction kettle made of stainless steel, and the filling degree of the liner in the reaction kettle is controlled to be 70%. The hydrothermal reaction kettle is placed in an oven, the temperature is set to 120 ℃, and the temperature is raised to 120 ℃ at a temperature rising rate of 5 ℃ / min, the reaction time is set to 24 h, and the reaction is completed after natural cooling to room temperature; (3) The product in the cooled reaction kettle is taken out and centrifuged, the precipitate after centrifugation is washed with distilled water twice and centrifuged for 3 times, then the centrifuge tube containing the precipitate sample is placed in a vacuum drying box at 40 ℃ for 18 h, and the dried indium sulfide powder is collected.

[0036] Figure 5 The SEM image of the indium sulfide powder prepared in this embodiment is shown in the figure, from which it can be seen that the diameter of the entire plug-in cage-shaped indium sulfide is about 10-15 μm, the main structure of the cage-shaped indium sulfide is a micrometer flower ball (α phase) assembled by folding a plurality of ultrathin indium sulfide nanosheets, the diameter of the micrometer flower ball is about 10 μm, and the thickness of the ultrathin indium sulfide nanosheet constituting the micrometer flower ball is about 50 nm. A plurality of indium sulfide quadrat sheets (β phase) with a thickness of 100-200 μm and a side length of 1-3 μm are inserted into the micrometer flower ball, and the indium sulfide quadrat sheets are stacked or crossed with each other, thereby forming a three-dimensional plug-in cage-shaped indium sulfide. The insertion of the β phase indium sulfide quadrat sheet effectively prevents the agglomeration of the spherical matrix, so that the cage-shaped indium sulfide exhibits excellent dispersibility, the sample morphology is complete and not broken, which proves that the three-dimensional plug-in cage-shaped indium sulfide has good structural stability. It can also be seen from Figure 5 that the three-dimensional plug-in cage-shaped structure of the indium sulfide is basically consistent with the morphology of Figure 1 , which proves that the preparation process of the present application has repeatability.

[0037] Example 3: (1) 0.1 mmol of indium chloride and 0.3 mmol of sodium thiosulfate are weighed into a 50 mL beaker, 30 mL of a mixed solvent of ethanol and propanol (the volume ratio of ethanol to propanol is 1:1) is added thereto, and the mixture is stirred at room temperature for 30 min to obtain a precursor dispersion liquid; (2) The precursor dispersion liquid prepared in step (1) is transferred into a 50 mL polytetrafluoroethylene liner, and then the liner is loaded into a simple hydrothermal reaction kettle made of stainless steel, and the filling degree of the liner in the reaction kettle is controlled to be 60%. The hydrothermal reaction kettle is placed in an oven, the temperature is set to 180 ℃, and the temperature is raised to 180 ℃ at a temperature rising rate of 5 ℃ / min, the reaction time is set to 10 h, and the reaction is completed after natural cooling to room temperature; (3) The product in the reactor after cooling is taken out, centrifugal separation is carried out, the precipitate after centrifugation is washed 3 times by centrifugation with distilled water twice, then is washed 3 times by centrifugation with anhydrous ethanol, then the centrifuge tube containing the precipitate sample is placed in a vacuum drying oven at 60 DEG C and dried for 8 hours, and the dried indium sulfide powder is collected.

[0038] Figure 6 The SEM image of the indium sulfide powder sample prepared in the embodiment is shown in the figure, from which it can be seen that the diameter of the entire indium sulfide cage with inserted sheets is about 10-15 μm, the main structure of the cage-shaped indium sulfide is a micron flower ball assembled by folding a plurality of ultrathin indium sulfide nanosheets, the diameter of the micron flower ball is about 10 μm, and the thickness of the ultrathin indium sulfide nanosheet constituting the micron flower ball is about 50 nm. A plurality of indium sulfide quadrat sheets with a thickness of 100-200 μm and a side length of 1-3 μm are inserted and inlaid on the micron flower ball, the indium sulfide quadrat sheets are stacked or intersected with each other, thereby forming a three-dimensional indium sulfide cage with inserted sheets. Figure 6 It can also be observed from the figure that the three-dimensional indium sulfide cage with inserted sheets has basically the same morphology as Figure 1 and Figure 5 , which proves that the preparation process of the embodiment has repeatability.

[0039] The three-dimensional indium sulfide cage with inserted sheets prepared in the embodiment has a novel structure, which is composed of an alpha-phase indium sulfide flower ball body and beta-phase indium sulfide quadrat sheets, the unique inserted sheet design greatly improves the specific surface area, dispersibility and structural stability of the material, the introduction of the beta-phase indium sulfide quadrat sheets and the heterostructure formed by the alpha-phase indium sulfide ball body effectively broaden and significantly enhance the light absorption capacity of the material, so that it has a wider ultraviolet-visible light absorption range and a stronger absorption intensity, which is particularly beneficial to the effective separation and transmission of photo-generated carriers, and has a great potential for performance improvement in ultraviolet-visible light detection applications, and has a broad application prospect in the fields of photocatalysis, photovoltaic devices, energy storage and environmental pollution control.

[0040] The above is only an embodiment of the present application, and does not limit the present application in any form, and the present application can also have other forms of embodiments according to the above structure and function, which will not be listed one by one. Therefore, any skilled person in the art, without departing from the scope of the technical scheme of the present application, according to the technical essence of the present application, any simple modification, equivalent change and modification of the above embodiment, still belongs to the scope of the technical scheme of the present application.

Claims

1. A three-dimensional insert-type cage-like indium sulfide, characterized in that, The diameter of the entire cage-like indium sulfide is 10~15 μm. The main structure of the cage-like indium sulfide is a micron flower sphere assembled by folding multiple ultrathin indium sulfide nanosheets. The diameter of the micron flower sphere is 10 μm. The thickness of the ultrathin indium sulfide nanosheets that make up the micron flower sphere is 50 nm. Multiple tetragonal indium sulfide sheets with a thickness of 100~200 nm and a side length of 1~3 μm are also embedded on the micron flower sphere.

2. A method for preparing a three-dimensional insert-type cage-like indium sulfide, characterized in that, Includes the following steps: (1) Take indium source precursor and sulfur source precursor and add them to solvent, stir at room temperature to obtain precursor dispersion; wherein, the molar ratio of indium atoms to sulfur atoms is <2:3, and the solvent is selected from at least one of ethanol, propanol, isopropanol, ethylene glycol and glycerol. (2) Transfer the precursor dispersion obtained in step (1) to a hydrothermal reactor and react it at 120~200 ℃ for 10~24 h. After the reaction is completed, allow it to cool naturally to room temperature. (3) Take out the product from the cooled reactor and centrifuge it. The precipitate after centrifugation is washed 3-5 times with double distilled water and then washed 3-5 times with anhydrous ethanol. Then, place the centrifuge tube containing the precipitate sample in a vacuum drying oven to dry it. Collect the dried sample, which is the three-dimensional insert cage-like indium sulfide.

3. The method for preparing three-dimensional insert-type cage-like indium sulfide as described in claim 2, characterized in that, The indium source precursor is selected from one of indium acetate, indium nitrate, and indium chloride.

4. The method for preparing three-dimensional insert-type cage-like indium sulfide as described in claim 2, characterized in that, The sulfur source precursor is selected from one of thioacetamide, sodium thiosulfate, and thiourea.

5. The method for preparing three-dimensional insert-type cage-like indium sulfide as described in claim 2, characterized in that, In step (2), the filling degree of the hydrothermal reactor lining is 50-80%.

6. The method for preparing three-dimensional insert-type cage-like indium sulfide as described in claim 2, characterized in that, In step (2), the heating rate during the hydrothermal reaction is 4~10 ℃ / min.

7. The method for preparing three-dimensional insert-type cage-like indium sulfide as described in claim 2, characterized in that, In step (3), the vacuum drying temperature is 40~80 ℃ and the drying time is 8~24 h.

8. An indium sulfide photodetector, characterized in that... The indium sulfide is a three-dimensional insert-type cage-like indium sulfide obtained by any one of the preparation methods of claims 2 to 7.

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