Application of charge-transfer-coated semiconductor material in gas sensor device

Abstract

The application of a charge-transfer-coated semiconductor material in a gas sensor device, the application comprising: bringing a charge-transfer-coated semiconductor material into contact with a gas to be detected, wherein the charge-transfer-coated semiconductor material is a gas-sensitive material formed by coating an outer surface of an initial semiconductor with organic components by means of a charge transfer effect. The presence of charge transfer interaction improves the carrier mobility and charge separation state lifetime of semiconductors, thereby improving the gas detection sensitivity and reducing the operating temperature; and the redox properties of organic coating components on the outside of semiconductors are utilized to improve the gas selectivity. The application retains the fundamental properties of initial semiconductors, and also reduces the application costs by means of simplifying a material preparation method; and has universality.

Description

Application of charge transfer coated semiconductor material in gas sensitive sensor device TECHNICAL FIELD

[0001] The application relates to an application of a charge transfer coated semiconductor material in a gas sensitive sensor device, and belongs to the technical field of semiconductor sensor materials. BACKGROUND

[0002] A gas sensitive sensor can identify and perceive the presence and concentration of a specific gas in a working environment, and is widely used in detection in the fields of environment, public safety, food and the like. A chemical resistance type gas sensitive sensor is a sensor that converts the composition and concentration of a detected gas into an electric signal, has the characteristics of simple preparation process, low cost, easy integration and miniaturization, and accounts for the current market mainstream. A gas sensitive material is a key component of the chemical resistance type gas sensitive sensor, and there are still some deficiencies at present: first, the room temperature sensitivity is low and the working temperature is high, that is, the sensitivity at room temperature is low or no response, and a working temperature of 200 DEG C or above is usually required, so that the gas sensitive sensor needs to be fixed in a socket, thereby being not conducive to on-demand layout, or causing the service life of a matched battery to be shortened, and causing maintenance to be troublesome; second, the selectivity is poor, and the gas sensitive sensor is easily disturbed by non-detection gases in a working environment, thereby causing false reporting or being unable to detect. In the prior art, the optimization methods of the semiconductor gas sensitive material mainly include nanocrystallization, doping, construction of a heterojunction, compounding and heat treatment and the like. These methods aim to improve the gas sensitive performance of the material, such as sensitivity, selectivity and stability, by changing the structure, composition or surface properties of the material. However, these methods also have some disadvantages: the nanocrystallization technology can significantly increase the specific surface area of the material and increase the gas adsorption sites, but the agglomeration of the nanoparticles may affect the gas diffusion and adsorption, and the surface energy of the nanomaterial is relatively high, which is easy to react with the gases in the environment, thereby causing the stability to decrease; the doping technology changes the energy band structure and electron distribution of the material by introducing other elements, but too much doping may cause the conductivity to be too strong, thereby reducing the gas sensitive performance, and the introduction of the doping elements may introduce new impurity phases, thereby affecting the purity and stability of the material; the construction of a heterojunction technology constructs a heterojunction of a semiconductor and a semiconductor, a semiconductor and a metal or a semiconductor and a carbon material (such as graphene, carbon nanotube and the like), and the charge transfer and energy band bending at the heterojunction interface will affect the conductivity of the gas sensitive material, thereby improving the gas sensitive performance, but the preparation of this technology is complex and has high cost; the compounding technology combines the advantages of multiple materials to improve the gas sensitive performance, but the preparation process of the composite material is complex, and the proportion and distribution of each component need to be accurately controlled, and the interaction between each component may cause the performance to be unstable; the heat treatment technology improves the performance by improving the crystal structure and surface properties of the material, but high-temperature treatment may cause the material to be phase changed or decomposed, thereby affecting the stability and performance.

[0003] Therefore, it is crucial to develop a simple and universal method to improve the sensitivity, selectivity and reduce the working temperature of the chemical resistance type gas sensor

[0004] SUMMARY

[0005] To solve the problems of low sensitivity, poor selectivity, high working temperature of the chemical resistance type gas sensor in the prior art and the problem that many gas sensing performances (stability, high sensitivity, fast response and recovery, normal temperature detection, good selectivity) are difficult to be considered, the application provides an application of a charge transfer coated semiconductor material in a gas sensing device, which applies the charge transfer coated semiconductor material as a gas sensing material in the gas sensing device, utilizes the existence of charge transfer interaction to improve the carrier mobility and charge separation state lifetime of the semiconductor, thereby improving the gas detection sensitivity and reducing the working temperature, and utilizes the redox characteristics of the organic coating component outside the semiconductor to improve the selectivity of the gas.

[0006] The application adopts the following technical scheme:

[0007] The application of a charge transfer coated semiconductor material in a gas sensing device, comprising: contacting the charge transfer coated semiconductor material with a to-be-detected gas.

[0008] The charge transfer coated semiconductor material is:

[0009] A gas sensitive material formed by coating the outer surface of an initial semiconductor with an organic component through charge transfer.

[0010] Optionally, the working temperature of the gas sensing device is 0-200 DEG C.

[0011] Optionally, the to-be-detected gas is an oxidizing gas and / or a reducing gas.

[0012] Optionally, the to-be-detected gas is selected from at least one of hydrogen sulfide, nitrogen dioxide, carbon monoxide, ammonia, sulfur dioxide, nitric oxide, and methane.

[0013] Optionally, the form of the initial semiconductor is selected from at least one of a micron or nano structure, a thin film, and a bulk.

[0014] Optionally, the micron or nano structure is selected from at least one of a nano or micron sized sheet, a rod, a sphere, and an array structure.

[0015] Optionally, the form of the initial semiconductor is preferably a thin film.

[0016] Compared with a bulk semiconductor, the thin film semiconductor material has a higher specific surface area, more sites can form a charge transfer complex with the organic coating component, and the gas sensing performance of the semiconductor material is improved.

[0017] Optionally, the initial semiconductor is selected from at least one of an elemental semiconductor, a metal compound semiconductor, an organic compound semiconductor.

[0018] Optionally, the elemental semiconductor is selected from at least one of silicon (Si), germanium (Ge), phosphorus (P), selenium (Se), antimony (Sb), boron (B).

[0019] Optionally, the metal compound semiconductor is selected from at least one of metal oxide, sulfide, selenide, telluride, phosphide, carbide, nitride, halide.

[0020] Optionally, the metal oxide is selected from at least one of ZnO, TiO2, SnO2, WO3, Fe2O3, In2O3, CuO, Co3O4, Cr2O3, NiO, Mn3O4, ZrO2.

[0021] Optionally, the sulfide is selected from at least one of ZnS, CdS, MoS2, WS2.

[0022] Optionally, the organic compound semiconductor is selected from at least one of coordination polymers, covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), conductive polymers, etc.

[0023] Optionally, the coordination polymers are selected from at least one of MOF-5, MOF-177, MOF-210, MOF-303, IRMOF series, UIO series, MIL series, HTTP series.

[0024] Optionally, the covalent organic frameworks (COFs) are selected from at least one of boron-containing COFs materials, imine-based COFs materials, triazine-based COFs materials, epoxy-based COFs materials, anhydride-based COFs materials.

[0025] Preferably, the initial semiconductor is selected from at least one of TiO2, SnO2, UIO-66 semiconductor, Cu-HTTP semiconductor.

[0026] Preferably, the morphology of the initial semiconductor is selected from thin film or powder.

[0027] Optionally, the organic component is selected from at least one of electron-donating organic component and / or electron-accepting organic component.

[0028] Optionally, the electron-donating organic component is selected from at least one of polythiophene (P3HT), polyphenylenevinylene (PPV) and its derivatives, polyaniline (PANI), polyfluorene (PF) and its derivatives, organic fullerene derivatives, polypyrrole, poly(p-phenylenevinylene).

[0029] Optionally, the electron-accepting organic component is selected from at least one of fullerene (C60), naphthalene diimide (NDI), perylene diimide (PDI), isoindigo (IC), methyl isoindigo (MeIC), viologen and its derivatives, 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its derivatives, polythiadiazole, poly(p-phenylene), polytrihenylamine (PTAA) and its derivatives.

[0030] The above-mentioned organic component is a molecule that is easy to form a charge transfer complex.

[0031] Preferably, the organic component is selected from at least one of mono-methyl viologen, bis-phenyl viologen, 7,7,8,8-tetracyanoquinodimethane (TCNQ).

[0032] Optionally, the charge transfer coated semiconductor material is prepared by a method comprising the following steps:

[0033] S1, mixing materials containing the organic component and a solvent to obtain a coating solution;

[0034] S2, immersing the initial semiconductor in the coating solution and stirring or dispersing the initial semiconductor and the coating solution mixture to form a coating layer, and then washing and drying to obtain the charge transfer coated semiconductor material.

[0035] Optionally, the solvent is selected from at least one of water, ethanol, methanol, acetone, ethylene glycol, N,N-dimethylformamide, N,N-dimethylacetamide.

[0036] Optionally, the content of the organic component in the charge transfer coated semiconductor material is 0.5-10%.

[0037] The application includes:

[0038] When the charge transfer coated semiconductor material is a bis-methyl viologen coated TiO2 nanometer array or TiO2 nanometer powder, the gas to be measured is H2S gas;

[0039] When the charge transfer coated semiconductor material is a bis-phenyl viologen coated SnO2 nanometer array or SnO2 nanometer powder, the gas to be measured is NO2 gas;

[0040] When the charge transfer coated semiconductor material is a bis-methyl viologen coated ZnO nanometer array or ZnO nanometer powder, the gas to be measured is H2S gas;

[0041] When the charge transfer coated semiconductor material is a 7,7,8,8-tetracyanoquinodimethane (TCNQ) coated UIO-66 powder, the gas to be measured is CO gas;

[0042] When the charge transfer coated semiconductor material is single-end methyl viologen coated Cu-HTTP powder, the gas to be detected is NO gas.

[0043] When the charge transfer coated semiconductor material is single-end methyl viologen coated ZnS powder, the gas to be detected is NH3 gas.

[0044] When the charge transfer coated semiconductor material is single-end methyl viologen coated MoS2 powder, the gas to be detected is H2S gas.

[0045] When the charge transfer coated semiconductor material is single-end ethyl viologen coated P3HT powder, the gas to be detected is CH4 gas.

[0046] When the charge transfer coated semiconductor material is double-end ethyl viologen coated COF-102 powder, the gas to be detected is C2H2 gas.

[0047] When the charge transfer coated semiconductor material is single-end methyl viologen coated Cu-HTTP powder, the gas to be detected is NO gas.

[0048] The beneficial effects that can be produced by the present application include:

[0049] The application provides the application of the charge transfer coated semiconductor material in a gas sensitive sensor device. Compared with the chemical resistance type semiconductor material in the prior art, the application uses the charge transfer coated semiconductor material as a gas sensitive material, introduces an organic matter to the surface of an initial semiconductor, and tightly coats the semiconductor with the organic component through charge transfer interaction. The charge transfer interaction improves and takes into account many gas sensitive sensing performances (stability, sensitivity, response and recovery speed, working temperature, selectivity) of the initial semiconductor material. Compared with the semiconductor material optimization method in the prior art, the application uses the method of introducing an organic matter to the finished semiconductor material to form a charge transfer coated composite material, that is, the basic properties of the initial semiconductor are retained, and the application cost is reduced by simplifying the material preparation method, and the application has universality. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is a morphology property change of TiO2 nanometer array before and after coating in the preparation example 1 of the application: (a) is a top view electron microscope graph of TiO2 nanometer array (AA), (b) and (c) are top view electron microscope graphs and cross section graphs of double-end methyl viologen coated TiO2 nanometer array (AA@double-end methyl viologen), and (d) is a schematic diagram of color change of TiO2 nanometer array film before and after charge transfer coating.

[0051] Figure 2 is the UV-Vis diffuse reflectance spectra of the double-tipped methyl viologen coated TiO2nanorod arrays (AA@double-tipped methyl viologen) and TiO2nanorod arrays (AA) prepared in Example 1 of the present application.

[0052] Figure 3 is the response time of (a) double-tipped methyl viologen coated TiO2nanorod arrays (AA@double-tipped methyl viologen) and (b) TiO2nanorod arrays (AA) to pure H2S gas at room temperature in Example 1 of the present application.

[0053] Figure 4 is the response percentage of double-tipped methyl viologen coated TiO2nanorod arrays (AA@double-tipped methyl viologen) to H2S and interfering gases at room temperature in Example 1 of the present application.

[0054] Figure 5 is the response time of double-tipped methyl viologen coated TiO2nanorod arrays (AA@double-tipped methyl viologen) and TiO2nanorod arrays (AA) to 10 ppm pure H2S gas at room temperature in Example 1 of the present application, showing its stability. DETAILED DESCRIPTION

[0055] The present application will be described in detail below with reference to Examples, but the present application is not limited to these Examples.

[0056] The raw materials in the Examples of the present application were purchased through commercial channels unless otherwise specified.

[0057] The double-tipped methyl viologen powder used in the Examples was synthesized based on the method reported in the prior literature: 4,4'-bipyridine (8.0 g, 51.2 mmol) and chloroacetic acid (12.2 g, 129.1 mmol) were dissolved in 80 mL of acetonitrile, and stirred at 88°C under reflux for 36 hours. After the reaction was turned off and cooled to room temperature, the solid product was collected by filtration under reduced pressure and washed with hot acetonitrile, N,N'-dimethylacetamide and dichloromethane 3-5 times until the sample color was washed to white. The collected product was placed in a vacuum oven at 80°C for vacuum drying, and the white powder was obtained.

[0058] The synthesis of the di-terminated phenyl viologen powder used in the examples followed a previously reported method: the entire synthesis process was divided into two key steps, the first step: 4,4'-bipyridine (12.0 g, 76.8 mmol) was first dissolved in 200 mL of acetonitrile with 1-chloro-2,4-dinitrobenzene (51.6 g, 254.4 mmol), and the solution was stirred and refluxed at a constant temperature of 95 °C for 60 h. After the reaction was completed, it was cooled to room temperature, and the resulting solid product was collected by filtration under reduced pressure. To remove residual impurities, the product was washed several times with hot acetonitrile, 3-5 times each time. Finally, the collected product was placed in a vacuum oven at 80 °C for vacuum drying to remove residual moisture and solvent, obtaining the pure white powder of the first step product. The second step: first, aniline (4575 μL, 50.2 mmol) was mixed with the first step product (13.5 g, 24.1 mmol), and then 100 mL of N,N'-dimethylacetamide was slowly added using a constant pressure dropping funnel. Stirring was maintained during the addition to ensure that the two substances were fully dissolved in N,N'-dimethylacetamide. Then, the resulting solution was stirred at a constant temperature of 93 °C for 12 h. After that, the temperature of the reaction system was lowered to 50 °C, and 500 mL of ethyl acetate was added dropwise using a constant pressure dropping funnel. After the reaction was completed, the crude product was again collected by filtration under reduced pressure, and the crude product was washed several times with hot N,N'-dimethylacetamide and ethyl acetate until the washing filtrate was colorless. To further improve the purity of the product, the powdered crude product was recrystallized in methanol. After removing the filter residue by filtration, the methanol solvent was removed using a rotary evaporator under reduced pressure, finally obtaining the red-brown crystalline di-terminated phenyl viologen product.

[0059] The TCNQ solid powder used in the examples was purchased commercially from Adamas.

[0060] The TiO2 nanorod array film used in the examples was prepared according to the literature (literature DOI: doi.org / 10.1002 / ange.202111519).

[0061] The SnO2 nanorod array film used in the examples was prepared according to the literature (literature DOI: 10.1002 / solr.201800133).

[0062] The UIO-66 semiconductor powder used in the examples was purchased commercially from Adamas.

[0063] The Cu-HTTP semiconductor powder used in the examples was prepared according to the literature (literature DOI: doi.org / 10.1002 / ange.202212797).

[0064] Unless otherwise specified, the test methods are all conventional methods, and the instrument settings are all recommended by the manufacturer.

[0065] The method for gas detection in the examples is the silver glue double probe method, that is, a silver wire with a diameter of 50 microns is attached to the silver glue as a conductive circuit. When preparing a chemical resistance sensor, a pair of parallel electrodes is connected at both ends of the thin film as the electrode part of the sensor using this method. These sensors are then tested in a self-made sensing system reported. The sensor device is placed in an opaque sealed quartz chamber, and dry air is used as the carrier gas of the target gas at room temperature. In order to carry out gas sensitive experiments, we monitor the change of direct current of the device under different concentrations of target gas. The measurement of the sensor device uses a direct current circuit and applies a bias voltage of 5V, and the electrical performance test is carried out by using a Keithley 2602B semiconductor measuring instrument. The target gas is accurately controlled by a mass flow controller (CS-200C, produced by Beijing Qixing Mass Flow Electronic Equipment Manufacturing Co., Ltd.), and after mixing the qualified gas mixture from Beijing Huayuan Gas Chemical Co., Ltd. with dry air in a proper ratio, it is introduced into the quartz tube. During the whole process, the gas flow remains constant at 200 mL / min. All sensing measurements are carried out under standard environmental conditions. The above gas detection method can obtain the performance data of the gas sensitive sensor such as response time, response degree and stability at the same time.

[0066] The gases used for testing the response degree of the gas in this application include hydrogen sulfide, nitrogen dioxide, nitric oxide, carbon monoxide, carbon dioxide, ammonia, methane, sulfur dioxide, sulfur trioxide, hydrogen, acetylene, ethylene, ethane, methanol, ethanol, acetone with the same concentration. In specific tests, the specific highly selective gas (the gas to be tested) corresponding to the charge transfer coated semiconductor material is one of the above gases, and the other gases with low selectivity are called interference gases.

[0067] The preparation of the charge transfer coated semiconductor material in this application refers to the patent with the publication number CN115672397A of the prior application of the applicant.

[0068] According to an embodiment of the present application, the charge transfer coated semiconductor material is prepared by a method comprising the following steps: mixing a material containing the organic component and a solvent to obtain a coating solution; immersing the initial semiconductor in the coating solution and stirring to form a coating layer, and then washing and drying to obtain the charge transfer coated semiconductor material.

[0069] According to an embodiment of the present application, the charge transfer coated semiconductor material is prepared by a method comprising the following steps: mixing a material containing the organic component and solvent to obtain a coating solution; dispersing the initial semiconductor in the coating solution mixture to form a coating layer, and then washing and drying to obtain the charge transfer coated semiconductor material.

[0070] The present application detects the change in conductivity or resistivity of the charge transfer coated semiconductor material after it is contacted with the gas to be detected. In the application of gas detection, the gas sensitive material is a semiconductor coated with an organic component and combined with the semiconductor through charge transfer interaction (i.e. the transfer of net charge between the two, thus generating electrostatic interaction). The presence of charge transfer interaction improves the carrier mobility and charge separation state lifetime of the semiconductor, thereby improving the sensitivity of gas detection and reducing the operating temperature. In addition, the redox properties of the organic coating component can improve the selectivity of the gas. Compared with the initial semiconductor, this type of material exhibits significant improvement in gas sensitive detection performance in terms of selectivity, stability, response speed, sensitivity, and operating temperature, and can detect gases at room temperature.

[0071] Preparation Example 1

[0072] The charge transfer coated semiconductor material was prepared by in-situ stirring-soaking synthesis method: 200 mg of bis-methyl viologen solid powder was completely dissolved in 20 ml of deionized water to prepare a bis-methyl viologen aqueous solution. A piece of TiO2 (initial semiconductor) nanometer array film was fixed with a clamp and suspended in the bis-methyl viologen aqueous solution (not touching the bottom and not touching the stirrer), and placed in a stirrer for 5 days of stirring. After the stirring was completed, the TiO2 nanometer array film was taken out and soaked in deionized water for 1 day to remove the unreacted bis-methyl viologen electron acceptor molecules. Finally, the charge transfer coated semiconductor, i.e. bis-methyl viologen coated TiO2 nanometer array, was obtained by natural drying from the deionized water, and was marked as AA@bis-methyl viologen.

[0073] The morphology changes of TiO2 (initial semiconductor) nanometer array before and after coating are shown in Figures 1a to 1d. The UV-visible diffuse reflectance spectra of TiO2 and AA@bis-methyl viologen were detected, and it can be seen from Figure 2 that the AA@bis-methyl viologen material has a wider light absorption range than the initial semiconductor. The red shift of the ultraviolet absorption edge can be observed after the formation of the charge transfer complex, indicating the formation of the charge transfer complex.

[0074] Example 1

[0075] A piece of TiO2 nanometer array film (AA) and a piece of AA@bis-methyl viologen obtained from Preparation Example 1 were respectively subjected to gas sensitive sensing test:

[0076] First, the air is passed to remove impurities, and then pure H2S gas is passed to test the electrical property change of the material. The test found that at room temperature (20-25℃), the response degree of the double-end methyl viologen coated TiO2 nanometer array to H2S gas at room temperature is 3000 times that of the TiO2 nanometer array, indicating that the charge transfer coated semiconductor material has a new adsorption reaction to the gas due to the surface coating of the organic matter. As can be known from the comparison of FIG. 3a and FIG. 3b, the AA@double methyl viologen gas sensitive material applied in the present application has excellent gas sensitive adsorption and desorption capacity. The response degree percentage comparison chart of AA@double methyl viologen to H2S and interfering gas at room temperature is shown in FIG. 4, indicating that AA@double methyl viologen has good selectivity to the measured gas. The response degree time chart of the double-end methyl viologen coated TiO2 nanometer array (AA@double-end methyl viologen) and the TiO2 nanometer array (AA) to 10 ppm pure H2S gas at room temperature is shown in FIG. 5, and it can be seen that AA@double-end methyl viologen has good stability.

[0077] Preparation Example 2

[0078] The charge transfer coated semiconductor material is prepared by in-situ stirring-soaking synthesis method, and the preparation method and conditions are the same as those of Preparation Example 1, except that the double-end methyl viologen solid powder is replaced by double-end phenyl viologen solid powder, and the TiO2 (initial semiconductor) nanometer array thin film is replaced by SnO2 nanometer array thin film, to obtain a charge transfer coated semiconductor, i.e. a double-end phenyl viologen coated SnO2 nanometer array, which is marked as AA@double-end phenyl viologen.

[0079] Example 2

[0080] A piece of SnO2 nanometer array thin film and a piece of AA@double-end phenyl viologen obtained in Preparation Example 2 are respectively subjected to gas sensitive sensing test.

[0081] First, the air is passed to remove impurities, and then pure NO2 gas is passed to test the electrical property change of the material. The test found that at room temperature (20-25℃), the response degree of the double-end phenyl viologen coated SnO2 nanometer array to NO2 gas at room temperature is 500 times that of the SnO2 nanometer array, indicating that the charge transfer coated semiconductor material has a new adsorption reaction to the gas due to the surface coating of the organic matter. The gas sensitive material provided in the present application has excellent gas sensitive adsorption and desorption capacity. The response degree results of AA@double-end phenyl viologen to NO2 and interfering gas at room temperature show good selectivity to the measured gas, as in Example 1. The response degree of the double-end phenyl viologen coated SnO2 nanometer array (AA@double-end phenyl viologen) and the TiO2 nanometer array (AA) to 10 ppm pure NO2 gas at room temperature is similar to the case in Example 1, and AA@double-end methyl viologen also has good stability.

[0082] Preparation Example 3

[0083] The charge transfer coated semiconductor material was prepared by in-situ stirring- soaking synthesis method: 200 mg of TCNQ solid powder was completely dissolved in 20 ml of ether to prepare a TCNQ ether solution, 3 mg of UIO-66 powder was soaked in the TCNQ ether solution, and was placed on a stirrer for stirring for 3 days, and after stirring, filtration, washing, centrifugation and drying were performed to remove unreacted TCNQ molecules, to obtain a charge transfer coated semiconductor, i.e. a UIO-66 powder coated with TCNQ, marked as UIO-66 semiconductor@TCNQ.

[0084] Example 3

[0085] Each 3 mg of UIO-66 powder and the UIO-66 semiconductor@TCNQ powder obtained in Preparation Example 3 was subjected to gas sensitive sensing test:

[0086] First, impurities were removed by passing air, and then pure CO gas was passed to test the change in electrical properties of the material. It was found that at room temperature (20-25°C), the response of the UIO-66 semiconductor@TCNQ powder to CO gas was 1200 times that of UIO-66 at room temperature, indicating that the charge transfer coated semiconductor material has a new adsorption reaction to the gas due to the surface coating of organic matter, and the gas sensitive material provided in the present application has excellent gas sensitive adsorption and desorption capacity. The response of UIO-66 semiconductor@TCNQ to CO and interfering gases at room temperature was tested, and the results showed good selectivity to the tested gas as in Example 1. The response of the UIO-66 powder coated with TCNQ (UIO-66 semiconductor@TCNQ) and the UIO-66 powder to 10 ppm pure CO gas at room temperature was tested, and the results were similar to those in Example 1, and the UIO-66 semiconductor@TCNQ also had good stability.

[0087] Preparation Example 4

[0088] The charge transfer coated semiconductor material was prepared by in-situ stirring- soaking synthesis method, and the preparation method and conditions were the same as those in Preparation Example 3, except that the TCNQ solid powder was replaced by a single-end methyl viologen solid powder, and the UIO-66 powder was replaced by a Cu-HTTP powder, to obtain a charge transfer coated semiconductor, i.e. a Cu-HTTP powder coated with a single-end methyl viologen, marked as Cu-HTTP@single-end methyl viologen.

[0089] Example 4

[0090] Each 3 mg of UIO-66 powder and the UIO-66 semiconductor@TCNQ powder obtained in Preparation Example 3 was subjected to gas sensitive sensing test:

[0091] First, the air is introduced to remove impurities, and then pure NO gas is introduced to test the change of the electrical properties of the material. Test found: at room temperature (20-25℃), the response degree of Cu-HTTP powder @ single-end methyl viologen to NO gas at room temperature is 800 times that of Cu-HTTP powder, indicating that the charge transfer coated semiconductor material has a new adsorption reaction to the gas due to the surface coating of organic matter. The gas-sensitive material provided by the application has excellent gas-sensitive adsorption and desorption capacity. The response degree of Cu-HTTP @ single-end methyl viologen to NO and interfering gases at room temperature was tested, and the results were the same as those of Example 1, showing good selectivity to the tested gas. The response degree of Cu-HTTP powder coated with single-end methyl viologen (Cu-HTTP @ single-end methyl viologen) and Cu-HTTP powder to 10 ppm pure NO gas at room temperature was tested, and the results were similar to those of Example 1. Cu-HTTP @ single-end methyl viologen also has good stability.

[0092] The above is only a few embodiments of the present application, and does not limit the present application in any form. Although the preferred embodiments are disclosed above, the present application is not limited thereto. Any person skilled in the art can make some changes or modifications to the disclosed technical content without departing from the scope of the technical solution of the present application, which are equivalent to equivalent embodiments and belong to the scope of the technical solution.

Claims

1. Use of a charge transfer coated semiconductor material in a gas sensitive sensing device, characterized in that, The application relates to a gas sensor device, comprising: contacting a charge transfer coated semiconductor material with a gas to be detected; the charge transfer coated semiconductor material is: a gas sensitive material formed by coating the outer surface of an initial semiconductor with an organic component through charge transfer.

2. Use according to claim 1, characterized in that, The working temperature of the gas sensitive sensor device is 0-200 DEG C.

3. Use according to any one of claims 1-2, characterized in that, The gas to be detected is an oxidizing gas and / or a reducing gas.

4. Use according to any one of claims 1 to 3, characterized in that, The gas to be detected is selected from at least one of hydrogen sulfide, nitrogen dioxide, carbon monoxide, ammonia, sulfur dioxide, nitric oxide and methane.

5. The use according to any one of claims 1 to 4, characterized in that, The form of the initial semiconductor is selected from at least one of a micro- or nano-structure, a thin film and a bulk. The micro- or nano-structure is selected from at least one of a nano- or micro-sized sheet, a rod, a sphere and an array structure.

6. Use according to any one of claims 1 to 5, characterized in that, The initial semiconductor is selected from at least one of an elemental semiconductor, a metal compound semiconductor and an organic compound semiconductor.

7. The use according to any one of claims 1 to 6, characterized in that, The elemental semiconductor is selected from at least one of silicon, germanium, phosphorus, selenium, antimony and boron.

8. Use according to any one of claims 1 to 7, characterized in that, The metal compound semiconductor is selected from at least one of a metal oxide, a sulfide, a selenide, a telluride, a phosphide, a carbide, a nitride and a halide.

9. Use according to any one of claims 1 to 8, characterized in that, The metal oxide is selected from at least one of ZnO, TiO2, SnO2, WO3, Fe2O3, In2O3, CuO, Co3O4, Cr2O3, NiO, Mn3O4 and ZrO2.

10. Use according to any one of claims 1 to 9, characterized in that, The sulfide is selected from at least one of ZnS, CdS, MoS2 and WS2.

11. Use according to any one of claims 1 to 10, characterized in that, The organic compound semiconductor is selected from a coordination polymer, a covalent organic framework (COF), a hydrogen-bonded organic framework and a conductive polymer.

12. The use according to any one of claims 1 to 11, characterized in that, The coordination polymer is selected from at least one of MOF-5, MOF-177, MOF-210, MOF-303, an IRMOF series, a UIO series, a MIL series and an HTTP series.

13. The use according to any one of claims 1 to 12, characterized in that, The covalent organic framework (COF) is selected from at least one of a boron-containing COF material, an imine-based COF material, a triazine-based COF material, an epoxy-based COF material and an anhydride-based COF material.

14. The use according to any one of claims 1 to 13, characterized in that, The organic component is selected from an electron-donating organic component and / or an electron-accepting organic component.

15. The use according to any one of claims 1 to 14, characterized in that, The electron-donating organic component is selected from at least one of a polythiophene, a polyphenylenevinylene and a derivative thereof, polyaniline, a polyfluorene and a derivative thereof, an organic fullerene derivative, a polypyrole, a poly(p-phenylenevinylene).

16. The use according to any one of claims 1 to 15, characterized in that, The electron-accepting organic component is selected from at least one of a fullerene, a perylenetetracarboxylic diimide, a perylenetetracarboxylic diimide, an isoindigo, a methylisoindigo, a viologen and a derivative thereof, 7,7,8,8-tetracyanoquinodimethane and a derivative thereof, a polythiadiazole, a poly(p-phenylene), a polytriarylamine and a derivative thereof.

17. The use according to any one of claims 1 to 16, characterized in that, The charge transfer coated semiconductor material is prepared by a method comprising the following steps: S1, mixing a material containing the organic component and a solvent to obtain a coating solution; S2, immersing the initial semiconductor in the coating solution and stirring or dispersing the initial semiconductor and the coating solution mixture, forming a coating layer, and then washing and drying to obtain the charge transfer coated semiconductor material.

18. The use according to any one of claims 1 to 17, characterized in that, The solvent is selected from at least one of water, ethanol, methanol, acetone, ethylene glycol, N,N-dimethylformamide, N,N-dimethylacetamide.

19. The use according to any one of claims 1 to 18, characterized in that, The content of the organic component in the charge transfer coated semiconductor material is 0.5-10%.

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