Composite photoelectric material for infrared photoelectric detection, detector and preparation method of composite photoelectric material

Abstract

The invention discloses a composite photoelectric material for infrared photoelectric detection, a detector and a preparation method thereof, and the composite photoelectric material is prepared by the following steps: etching an MAX phase into multiple layers by using an etching agent, adding an intercalator, carrying out centrifugal ultrasonic stripping, freeze-drying into a single-layer or few-layer MXene, taking the MXene material, cesium bromide and lead bromide, putting into a dimethyl sulfoxide solution, carrying out ultrasonic oscillation, and carrying out vacuum drying to obtain the composite photoelectric material. Heating and preserving heat for 1 to 1.5 hours to obtain the V2C MXene-coated CsPbBr3 composite photoelectric material. The detector is a self-powered human body infrared detector prepared by spin-coating a composite photoelectric material on a corresponding substrate, selecting an appropriate electrode and placing the appropriate electrode on the surface of the material. According to the V2CMXene-coated CsPbBr3 composite photoelectric material, the photon-generated carrier separation efficiency is effectively improved, and the problem that a traditional infrared detector needs a low working temperature to reduce dark current is solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of human body infrared optoelectronic detection materials and devices, and particularly relates to a composite optoelectronic material for infrared optoelectronic detection, a detector and a preparation method thereof. Background Art

[0002] Human body infrared detectors play a key role in important fields such as thermal imaging, biomedical imaging, communication and military. Although traditional infrared detectors have been widely commercialized, many challenges still exist in the process of expanding applications.

[0003] Traditional infrared detectors (such as InGaAs, HgCdTe) need to rely on cryogenic refrigeration (liquid nitrogen or Stirling cryocooler) to suppress dark current noise, which results in large device volume, high power consumption and a sharp increase in deployment cost. This severely limits their popularity in consumer electronics and wearable devices. Although uncooled microbolometers (such as vanadium oxide thin films) have developed in recent years, their sensitivity and response speed are still difficult to meet the requirements of high-end applications. III-V compounds (such as InSb, HgCdTe) have excellent responses in the mid-infrared and far-infrared bands (8 - 14 μm) and have become the mainstream materials for human body infrared detectors. However, due to the presence of highly toxic heavy metals, their production and waste treatment require strict supervision. Promoting the industry to seek alternative materials has become an issue.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a composite optoelectronic material for infrared optoelectronic detection, a detector and a preparation method thereof, which can effectively improve the separation efficiency of photo-generated carriers, and realize the efficient response to human body infrared rays under zero bias voltage, thereby solving the problems existing in the prior art.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A composite optoelectronic material for infrared optoelectronic detection, which is obtained by etching the MAX phase of two-dimensional material MXene into multiple layers with an etchant, then adding an intercalating agent, centrifuging, ultrasonically exfoliating and freeze-drying to obtain a single-layer or few-layer two-dimensional material MXene, and then placing the obtained single-layer or few-layer two-dimensional material MXene, cesium bromide and lead bromide in a dimethyl sulfoxide solution, ultrasonically oscillating for a predetermined time, heating and keeping warm to obtain the V 2 C MXene@CsPbBr 3 composite optoelectronic material.

[0008] A preparation method for a composite optoelectronic material for infrared optoelectronic detection, comprising:

[0009] Using two-dimensional material MXene, cesium bromide, and lead bromide as raw materials;

[0010] Etching the MAX phase of the two-dimensional material MXene into multiple layers with an etchant, then adding an intercalating agent, centrifuging, ultrasonically exfoliating, and freeze-drying to obtain monolayer or few-layer two-dimensional material MXene;

[0011] Placing the obtained monolayer or few-layer two-dimensional material MXene, cesium bromide, and lead bromide in dimethyl sulfoxide solution, ultrasonically oscillating for a predetermined time, heating and keeping warm, and then obtaining VC MXene@CsPbBr 2 C MXene@CsPbBr 3 The composite optoelectronic material is the composite optoelectronic material.

[0012] A detector for infrared optoelectronic detection, comprising:

[0013] A substrate, a composite optoelectronic material thin film, and an electrode; wherein,

[0014] The composite optoelectronic material thin film is disposed on the substrate, and the composite optoelectronic material thin film is a thin film formed by spin-coating the VC MXene@CsPbBr 2 C MXene@CsPbBr 3 composite optoelectronic material of the present invention on the substrate and drying;

[0015] One end of the electrode forms an electrical contact with the composite optoelectronic material thin film.

[0016] A preparation method of a detector for infrared optoelectronic detection, comprising:

[0017] Taking a substrate, spin-coating the VC MXene@CsPbBr 2 C MXene@CsPbBr 3 composite optoelectronic material of the present invention on the substrate and drying to form a composite optoelectronic material thin film;

[0018] Taking an electrode and placing it on the surface of the composite optoelectronic material thin film, so that one end of the electrode forms an electrical contact with the composite optoelectronic material thin film.

[0019] Compared with the prior art, the composite optoelectronic material, detector, and preparation method thereof for infrared optoelectronic detection provided by the present invention have the following beneficial effects:

[0020] (1) The present invention selects the two-dimensional material MXene. Due to its novel structure and properties, two-dimensional materials exhibit great potential in next-generation high-performance logic devices, optoelectronic devices, and flexible devices, especially showing significant advantages in photodetection. This material has a large specific surface area and active surface chemical properties, enabling surface modification and functionalization. Its surface groups provide rich active sites for the load, and by introducing different functional groups or nanoparticles, specific functions can be imparted to it, further expanding its application potential.

[0021] (2) The two-dimensional material V 2 C MXene has good electrical conductivity, and after forming a composite optoelectronic material with CsPbBr 3 , a heterostructure can be formed. The perovskite material has excellent optical absorption and luminescence characteristics, shows good absorption ability in the visible to near-infrared band, and has high carrier mobility and low exciton binding energy. The internal carriers can be efficiently transported, facilitating the separation and transfer of electrons and holes. After the two are combined, the separation efficiency of photo-generated carriers can be effectively improved, generating a synergistic enhancement effect. Especially under weak light conditions (such as cloudy days, mornings, evenings, etc.), the material can still maintain a high photoelectric conversion efficiency.

[0022] (3) The detector designed by the present invention can operate at room temperature, avoiding the limitations of traditional infrared detectors operating under low-temperature conditions, thus reducing the problem of dark current and improving the convenience and stability of applications.

[0023] (4) The present invention supports a self-powered mode and can operate independently without an external power supply, saving costs. In practical applications, it can be used in security fields such as intrusion detection and monitoring alarms, and also has extensive applications in the field of healthcare, such as for patient activity monitoring. Its high sensitivity enables it to monitor speed and human sensing through current changes, achieving precise detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0025] Figure 1 It is a flowchart of the preparation method of the composite optoelectronic material provided by the embodiment of the present invention.

[0026] Figure 2 It is the micron-scale V prepared in Embodiment 1 of the present invention 2 C MXene@CsPbBr 3Schematic diagram of the detector structure for infrared optoelectronic detection using a composite optoelectronic material.

[0027] Figure 3 For the micron-scale V prepared in Example 1 of the present invention 2 C MXene@CsPbBr 3 Schematic diagram of the detector structure for infrared optoelectronic detection using another substrate of the composite optoelectronic material.

[0028] Figure 4 For the micron-scale V prepared in Example 2 of the present invention 2 C MXene@CsPbBr 3 Amplified scanning electron microscopy (SEM) image of the composite optoelectronic material.

[0029] Figure 5 For the micron-scale V prepared in Example 2 of the present invention 2 C MXene@CsPbBr 3 X-ray diffraction (XRD) pattern of the composite optoelectronic material.

[0030] Figure 6 For the micron-scale V prepared in Example 2 of the present invention 2 C MXene@CsPbBr 3 I-T image of the detector for infrared optoelectronic detection using the composite optoelectronic material.

[0031] Figure 7 For the micron-scale V prepared in Example 3 of the present invention 2 C MXene@CsPbBr 3 I-T image of the detector for infrared optoelectronic detection using the composite optoelectronic material under illumination with different powers. Detailed implementation manners

[0032] Next, in combination with the specific content of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described; obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments, which does not constitute a limitation to the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0033] First, the following explanations are given for the terms that may be used in this article:

[0034] The term "and / or" means that either one or both of the two can be realized. For example, X and / or Y means that it includes both the case of "X" or "Y" and the three cases of "X and Y".

[0035] Descriptions using terms such as "comprising", "including", "containing", "having" or other similar semantics shall be construed as non-exclusive inclusion. For example, including a technical feature element (such as raw material, component, ingredient, carrier, dosage form, material, dimension, part, component, mechanism, device, step, process, method, reaction condition, processing condition, parameter, algorithm, signal, data, product or article, etc.) shall be construed as not only including the explicitly listed technical feature element, but also other technical feature elements well-known in the art that are not explicitly listed.

[0036] The term "parts by mass" represents the mass ratio relationship between multiple components. For example, if it is described that component X is x parts by mass and component Y is y parts by mass, then it means the mass ratio of component X to component Y is x:y; 1 part by mass can represent any mass. For example, 1 part by mass can be represented as 1 kg or 3.1415926 kg, etc. The sum of the parts by mass of all components is not necessarily 100 parts, and can be greater than 100 parts, less than 100 parts or equal to 100 parts. Unless otherwise specified, the parts, ratios and percentages described in this article are all by mass.

[0037] Unless otherwise clearly specified or limited, terms such as "installed", "connected", "joined", "fixed", etc. shall be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in this article can be understood according to specific circumstances.

[0038] When a concentration, temperature, pressure, dimension or other parameter is expressed in the form of a numerical range, this numerical range shall be understood as specifically disclosing all ranges formed by the pairing of any upper limit value, lower limit value, and preferred value within this numerical range, regardless of whether it is explicitly recorded; for example, if the numerical range "2 - 8" is recorded, then this numerical range shall be construed as including ranges such as "2 - 7", "2 - 6", "5 - 7", "3 - 4 and 6 - 7", "3 - 5 and 7", "2 and 5 - 7", etc. Unless otherwise specified, the numerical ranges recorded in this article include both their end values and all integers and fractions within this numerical range.

[0039] An embodiment of the present invention provides a composite optoelectronic material for infrared optoelectronic detection. The MAX phase of the two-dimensional material MXene is etched into multiple layers with an etchant, and an intercalating agent is added, followed by centrifugation, ultrasonic stripping, and freeze-drying to obtain a single-layer or few-layer two-dimensional material MXene. Then, the obtained single-layer or few-layer two-dimensional material MXene is combined with cesium bromide (CsBr) and lead bromide (PbBr 2V prepared by ultrasonic oscillation in dimethyl sulfoxide solution (DMSO) for a predetermined duration and then heating and insulation 2 C MXene@CsPbBr 3 composite optoelectronic material

[0040] Preferably, in the above composite optoelectronic material, the concentration of the dimethyl sulfoxide solution is 10 - 20 mg / mL, and the ultrasonic oscillation in the dimethyl sulfoxide solution for a predetermined duration is 1 - 1.5 h;

[0041] The mass ratio of cesium bromide, lead bromide and few-layer or single-layer two-dimensional material V 2 C MXene is 1:1:1 - 1:4:1

[0042] Among the above raw materials, two-dimensional material Mxene is a two-dimensional nanomaterial, which has received extensive attention in recent research due to its unique structural characteristics and diverse chemical properties. Mxene materials are usually composed of transition metal carbides, nitrides or carbonitrides, and are prepared by removing the A-layer elements (such as Al or Si) from MAX-phase materials to form a two-dimensional layered structure. This structure not only endows Mxene materials with a high specific surface area, but also gives them excellent electrical conductivity and the ability to regulate the bandgap, showing significant application potential in the fields of electronics, energy storage and catalysis. The two-dimensional layered structure of Mxene materials brings a very high specific surface area and abundant surface active sites, suitable for a variety of application environments. At the same time, its surface contains functional groups such as -O, -OH, -F, endowing the material with good hydrophilicity and chemical stability. In electronic devices, the high electron mobility and tunable conductivity characteristics of Mxene materials make them suitable for a variety of device structures; in the optoelectronic field, its high light absorption and wide spectral response capabilities provide a good basis for light detection and optoelectronic conversion applications. The structure and properties of Mxene materials can also be regulated by changing the types of transition metal elements or surface terminal groups to meet the performance requirements of different applications.

[0043] The embodiment of the present invention also provides a preparation method for a composite optoelectronic material used for infrared optoelectronic detection, including:

[0044] Using two-dimensional material MXene, cesium bromide and lead bromide as raw materials;

[0045] Etching the MAX phase of two-dimensional material MXene into multiple layers with an etchant, then adding an intercalating agent, centrifuging, ultrasonically exfoliating and freeze-drying to obtain few-layer or single-layer two-dimensional material MXene;

[0046] Placing the obtained few-layer or single-layer two-dimensional material MXene, cesium bromide and lead bromide in dimethyl sulfoxide solution and ultrasonic oscillating for a predetermined duration, and then heating and insulating to obtain V 2 C MXene@CsPbBr 3The composite optoelectronic material is the composite optoelectronic material itself.

[0047] See Figure 1 , preferably, the above method specifically includes the following steps:

[0048] Step 1, prepare multi-layer two-dimensional material V 2 C MXene: Add LiF powder and HCl solution or HF solution to a polytetrafluoroethylene container for reaction, and then add V 2 AlC powder to react to obtain multi-layer two-dimensional material V 2 C MXene;

[0049] Step 2, add an intercalating agent to the multi-layer two-dimensional material V 2 C MXene obtained in Step 1, centrifuge, ultrasonically exfoliate, and then freeze-dry to obtain single-layer or few-layer two-dimensional material V 2 C MXene;

[0050] Step 3, prepare the composite optoelectronic material: Take the single-layer or few-layer two-dimensional material V 2 C MXene obtained in Step 2, add cesium bromide and lead bromide to dimethyl sulfoxide solution, ultrasonically oscillate for a predetermined time, heat and keep warm, and then obtain micron-scale V 2 CMXene@CsPbBr3 composite optoelectronic material.

[0051] Preferably, in the above method, the specific treatment of Step 1 is: Add 2-5 parts by weight of LiF powder and V 2 C:HCl or V 2 C:HF with a molar ratio of 1:1 to 1:2 HCl solution or HF solution, and the concentration of both HCl solution and HF solution is 6 mol / L. Stir with a magnetic stirrer for 0.5-1 hour to fully mix them. Mix 2-4 parts by weight of V 2 AlC powder with the solution in the polytetrafluoroethylene container, stir for 10-30 min, the reaction time is 48-72 h, control the temperature during the reaction to be 70-90 °C, take out the cooled solution after the reaction from the polytetrafluoroethylene container for centrifugal separation, and wash the sediment with alcohol and deionized water multiple times to remove impurities until the pH value of the solution is 6-7, thus obtaining multi-layer two-dimensional material V 2 C MXene.

[0052] Preferably, in the above method, the treatment of Step 2 is:

[0053] Take the multi-layer two-dimensional material V 2 C MXene prepared in Step 1, add it to a mixed solution of deionized water and tetramethylammonium hydroxide with a molar ratio of 1:1 to 2:1. The two-dimensional material V 2The molar ratio of C MXene to tetramethylammonium hydroxide solution is 1:1 to 2:1, and they are stirred at room temperature for 1 to 2 hours. Subsequently, the excess tetramethylammonium hydroxide is separated from the product by repeating centrifugal washing at 2000 rpm for 3 to 6 times. During the centrifugal washing process, the supernatant of the first two centrifugations is discarded, and the supernatant suspensions of the last 3 times are collected and freeze-dried to obtain powdery few-layer or single-layer two-dimensional material V 2 C MXene

[0054] Preferably, in the above method, the treatment in step 3 is as follows:

[0055] Cesium bromide, lead bromide and the few-layer or single-layer two-dimensional material V 2 C MXene prepared in step 2 with a mass ratio of 1:1:1 to 1:4:1 are added to dimethyl sulfoxide solution, ultrasonically dispersed for 15 to 20 minutes, and then ultrasonically oscillated for 1 to 1.5 hours. The mixture is heated in an oil bath at 80 to 100 °C for 5 to 9 hours, and finally kept warm at 100 to 180 °C for 1 to 4 hours. After taking it out, it is washed 3 to 5 times with absolute ethanol or toluene, and then dried in an oven for 8 to 12 hours to obtain micron-scale V 2 C MXene@CsPbBr 3 Composite optoelectronic material

[0056] The micron-scale V 2 C MXene@CsPbBr 3 Composite optoelectronic material prepared by the above method uses two-dimensional material MXene as a loading platform and CspbBr 3 as the loading material. The two-dimensional material MXene effectively improves the strength of material composite, solves the adhesion problem of the loading material, and improves the infrared sensing ability when used in infrared detectors

[0057] The embodiment of the present invention also provides a detector for infrared optoelectronic detection, which is a human body infrared detector that can work self-powered at room temperature and has high sensitivity, including:

[0058] A substrate, a composite optoelectronic material thin film and an electrode; wherein,

[0059] The composite optoelectronic material thin film is disposed on the substrate, and the composite optoelectronic material thin film is a film formed by spin-coating the above-mentioned V 2 CMXene@CsPbBr 3 composite optoelectronic material on the substrate and drying;

[0060] One end of the electrode is in electrical contact with the composite optoelectronic material thin film

[0061] Preferably, in the above detector, the substrate is a single-sided growth of 100 nm SiO2 Substrate or PDMS film substrate

[0062] The electrode uses an indium gallium alloy electrode.

[0063] The embodiment of the present invention further provides a preparation method for a detector for infrared optoelectronic detection, including:

[0064] Take a substrate and spin-coat the above-mentioned V 2 C MXene@CsPbBr 3 composite optoelectronic material on the substrate and dry it to form a composite optoelectronic material film;

[0065] Take an electrode and place it on the surface of the composite optoelectronic material film so that one end of the electrode makes electrical contact with the composite optoelectronic material film.

[0066] In summary, the infrared optoelectronic detector of the present invention, due to the preparation with micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material, can realize self-powered human body infrared sensing. This V 2 C MXene@CsPbBr 3 composite optoelectronic material uses two-dimensional material MXene as a loading platform and CsPbBr 3 as a loading material, effectively improving the separation efficiency of photo-generated carriers and realizing efficient response to human body infrared rays under zero bias voltage.

[0067] In order to more clearly show the technical solutions provided by the present invention and the technical effects produced, the following uses specific examples to describe in detail the solutions provided by the embodiments of the present invention.

[0068] The preparation method of micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material and detector in each embodiment of the present invention is as follows Figure 1 shown.

[0069] Example 1

[0070] This embodiment provides a method for first preparing a composite optoelectronic material and then preparing a self-powered human body infrared detector, including:

[0071] It is to etch the MAX phase into multiple layers with an etchant and add an intercalating agent, and separate it into single-layer or few-layer MXene materials by centrifugation and ultrasonic treatment; take the processed single-layer or few-layer MXene materials, cesium bromide (CsBr) and lead bromide (PbBr 2 ) and place them in dimethyl sulfoxide solution (DMSO) and ultrasonically oscillate for 1 - 1.5 h, and heat and keep warm to obtain V 2C MXene@CsPbBr 3 The composite optoelectronic material is the composite optoelectronic material, where the concentration of the mixed solution is 10 - 20 mg / mL;

[0072] Subsequently, take a certain amount V 2 C MXene@CsPbBr 3 Spin-coat the solution on the corresponding substrate, select a suitable electrode, place it on the surface of the material, and prepare a self-powered human infrared detection device. The electrode is an indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. Place the device on a semiconductor tester, and under the zero-bias voltage mode, irradiate it with a light source (emission wavelength of 9 μm and power of 250 w) that mimics the human infrared radiation band, and process the I-T image on the test system.

[0073] The specific implementation steps are as follows:

[0074] Step 1: Prepare V 2 C powder using V 2 AlC powder as the raw material. Prepare a polytetrafluoroethylene container, a certain amount of LiF powder, and a certain amount of HCl solution or HF solution, and set the reaction conditions to prepare V 2 C powder. V 2 C powder is the multi-layer two-dimensional material V 2 C MXene;

[0075] The set reaction conditions are: add 2 - 5 g of LiF powder and 40 - 80 mL of 6 mol / L HCl solution or 6 mol / L HF solution, and stir it with a magnetic stirrer for 0.5 - 1 hour to make it fully mixed. Subsequently, mix 2 - 4 g of V 2 AlC powder with the solution in the container and stir for 10 - 30 min to promote full contact between the reactants. The reaction duration is 48 - 72 h, and control the temperature during the reaction to be 70 - 90 degrees Celsius. Take out the cooled solution after the reaction from the container for centrifugation, and wash the sediment with alcohol and deionized water multiple times to remove impurities until the pH value of the solution is 6 - 7.

[0076] Step 2: Peel the multi-layer V 2 C MXene material into single-layer or few-layer;

[0077] Take the multi-layer two-dimensional material V 2C MXene, add 20 mL of deionized water containing 3 - 6 mL of tetramethylammonium hydroxide (TMAOH), and stir at room temperature for 1 - 2 h; subsequently, the excess TMAOH is separated from the product by repeating centrifugal washing at 2000 rpm for 3 - 6 times. During the centrifugal washing process, pour out the supernatant of the first two centrifugations, collect the supernatant suspension of the last 3 times, and after freeze-drying, few-layer or single-layer V 2 C MXene powder, which is few-layer or single-layer two-dimensional material V 2 CMXene.

[0078] Step 3: Prepare micron-scale V 2 cMXene@CsPbBr 3 Composite optoelectronic material, take an appropriate amount of V 2 cMXene powder and a certain amount of cesium bromide (CsBr) and lead bromide (PbBr 2 ), dimethyl sulfoxide solution (DMSO);

[0079] In this step, cesium bromide (CsBr), lead bromide (PbBr2) and V in a ratio of 1:1:1 to 1:4:1 2 C MXene material is added to dimethyl sulfoxide (DMSO) solution, ultrasonically dispersed for 15 - 20 minutes, then ultrasonically oscillated for 1 - 1.5 h, and then the mixture is heated in an oil bath at 80 - 100 °C for 5 - 9 h, and finally kept warm at 100 - 180 °C for 1 - 4 h. After taking out, wash with anhydrous ethanol or toluene for 3 - 5 times, and put it in an oven to dry for 8 - 12 h to obtain micron-scale V 2 CMXene@CsPbBr3 composite optoelectronic material.

[0080] Based on the micron-scale V 2 C MXene@CsPbBr3 composite optoelectronic material prepared above, prepare a human body infrared detector according to the following steps, including:

[0081] Take a Si wafer (with 100 nm SiO grown on one side 2 )(see Figure 2 ) or PDMS film as the substrate (see Figure 3 ), spin-coat the mixed solution on the substrate and dry it, select a suitable electrode, place it on the surface of the material, and prepare a self-powered human body infrared detection device. The electrode is indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. Preparation is completed.

[0082] Example 2

[0083] This example provides a preparation method for a detector used for infrared optoelectronic detection, including:

[0084] Step 1: Using V 2 AlC powder as raw material to prepare V 2 C powder, add 2 g of LiF powder and 40 mL of HCl solution with a concentration of 6 mol / L, and stir it with a magnetic stirrer for 0.5 h to make it fully mixed. Subsequently, mix 2 g of V 2 AlC powder with the solution in the container and stir for 10 min to promote full contact between the reactants. The reaction duration is 72 h, and the temperature during the reaction is controlled at 90 °C. Take out the cooled solution after the reaction from the container for centrifugation, and wash the sediment with alcohol and deionized water multiple times to remove impurities until the pH value of the solution is neutral.

[0085] Step 2: Exfoliate multi-layer V 2 C MXene into single-layer or few-layer. Take the sample V 2 C MXene prepared in step 1), add 20 mL of deionized water containing 5 mL of tetramethylammonium hydroxide (TMAOH), and stir at room temperature for 1 h. Subsequently, separate the excess TMAOH from the product by repeating centrifugal washing at 2000 rpm for 5 times. During the centrifugal washing process, pour out the supernatant of the first 2 centrifugations, collect the supernatant suspension of the last 3 times, and freeze-dry to obtain few-layer or even single-layer V 2 C MXene powder.

[0086] Step 3: Prepare micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material. Take 0.5 g of V 2 C MXene material, 0.5 mol of cesium bromide (CsBr) and 0.5 mol of lead bromide (PbBr 2 ) and add them to 10 ml of dimethyl sulfoxide (DMSO) solution, and ultrasonically disperse for 15 minutes. Then heat the mixture in an oil bath at 80 °C for 6 h, and finally keep it at 120 °C for 1 h. After taking it out, wash it 3 times with absolute ethanol and put it in an oven at 80 °C to dry for 6 h to obtain micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material. As Figure 4 shown is the scanning electron microscopy (SEM) image of the micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material prepared in Example 1 of the present invention. As Figure 4 can be seen, the composite optoelectronic material still maintains a high crystalline form, CsPbBr 3 still maintains a complete cubic state, and the size is relatively uniform. MXene as a lamellar structure has a good composite effect with CsPbBr 3 .

[0087] Step 4: Prepare a self-powered human body infrared detector. Take a Si wafer (with 100 nm SiO grown on one side) as the substrate, and spin-coat the mixed solution on the Si wafer (with 100 nm SiO grown on one side) at a rotation speed of 1000 rpm. After 1 minute, dry it at 80 °C for 6 hours. 2 ) as the substrate, and spin-coat the mixed solution on the Si wafer (with 100 nm SiO grown on one side) at a rotation speed of 1000 rpm. 2 ) for 1 minute and then dry it at 80 °C for 6 hours. Figure 5 The X-ray diffraction (XRD) pattern of the micron-scale VC MXene@CsPbBr composite optoelectronic material prepared in this embodiment is shown. 2 C MXene@CsPbBr 3 composite optoelectronic material is shown. The horizontal axis in Figure 5 represents the diffraction angle, and the vertical axis represents the relative intensity of the diffraction peak. As Figure 5 can be seen, the coexistence of the characteristic peaks of these two phases in the composite system without significant peak position overlap confirms that VC MXene and CsPbBr 2 form a heterostructure rather than a simple physical mixture. Another suitable electrode is selected and placed on the surface of the material. The electrode is an indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. The preparation is completed. 3 formed a heterostructure rather than a simple physical mixture. Another suitable electrode is selected and placed on the surface of the material. The electrode is an indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. The preparation is completed.

[0088] Effect measurement: Place the prepared sample on a semiconductor tester, use a light source (emission wavelength of 9 μm, power of 250 w) that mimics the human body radiation band to illuminate the sample at a distance of 0.5 m, and process it on the test system under the setting condition of 0 bias voltage to obtain an I-T image. As Figure 6 shown is the self-powered human body infrared I-T image detected by the micron-scale MXene@CsPbBr 3 composite optoelectronic material prepared in this embodiment. Figure 6 The horizontal axis in it represents time, and the vertical axis represents the current value at present. It can be seen that when the light source is within the detection range, the current changes instantaneously and increases by 8 orders of magnitude.

[0089] Example 3

[0090] This embodiment provides a preparation method for a detector used for infrared optoelectronic detection, including:

[0091] Step 1: Prepare VC powder using V 2 AlC powder as the raw material, add 2 g of LiF powder and 40 mL of HCl solution with a concentration of 6 mol / L, and stir it with a magnetic stirrer for 0.5 h to make it fully mixed. Subsequently, add 2 g of V 2 C powder, add 2 g of LiF powder and 40 mL of HCl solution with a concentration of 6 mol / L, and stir it with a magnetic stirrer for 0.5 h to make it fully mixed. Subsequently, add 2 g of V 2The AlC powder is mixed with the solution in the container and stirred for 10 min to promote sufficient contact between the reactants. The reaction duration is 72 h, and the temperature during the reaction is controlled at 100 °C. The cooled solution after the reaction is taken out from the container and centrifuged, and the sediment is washed repeatedly with alcohol and deionized water to remove impurities until the pH value of the solution is 7.

[0092] Step 2, exfoliate the multi-layer V 2 C MXene into single-layer or few-layer. Take the sample V 2 C MXene prepared in step 1), add it to 20 mL of deionized water containing 3 mL of tetramethylammonium hydroxide (TMAOH), and stir at room temperature for 1 h. Subsequently, the excess TMAOH is separated from the product by centrifugal washing at 2000 rpm for 5 times. During the centrifugal washing process, the supernatant of the first 2 centrifugations is discarded, and the supernatant suspensions of the last 3 times are collected. After freeze-drying, few-layer or even single-layer V 2 C MXene powder is obtained.

[0093] Step 3, prepare the micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material. Take 0.5 g of V 2 C MXene material, 0.5 mol of cesium bromide (CsBr) and 0.5 mol of lead bromide (PbBr 2 ) and add them to 10 ml of dimethyl sulfoxide (DMSO) solution, and ultrasonically disperse for 15 minutes. Then the mixture is heated in an oil bath at 80 °C for 6 h, and finally kept at 120 °C for 1 h. After taking it out, wash it 3 times with toluene to obtain the micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material.

[0094] Step 4, prepare a self-powered human infrared detector. Take a Si wafer (with 100 nm SiO 2 ) grown on one side as the substrate, and spin-coat the mixed solution on the Si wafer (with 100 nm SiO 2 ) grown on one side at a rotation speed of 1000 rpm. After 1 min, dry it at 80 °C for 6 h, select a suitable electrode and place it on the surface of the material. The electrode is indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. The preparation is completed.

[0095] Effect measurement: Place the prepared sample on a semiconductor tester. Use a light source (emission wavelength of 9 μm, power 250 w) that mimics the human radiation band, illuminate the sample at a distance of 0.5 m from the light, and change the illumination power, and process it on the corresponding software to obtain the I-T image (see Figure 7, Figure 7 The horizontal axis in Figure 7 represents time, and the vertical axis represents the current value at the moment). It can be seen that by changing the light power, the current value also changes accordingly, and the greater the power, the greater the current. This also lays the foundation for measuring the speed of the device.

[0096] Example 4

[0097] This example provides a preparation method for a detector used in infrared photoelectric detection, including:

[0098] Step 1: Prepare V 2 C powder using V 2 AlC powder as the raw material. Add 40 mL of HF solution with a concentration of 6 mol / L, and stir it with a magnetic stirrer for 0.5 h to make it fully mixed. Subsequently, mix 2 g of V 2 AlC powder with the solution in the container, and stir for 10 min to promote sufficient contact between the reactants. The reaction duration is 24 h, and the temperature during the reaction is controlled at 90 °C. Take out the cooled solution after the reaction from the container for centrifugal separation, and wash the sediment with alcohol and deionized water multiple times to remove impurities until the pH value of the solution is neutral.

[0099] Step 2: Exfoliate multilayer V 2 C MXene into single-layer or few-layer. Take the sample V 2 C MXene prepared in step 1), place it in an ice-water bath and ultrasonicate it for 1 h in an inert gas (N 2 ) environment. Subsequently, repeat centrifugal washing 5 times to separate it from the product. During centrifugal washing, pour out the supernatant of the first 2 centrifugations, collect the supernatant suspension of the last 3 times, and freeze-dry it to obtain few-layer or even single-layer V 2 C MXene powder.

[0100] Step 3: Prepare micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material. Take 0.5 g of V 2 C MXene material, 0.5 mol of cesium bromide (CsBr), and 0.5 mol of lead bromide (PbBr 2 ) and add them to 10 ml of dimethyl sulfoxide (DMSO) solution, and ultrasonically disperse for 15 minutes. Then heat the mixture in an oil bath at 80 °C for 6 hours, and finally keep it at 120 °C for 1 hour. After taking it out, wash it 3 times with absolute ethanol and put it in an oven to dry to obtain micron-scale V 2 C MXene@CsPbBr 3 composite optoelectronic material.

[0101] Step 4: Prepare a self-powered human body infrared detector. Take a Si wafer (with 100 nm SiO grown on one side) as the substrate, spin-coat the mixed solution on the Si wafer (with 100 nm SiO grown on one side) at a rotation speed of 1000 rpm, dry it at 80 °C for 6 h after 1 min, and select a suitable electrode and place it on the surface of the material. The electrode is an indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. Preparation is completed. 2 ) as the substrate, spin-coat the mixed solution on the Si wafer (with 100 nm SiO 2 ) at a rotation speed of 1000 rpm, dry it at 80 °C for 6 h after 1 min, and select a suitable electrode and place it on the surface of the material. The electrode is an indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. Preparation is completed.

[0102] Example 5

[0103] This example provides a method for preparing a detector for infrared optoelectronic detection, including:

[0104] 1) Prepare V 2 C MXene@CsPbBr 3 The raw materials and treatment methods refer to Example 1;

[0105] 2) Prepare a self-powered human body infrared detector. Mix the PDMS prepolymer and curing agent (Dow Corning) in a mass ratio of 10:1, stir well on a heating table at 40 °C to eliminate any bubbles. Then disperse the V 2 C MXene@CsPbBr 3 composite optoelectronic material prepared in the previous step on the surface of a glass disk. Add a small amount of PDMS copolymer for precoating, and then spin-coat at 2000 rpm for 1 min to ensure uniform coating of PDMS. The resulting mixture is heated on a heating table at 75 °C for 60 minutes until cured, and then washed with absolute ethanol to obtain a thin film. Finally, the thin film is attached to wax paper for easy transfer and transportation. Select a suitable electrode and place it on the surface of the material. The electrode is an indium gallium (In / Ga) alloy, which can form a good ohmic contact with the material. Preparation is completed. Preparation is completed.

[0106] It should be noted that the content not described in detail in the embodiments of the present invention belongs to the prior art well-known to those skilled in the art.

[0107] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims. The information disclosed in the background art part of this article is only intended to deepen the understanding of the overall background art of the present invention, and should not be regarded as an admission or any form of implication that this information constitutes the prior art already known to those skilled in the art.

Claims

1. A composite photoelectric material for infrared photoelectric detection, characterized in that: The composite photoelectric material is prepared by etching the MAX phase of a two-dimensional material MXene into multiple layers with an etchant, adding an intercalating agent, centrifuging and ultrasonically exfoliating, and freeze-drying the two-dimensional material MXene material to obtain a single-layer or few-layer MXene material, placing the obtained single-layer or few-layer MXene material with cesium bromide and lead bromide in a dimethyl sulfoxide solution, ultrasonically oscillating for a predetermined period of time, and heating and heat preservation to obtain a V2C MXene@CsPbBr3 composite photoelectric material.

2. The composite optoelectronic material for infrared photoelectric detection according to claim 1, characterized in that: The concentration of the dimethyl sulfoxide solution is 10-20 mg / mL; Place in dimethyl sulfoxide solution and ultrasonically vibrate for a predetermined time of 1 to 1.5 hours; The mass ratio of cesium bromide, lead bromide and few-layer or single-layer two-dimensional material V2C MXene is 1:1:1 to 1:4:

1.

3. A method for preparing a composite photoelectric material for infrared photoelectric detection, characterized in that: include: Using two-dimensional materials MXene, cesium bromide, and lead bromide as raw materials; The MAX phase of the two-dimensional material MXene is etched into multiple layers with an etchant, and then an intercalating agent is added for centrifugal ultrasonic stripping and freeze-dried into a single layer or a few layers of the two-dimensional material MXene; The obtained single-layer or few-layer two-dimensional material MXene material, cesium bromide and lead bromide are placed in a dimethyl sulfoxide solution and ultrasonically oscillated for a predetermined period of time, and the V2C MXene@CsPbBr3 composite photoelectric material obtained after heating and heat preservation is the composite photoelectric material.

4. The method for preparing a composite photoelectric material for infrared photoelectric detection according to claim 3, characterized in that: The method specifically comprises: Step 1, preparing a multi-layer two-dimensional material V2C MXene: adding LiF powder and HCl solution or HF solution into a polytetrafluoroethylene container for reaction, and then adding V2AlC powder for reaction to prepare a multi-layer two-dimensional material V2C MXene; Step 2, adding an intercalating agent to the multilayer two-dimensional material V2C MXene prepared in step 1, centrifugal ultrasonic exfoliation, and then freeze-drying to obtain a single-layer or few-layer two-dimensional material V2C MXene; Step 3, preparing a composite optoelectronic material: taking the single-layer or few-layer two-dimensional material V2C MXene obtained in step 2, cesium bromide and lead bromide, adding them to a dimethyl sulfoxide solution and ultrasonically oscillating for a predetermined time, and heating and keeping warm to obtain a micron-sized V2CMXene@CsPbBr3 composite optoelectronic material.

5. The method for preparing a composite photoelectric material for infrared photoelectric detection according to claim 4, characterized in that: The specific process of step 1 is as follows: add 2 to 5 parts by weight of LiF powder and HCl solution or HF solution with a molar ratio of V2C:HCl or V2C:HF of 1:1 to 1:2 into a polytetrafluoroethylene container, wherein the concentration of the HCl solution or the HF solution is 6 mol / L, stir them with a magnetic stirrer for 0.5 to 1 hour to fully mix them, mix 2 to 4 parts by weight of V2AlC powder with the solution in the polytetrafluoroethylene container, stir for 10 to 30 minutes, react for 48 to 72 hours, control the temperature during the reaction to be 70 to 90°C, take out the cooled solution after the reaction from the polytetrafluoroethylene container for centrifugal separation, and wash the sediment with alcohol and deionized water for multiple times to remove impurities until the pH value of the solution is 6 to 7, thereby obtaining a multi-layered two-dimensional material V2C MXene.

6. The method for preparing a composite photoelectric material for infrared photoelectric detection according to claim 4 or 5, characterized in that: The processing of step 2 is: Take the multilayer two-dimensional material V2C MXene prepared in step 1, add it to a mixed solution with a molar ratio of deionized water and tetramethylammonium hydroxide of 1:1 to 2:1, the molar ratio of the two-dimensional material V2C MXene to the tetramethylammonium hydroxide solution is 1:1 to 2:1, stir at room temperature for 1 to 2 hours, then repeat centrifugal washing at 2000 rpm for 3 to 6 times to separate the excess tetramethylammonium hydroxide from the product, pour out the upper clear liquid of the first two centrifugations during the centrifugal washing process, collect the upper suspension of the last three times and freeze-dry to obtain a powdery two-dimensional material V2C MXene with few layers or a single layer.

7. The method for preparing a composite photoelectric material for infrared photoelectric detection according to claim 4 or 5, characterized in that: The processing of step 3 is as follows: Cesium bromide, lead bromide and the few-layer or single-layer two-dimensional material V2CMXene obtained in step 2 in a mass ratio of 1:1:1 to 1:4:1 are added to a dimethyl sulfoxide solution, ultrasonically dispersed for 15 to 20 minutes, then ultrasonically oscillated for 1 to 1.5 hours, heated in an oil bath at 80 to 100°C for 5 to 9 hours, and finally kept at 100 to 180°C for 1 to 4 hours. After taking out, wash with anhydrous ethanol or toluene 3 to 5 times, and put into an oven for drying for 8 to 12 hours to obtain a micron-sized V2C MXene@CsPbBr3 composite optoelectronic material.

8. A detector for infrared photoelectric detection, characterized in that: include: Substrate, composite optoelectronic material film and electrode; wherein, The composite photoelectric material film is arranged on the substrate, and the composite photoelectric material film is a film formed by spin coating the V2C MXene@CsPbBr3 composite photoelectric material according to any one of claims 1 to 2 on the substrate and drying it; One end of the electrode forms electrical contact with the composite photoelectric material film.

9. The detector for infrared photoelectric detection according to claim 8, characterized in that: The substrate adopts a single-sided SiO2 substrate or a PDMS thin film substrate with a thickness of 100 nm. The electrode is an indium gallium alloy electrode.

10. A method for preparing a detector for infrared photoelectric detection, characterized in that: include: Take a substrate, spin-coat the V2C MXene@CsPbBr3 composite photoelectric material according to any one of claims 1 to 2 on the substrate and dry it to form a composite photoelectric material film; An electrode is placed on the surface of the composite photoelectric material film so that one end of the electrode forms electrical contact with the composite photoelectric material film.

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