Preparation method and application of flexible one-dimensional nanometer sulfur-iodine antimony composite material

Abstract

The present application relates to a kind of flexible one-dimensional nanometer sulfur iodine antimony composite material preparation method and its application, by, with nanometer elemental sulfur powder, nanometer elemental iodine powder, nanometer elemental antimony powder, MCM-41 molecular sieve, nanometer titanium dioxide powder, nanometer silicon dioxide powder as raw material, by ultrasonic chemical method preparation flexible one-dimensional nanometer sulfur iodine antimony gel composite material, simultaneously, the present application utilizes the flexible one-dimensional nanometer sulfur iodine antimony gel composite material prepared pyroelectric sensor.The pyroelectric detector prepared from the material of the present application has excellent performance, fast response time, and can be used in subsequent integrated sensors.The one-dimensional nanocrystals generated have good morphology distribution.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials, and more particularly to a method for preparing a flexible one-dimensional nano-antimony sulfide composite material and its application. Background Technology

[0002] Pyroelectric and photodetectors are devices that can convert light / thermal signals into electrical signals, playing a vital role in fields such as imaging technology, environmental monitoring, and optical communication.

[0003] Most commercially available detectors are designed based on crystalline silicon and silicon-germanium heterojunctions or III-V semiconductor bulk materials. However, these materials have many drawbacks, such as fragility, high cost, and demanding fabrication processes, making it difficult to meet the requirements of next-generation optoelectronic devices in terms of low power consumption, lightweight design, portability, mechanical flexibility, scalability, and low manufacturing cost.

[0004] To date, numerous different techniques have been proposed for fabricating antimony sulfide (SbSI) nanomaterials, including electron beam evaporation, flash evaporation, physical vapor deposition, pulsed laser deposition, and hydrothermal synthesis. Most of these techniques require expensive equipment, limiting their large-scale application due to factors such as complexity or the need for high-temperature processing. A typical method for fabricating continuous SbSI nanowire films is based on the application of a bonding polymer matrix, such as polyacrylonitrile (PAN). However, the electrical properties of such composites may be inferior to those of the original SbSI nanowires. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a method for preparing a flexible one-dimensional nano-antimony sulfide composite material and its application. The one-dimensional nano-antimony sulfide composite material is synthesized using ultrasonic chemical synthesis, which features fast reaction speed, mild conditions, and good morphology of the nanocrystalline material.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material is provided, comprising the following steps:

[0008] Step 1: Mix nano-sulfur powder, nano-iodine powder, nano-antimony powder, MCM-41 molecular sieve (catalytic effect), and binder powder in a specific ratio to obtain a mixed powder; wherein the binder powder includes one or more of nano-titanium dioxide powder and nano-silica powder.

[0009] Step 2: Mix the obtained powder mixture with anhydrous ethanol and transfer the mixture to a container;

[0010] Step 3: Add an ultrasonic reaction device and a constant temperature control device to the container or the bottom of the container. Under constant temperature conditions, perform an ultrasonic chemical reaction through the ultrasonic reaction device to obtain a gel material and obtain a flexible one-dimensional nano-antimony sulfide gel composite material.

[0011] As a further optimization, in step 1, the nano-sulfur powder, nano-iodine powder, and nano-antimony powder are mixed according to the SbSI stoichiometry, and the molar mass ratio of the nano-sulfur powder, nano-iodine powder, and nano-antimony powder is 1:1:1.

[0012] As a further optimization scheme, the particle size of nano-titanium dioxide powder is between 20-100 nanometers, and the particle size of nano-silica powder is between 50-100 nanometers, wherein the binder powder accounts for 1%-30% of the total mass of the mixed powder.

[0013] As a further optimization, the mass ratio of anhydrous ethanol in the container to the mass of the mixed powder is between 1:3 and 1:10.

[0014] As a further optimization, in step 3, the operating temperature of the constant temperature control device is between 40-60℃, the output ultrasonic frequency of the ultrasonic reaction device is between 10-100KHZ, and the reaction time is 3-5 hours.

[0015] As a further optimization, in step 3, the space group of the flexible one-dimensional nano-antimony sulfide gel composite material is the orthorhombic crystal structure of Pnma.

[0016] As a further optimization, the flexible one-dimensional nano-antimony sulfide gel composite material has a band gap of about 2.3 eV and a pyroelectric coefficient of tp = 240 nC / (cm2·K).

[0017] This application also provides a method for preparing a pyroelectric sensor based on a flexible one-dimensional nano-antimony sulfide-iodide composite material.

[0018] Step 1: Take the flexible one-dimensional nano-antimony sulfide gel composite material obtained by the above preparation method; dilute the flexible one-dimensional nano-antimony sulfide gel composite material with ethanol to a viscosity suitable for drop casting;

[0019] Step 2: The flexible one-dimensional nano-antimony sulfide gel composite material is drop-cast onto the flexible ITO conductive substrate material, and the drop-cast thickness is between 1 and 100 micrometers.

[0020] Step 3: Apply a pressure of 5 atmospheres to the top of the flexible one-dimensional nano-antimony sulfide gel composite material to make it dense, and then sputter a layer of noble metal electrode on it to form a composite material pyroelectric sensor; wherein the thickness of the noble metal electrode is between 200-300 nanometers.

[0021] As a further optimization, in step 2, the flexible ITO conductive substrate material is PET or PI; in step 3, the noble metal electrode includes gold or platinum.

[0022] As a further optimization scheme, there is a step 2a between step 2 and step 3, wherein step 2a: the flexible one-dimensional nano antimony sulfide gel composite material flexible ITO conductive matrix material is placed in a vacuum drying oven and dried at a temperature of 60 degrees for 10-30 minutes.

[0023] The beneficial effects of the present invention are as follows: 1. The novel one-dimensional semiconductor nanowire material of the present invention, antimony sulfide, belongs to the orthorhombic crystal system with space group Pmna, and is extremely stable at room temperature.

[0024] 2. The ultrasonic method can be used to obtain crystals simply and directly, resulting in high-quality crystals, low cost, excellent performance, and large-scale reproducible production without environmental pollution.

[0025] 3. Using inert materials such as nano-titanium dioxide and nano-silica as fillers and binders can effectively form thin films while simultaneously short-circuiting the sputtering electrodes. Using traditional acrylic or PVDF binders would significantly impact the pyroelectric coefficient. Attached Figure Description

[0026] Figure 1 This is a schematic flowchart of the method for manufacturing the flexible one-dimensional nano-antimony sulfide composite material of the present invention;

[0027] Figure 2 This is a SEM image of the flexible one-dimensional antimony sulfide nanocomposite material prepared by the method described in this invention;

[0028] Figure 3 This is a temperature-current response graph of the flexible pyroelectric detector prepared by the method described in this invention under a bias voltage of 0.1V;

[0029] Figure 4 The current response diagram of the flexible pyroelectric detector prepared by the method described in this invention under cyclic temperature changes;

[0030] Figure 5 This is a schematic diagram of the width and length distribution of nanowires in the composite material. Detailed Implementation

[0031] Please see Figure 1 As shown, this invention provides a method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material, comprising the following steps:

[0032] Specific step 1: Prepare nano-sulfur powder (0.015mol), nano-iodine powder (0.015mol), and nano-antimony powder (0.015mol), with the purity of the three reaching 99.99%;

[0033] In addition, continue to prepare MCM-41 molecular sieve (catalytic effect), nano titanium dioxide powder, and nano silica powder, wherein the mass of nano titanium dioxide is 10% of the total mass of the mixed powder and the particle size is 20 nanometers; the mass of nano silica is 10% of the total mass of the mixed powder and the particle size is 20 nanometers; and the mass of MCM-41 molecular sieve is 8-10% of the total mass of the mixed powder.

[0034] Mix all prepared powders thoroughly in a glove box under an inert protective gas atmosphere to form a mixed powder. (After mixing all powders thoroughly, store them under an inert gas atmosphere to prevent contamination or oxidation of the material due to contact with air.)

[0035] In specific step 2, the obtained mixed powder is mixed with 20 ml of anhydrous ethanol, and the mixture is transferred to a 100 ml container. The anhydrous ethanol container should be sealable. If other solvents (acetone, methanol) are used, the crystal length distribution will be discrete, which is not conducive to subsequent testing.

[0036] In this specific embodiment, anhydrous ethanol exhibits excellent dispersibility for nanomaterials, effectively preventing particle aggregation and deposition, thus helping to maintain the dispersibility and stability of the material. Furthermore, choosing anhydrous ethanol avoids unnecessary reactions with other reagents.

[0037] Step 3: Add an ultrasonic reaction device and a constant temperature control device to the container. Under constant temperature conditions, perform an ultrasonic chemical reaction through the ultrasonic reaction device to obtain a gel material. Keep the overall temperature constant at 40 degrees Celsius using the constant temperature control device. At the same time, insert an ultrasonic transducer into a constant temperature water bath. Set the ultrasonic frequency to 35 kHz and the ultrasonic time to 3 hours. Wait for the anhydrous ethanol suspension to turn orange. Use a pipette to remove the orange gel to obtain a flexible one-dimensional nano-antimony sulfide gel composite material.

[0038] As a further optimization, in step 3, the space group of the flexible one-dimensional nano-antimony sulfide gel composite material is the orthorhombic crystal structure of Pnma.

[0039] As a further optimization, the flexible one-dimensional nano-antimony sulfide gel composite material has a band gap of about 2.3 eV and a pyroelectric coefficient of tp = 240 nC / (cm2·K).

[0040] In addition, this application also utilizes a flexible one-dimensional nano-antimony sulfide iodide gel composite material to prepare a pyroelectric sensor, wherein the preparation method...

[0041] Specific step 1: Take out the flexible one-dimensional nano-antimony sulfide gel composite material obtained by the above preparation method with a pipette; dilute the flexible one-dimensional nano-antimony sulfide gel composite material with ethanol to a viscosity suitable for drop casting;

[0042] Step 2: Flexible one-dimensional antimony sulfide nanogel composite material was drop-cast onto a flexible ITO conductive substrate (PET as the substrate) using vacuum assistance. The drop-cast area was controlled at 9 square centimeters, and the drop-cast thickness was 10 micrometers. Its SEM morphology is shown in [Figure number missing]. Figure 2 The layer structure of the pyroelectric detector, a scanning electron microscope image of the SbSI-TiO2 thin film, the white long line material in the middle is SbSI nanowire, and the white dot-like material around it is the binder titanium dioxide.

[0043] The one-dimensional antimony iodide nanowire crystals of the flexible one-dimensional antimony iodide nanogel composite material prepared in this embodiment have intact morphology. EDS test shows that the ratio of Sb, S, and I elements is close to 1:1:1. SEM shows that nano-titanium dioxide and nano-silica act as binders to form a dense composite film.

[0044] In the preparation of flexible one-dimensional nano-antimony sulfide iodide gel composite materials, vacuum-assisted technology can play the following roles:

[0045] 1. Removal of air bubbles and air: Vacuum treatment can remove air bubbles and air from the sample, thereby increasing the sample's density and compactness, and enhancing its mechanical properties and stability.

[0046] 2. Promotes material diffusion: In a vacuum environment, molecules, atoms and ions on the sample surface can diffuse into the surrounding environment more quickly, thereby promoting the reaction rate and product formation.

[0047] 3. Improve crystal structure and morphology: Vacuum assistance can eliminate the interference of impurities such as oxygen on the crystal structure and morphology of materials, resulting in a more uniform and regular crystal structure and morphology.

[0048] 4. Improve reaction efficiency and purity: When the reaction is carried out in a vacuum environment, the reaction temperature and pressure can be effectively reduced, thereby reducing the generation of side reactions and impurities, and improving the purity and yield of the reaction products.

[0049] As a further optimization scheme, there is a step 2a between step 2 and step 3, wherein step 2a: the flexible one-dimensional nano antimony sulfide gel composite material flexible ITO conductive matrix material is placed in a vacuum drying oven and dried at a temperature of 60 degrees for 10-30 minutes.

[0050] The flexible one-dimensional nano-antimony sulfide-iodide gel composite material with a flexible ITO conductive matrix was dried in a vacuum drying oven. The main purpose was to remove moisture and other solvents from the composite material, improving sample stability and shelf life, and facilitating subsequent processing. Simultaneously, drying also helps improve the physical properties of the sample.

[0051] Step 3: Apply a pressure of 5 atmospheres to the top of the flexible one-dimensional nano-antimony sulfide gel composite material to make it dense, and then sputter a layer of noble metal electrode on it to form a composite material pyroelectric sensor; wherein the thickness of the noble metal electrode is between 200-300 nanometers.

[0052] As a further optimization, in step 3, the noble metal electrode includes gold or platinum.

[0053] The role played in step 3 above is as follows:

[0054] Improving sample density: Applying pressure allows the flexible one-dimensional antimony sulfide nanogel composite material to assemble more tightly, forming a dense structure. This helps improve the physical properties of the sample, such as strength, and also facilitates the subsequent preparation and fixation of electrodes.

[0055] Sputtered noble metal electrodes: By sputtering a noble metal electrode with a thickness of approximately 200-300 nanometers onto the sample surface, electrical and thermal properties can be provided to the sample. Noble metal electrodes have excellent conductivity and stability, can effectively connect the sample to external circuits, and respond to changes in external temperature.

[0056] A composite material pyroelectric sensor is constructed by combining a pressure-applied flexible one-dimensional nano-antimony sulfide-iodide gel composite material with a noble metal electrode. This sensor can utilize the sample's unique structure and thermosensitive properties to achieve sensitive detection and response to changes in ambient temperature, making it highly valuable for applications.

[0057] Furthermore, this pyroelectric sensor exhibits extremely high current response speed and sensitivity to temperature, in which... Figure 3 middle,

[0058] (a) The relationship between temperature and current of the SbSI-TiO2 pyroelectric detector and the corresponding Arrhenius curve under a constant bias voltage of 0.1V.

[0059] (b) The two curves represent the best-fit curves for the paraelectric and ferroelectric phases, respectively, and the vertical dashed line represents the reciprocal of the determined Curie temperature.

[0060] Figure 4In the figure, the SbSI-TiO2 pyroelectric detector is shown to cycle under different temperature (a, c) ranges and the corresponding output current (b, d) changes cyclically. The horizontal line represents the Curie temperature TC = 294(2) K. Figure 4 This demonstrates the extremely high temperature response capability of the SbSI-TiO2 pyroelectric detector.

[0061] In summary, this invention presents a simple one-step ultrasonic chemical synthesis method for SbSI-TiO2 / SiO2. Ultrasonic chemistry, due to the unique physicochemical properties caused by ultrasonic cavitation, plays an important role in polymer synthesis, nanomaterial preparation, catalytic reactions, and wastewater treatment. Furthermore, ultrasonic chemical processes are widely applicable due to their low pollution, simple equipment, high reaction efficiency, and broad applicability.

[0062] This invention employs ultrasonic chemical synthesis of one-dimensional antimony sulfide nanowires and uses TiO2 / SiO2 nanoparticles as a binder in a composite material to form a pyroelectric sensor film. The resulting pyroelectric detector exhibits excellent performance and fast response time, making it suitable for subsequent sensor integration. The generated one-dimensional nanocrystals possess a good morphological distribution, with a length of 2-3 micrometers and a width of 60 nanometers, exhibiting a well-defined normal distribution. (See details...) Figure 5 ,in Figure 5 'a' refers to the normal distribution diagram (nm) of the SbSI nanowire diameter. Figure 5 b refers to the length of the nanowire (um), and the black line is the fitted curve, which is a composite normal distribution.

[0063] The above embodiments are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material, characterized in that: Includes the following steps: Step 1: Mix nano-sulfur powder, nano-iodine powder, nano-antimony powder, MCM-41 molecular sieve, and adhesive powder in a specific ratio to obtain a mixed powder; wherein the adhesive powder includes one or more of nano-titanium dioxide powder and nano-silica powder. Step 2: Mix the obtained powder mixture with anhydrous ethanol and transfer the mixture to a container; Step 3: Add an ultrasonic reaction device and a constant temperature control device to the container or the bottom of the container. Under constant temperature conditions, perform an ultrasonic chemical reaction through the ultrasonic reaction device to obtain a gel material and obtain a flexible one-dimensional nano-antimony sulfide gel composite material.

2. The method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 1, characterized in that: In step 1, the nano-sulfur powder, nano-iodine powder, and nano-antimony powder are mixed according to the SbSI stoichiometry, and the molar mass ratio of the nano-sulfur powder, nano-iodine powder, and nano-antimony powder is 1:1:

1.

3. The method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 1, characterized in that: The particle size of the nano titanium dioxide powder is between 20 and 100 nanometers, and the particle size of the nano silica powder is between 50 and 100 nanometers. The binder powder accounts for 1-30% of the total mass of the mixed powder.

4. The method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 1, characterized in that: The mass ratio of anhydrous ethanol in the container to the mass of the mixed powder is between 1:3 and 1:

10.

5. The method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 1, characterized in that: In step 3, the operating temperature of the constant temperature control device is between 40-60℃, and the output ultrasonic frequency of the ultrasonic reaction device is between 10-100KHZ, with a reaction time of 3-5 hours.

6. The method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 1, characterized in that: In step 3, the space group of the flexible one-dimensional nano-antimony sulfide gel composite material is the orthorhombic crystal structure of Pnma.

7. The method for preparing a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 1, characterized in that: The flexible one-dimensional nano-antimony sulfide gel composite material has a band gap of about 2.3 eV and a pyroelectric coefficient of tp = 240 nC / (cm2·K).

8. A method for preparing a pyroelectric sensor based on a flexible one-dimensional nano-antimony sulfide-iodide composite material, characterized in that: Step 1: Take the flexible one-dimensional antimony sulfide nanogel composite material obtained by the preparation method according to any one of claims 1-7; dilute the flexible one-dimensional antimony sulfide nanogel composite material to a drop-castable viscosity; Step 2: The flexible one-dimensional nano-antimony sulfide gel composite material is drop-cast onto the flexible ITO conductive substrate material, and the drop-cast thickness is between 1 and 100 micrometers. Step 3: Apply a pressure of 5 atmospheres to the top of the flexible one-dimensional nano-antimony sulfide gel composite material to make it dense, and then sputter a layer of noble metal electrode on it to form a composite material pyroelectric sensor; wherein the thickness of the noble metal electrode is between 200-300 nanometers.

9. The method for preparing a pyroelectric sensor based on a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 8, characterized in that: In step 2, the flexible ITO conductive substrate material is PET or PI; in step 3, the noble metal electrode includes gold or platinum.

10. The method for preparing a pyroelectric sensor based on a flexible one-dimensional nano-antimony sulfide-iodide composite material according to claim 8, characterized in that: Between step 2 and step 3 there is step 2a, in which: the flexible one-dimensional nano antimony sulfide gel composite material and the flexible ITO conductive matrix material are placed in a vacuum drying oven and dried at a temperature of 60 degrees for 10-30 minutes.

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