CN103852494A - Method for preparing nitrogen dioxide gas sensor element with ultra-fast response characteristics - Google Patents
Method for preparing nitrogen dioxide gas sensor element with ultra-fast response characteristics Download PDFInfo
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- CN103852494A CN103852494A CN201410082860.4A CN201410082860A CN103852494A CN 103852494 A CN103852494 A CN 103852494A CN 201410082860 A CN201410082860 A CN 201410082860A CN 103852494 A CN103852494 A CN 103852494A
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Abstract
The invention discloses a method for preparing a nitrogen dioxide gas sensor element with ultra-fast response characteristics. Direct in-situ assembly of a multi-level tungsten oxide nanostructure on the surface of a sensor substrate is realized through a seed layer induction growth path, a high-performance tungsten oxide-based nitrogen dioxide gas sensor element with room-temperature operating characteristics and an ultra-high response speed is formed, and a secondary transfer technical process of a gas-sensitive material is avoided. The multi-level nanostructure formed on the substrate in situ has continuous, porous and loosen microstructure characteristics and has obviously high specific surface area. Reliable electrical contact is formed between a gas-sensitive film and an electrode. The sensor element has high sensitivity and ultra-high response speed on the nitrogen dioxide gas at room temperature and has the advantages of simple equipment, easily controlled process parameters and low cost, and is convenient to operate.
Description
Technical field
The invention relates to gas sensor, relate in particular to a kind of preparation method based on tungstic acid multi-level nano-structure with the nitrogen dioxide gas sensor element of working and room temperature characteristic, super fast response speed.
Background technology
The development of modern society; the discharge of industrial gaseous waste makes that security issues become increasingly urgent; PM2.5 also more and more comes into one's own to the healthy threat of people; therefore more and more higher to reliability gas testing requirement; all need to there is high sensitivity in biology, chemical industry, medical science and food service industry, the nitrogen dioxide gas sensor of stability, selectivity and the feature such as portable, this is all significant to environmental protection and health.At present, many metal oxide semiconductors comprise ZnO, In
2o
3, SnO
2, TiO
2be widely used in the detection of nitrogen dioxide gas with NiO etc., its sensitive mechanism all belongs to surface resistance control type, to the detection of nitrogen dioxide gas be based on airborne oxygen and detected nitrogen dioxide gas at metal oxide semiconductor adsorption and reaction the resistance modulated process to semiconductor material.But the gas-sensitive property problems such as this class nitrogen dioxide gas sensor ubiquity working temperature is higher, the reaction time is long, gas-selectively is poor, microminiaturization to gas sensing technology, integrated, low-power consumption development have increased many complicacy and instability, but the today reaching its maturity based on radio sensing network, more and more stronger for the low-power consumption of device and integrated requirement.
There is more high performance nitrogen dioxide gas sensor in order to research and develop, researchist one constantly improves the sensitive property of gas sensor straight through the structure and composition of research new material, such as surface modification, form composite oxides, prepare the nano material of heterojunction structure etc.The particularly broad research of people to metal-oxide semiconductor (MOS) tungstic acid in recent years, find that it has good sensitivity characteristic to nitrogen dioxide, especially based on monodimension nano stick, nanotube, nano wire and the multi-stage oxidizing tungsten nanostructured forming with the self-organization of two-dimensional nano sheet, present porous, loose shape microstructure features, thereby there is higher specific surface area, this loose structure makes gas free in and out nano material more easily to realize, thereby the simultaneously low-dimensional size of its Component Structure and Debye length is comparable can obtain higher sensitivity, better selectivity and lower working temperature, for its application at high-performance nitrogen dioxide gas sensor provides more wide stage.But, find that based on previous researcher research its optimum working temperature is higher, conventionally 150 ℃ of left and right, be unfavorable for the research of low energy-consumption electronic device, and most gas sensors adopt secondary transferring technique, be the synthetic of gas sensitive, disperse, and transfer to gas sensor substrate, finally form gas sensor by thermal treatment, such secondary transferring technique is difficult to make the sensitive property of nanostructured gas sensitive to be not fully exerted, and the reliability that between the air-sensitive film being formed by secondary transferring and electrode, electricity contacts is difficult to guarantee, thereby affect stability and the reliability of gas sensor, in addition, complicated technological process is also unfavorable for the miniaturization of device, integrated.
Summary of the invention
Object of the present invention, be to overcome that current tungstic acid base nitrogen dioxide gas sensor working temperature is higher, response speed is slow, the adverse effect of the secondary transferring preparation technology of sensor to device air-sensitive performance, a kind of direct in-situ assembling that realizes sensor base surface tungstic acid multi-level nano-structure with Seed Layer induced growth approach is provided, forms the preparation method of the tungstic acid base nitrogen dioxide gas sensor element with working and room temperature characteristic, ultrafast response speed.
The present invention is achieved by following technical solution.
The preparation method with the nitrogen dioxide gas sensor element of super fast response characteristic, has following steps:
(1) prepare the interdigital platinum electrode of sensor
Aluminium oxide sensor base is successively cleaned and thoroughly dried and be placed in the vacuum chamber of ultrahigh vacuum facing-target magnetron sputtering system equipment in acetone solvent, absolute ethyl alcohol, deionized water for ultrasonic, using high pure metal platinum as target, using argon gas as working gas, sputter operating pressure is 2.0Pa, sputtering power 80～90W, sputtering time 8～10min, base reservoir temperature is room temperature, forms interdigital platinum electrode at alumina surface;
(2) prepare seed solution
Sodium tungstate is dissolved in the deionized water of 15ml, magnetic agitation makes it whole dissolvings, dropwise adds watery hydrochloric acid, until no longer produce precipitation, subsequently, heated solution to 40 ℃, and drip 2ml H
2o
2enter solution, continue to stir, it is the sodium tungstate seed solution of 0.2M～0.5M yellow transparent that precipitation is dissolved formation concentration;
(3) prepare Seed Layer
Sodium tungstate seed solution prepared by step (2) is coated in the aluminium oxide sensor base that is covered with interdigital electrode prepared by step (1), then be placed in annealing furnace, annealing in process under air atmosphere, annealing temperature is 500～600 ℃, temperature retention time 2～3h, heating rate is 2-3 ℃/min;
(4) prepare hydro-thermal reaction solution
The sodium tungstate solution of preparation 0.06M～0.1M, sodium tungstate is dissolved in deionized water, magnetic agitation is to all dissolving, add 0.08M～0.15M potassium chloride, adding template P123 is triblock copolymer again, forms the colloidal solution of homogeneous, dropwise adds watery hydrochloric acid, make the pH of solution be controlled at 2.1～2.5, form the sodium tungstate solution of milky homogeneous;
(5) prepare tungstic acid multi-level nano-structure
There is the aluminium oxide of sodium tungstate Seed Layer sensor base to be placed in the stainless steel hydrothermal reaction kettle that liner is teflon by covering in step (3), the sodium tungstate solution of simultaneously being prepared by step (4) is also transferred in reactor, sealing, then at 160～200 ℃ of temperature, adopt hydro-thermal method at the directly synthetic tungstic acid multi-stage nano material in aluminium oxide sensor base surface, the hydro-thermal reaction time is 6～12 hours, react complete, make reactor naturally cool to room temperature;
(6) rinse water thermal response rear oxidation aluminium sensor substrate
By the aluminium oxide sensor base after hydro-thermal reaction in step (5), repeatedly clean through deionized water and soaked in absolute ethyl alcohol, dry in the vacuum drying chamber of 60 ℃, make the nitrogen dioxide gas sensor element with super fast response characteristic based on tungstic acid multi-level nano-structure.
The metal platinum that the quality purity of the high pure metal platinum target of described step (1) is 99.95%.
The quality purity of the working gas argon gas of described step (1) is 99.999%.
The Platinum Electrode Thickness that described step (1) adopts radio-frequency magnetron sputter method to prepare is 80～120nm.
The seed solution of described step (3) adopts spin-coating method, dipping, spraying or drips the methods such as painting and is coated in the aluminium oxide sensor base that is covered with interdigital electrode.
After the Seed Layer annealing of described step (3), in aluminium oxide sensor base, forming equally distributed diameter is 100nm～1 μ m, and length is the little crystal grain of 1～5 μ m.
Beneficial effect of the present invention:
(1) provide a kind of direct in-situ assembling that realizes sensor base surface tungstic acid multi-level nano-structure with Seed Layer induced growth approach, formation has the preparation method of the tungstic acid base nitrogen dioxide gas sensor element of high-performance, the ultrafast response speed of working and room temperature characteristic, has avoided the secondary transferring technological process of gas sensitive; The multi-level nano-structure that original position forms on substrate presents continuously, porous, loose shape microstructure features, has obviously high specific surface area, and the free diffusing that the array growth of nano wire is more conducive to gas passes in and out, and is conducive to improve air-sensitive performance; Between air-sensitive film and electrode, having formed reliable electricity contacts.
(2) the nitrogen dioxide gas sensor based on tungstic acid multi-level nano-structure has super fast response characteristic, nitrogen dioxide gas has been represented the gas-sensitive properties such as good response-recovery characteristic, gas-selectively, high sensitivity when room temperature (20 ℃).This invention has vital role to the development of high-performance low-power-consumption nitrogen dioxide gas sensor, can further improve range of application and the application of nitrogen dioxide gas sensor.
(3) there is the advantages such as equipment is simple, easy to operate, and technological parameter is easy to control, with low cost.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the prepared Seed Layer of embodiment 1;
Fig. 2 is the electron scanning micrograph of the prepared tungstic acid material of embodiment 1;
Fig. 3 is the electron scanning micrograph of the prepared tungstic acid material of embodiment 2;
Fig. 4 is the electron scanning micrograph of the prepared tungstic acid material of embodiment 3;
Fig. 5 is the electron scanning micrograph of the prepared tungstic acid material of embodiment 4;
Fig. 6 is the electron scanning micrograph of the prepared tungstic acid material of embodiment 5;
Fig. 7 is the prepared tungstic acid multi-level nano-structure sensor element sensitivity to 5ppm nitrogen dioxide gas at different operating temperature of embodiment 4;
Fig. 8 is the prepared tungstic acid multi-level nano-structure sensor element of embodiment 4 dynamic response curve to nitrogen dioxide gas under room temperature (20 ℃);
Fig. 9 is that the prepared tungstic acid multi-level nano-structure sensor element of embodiment 4 is at room temperature to gas with various selectivity schematic diagram.
Embodiment
The present invention is raw materials used all adopts commercially available chemically pure reagent, below in conjunction with specific embodiment, the present invention is described in more detail.
(1) prepare the interdigital platinum electrode of aluminium oxide
Aluminium oxide sensor base is successively cleaned and thoroughly dried and be placed in the vacuum chamber of ultrahigh vacuum facing-target magnetron sputtering system equipment in acetone solvent, anhydrous nitrogen dioxide, deionized water for ultrasonic, metal platinum using quality purity as 99.95% is as target, argon gas using quality purity as 99.999% is as working gas, sputter operating pressure is 2.0Pa, sputtering power 80W, sputtering time 8min, base reservoir temperature is room temperature, form interdigital platinum electrode at alumina surface, the thickness of interdigital platinum electrode is 80nm;
(2) prepare seed solution
Sodium tungstate is dissolved in the deionized water of 15ml, magnetic agitation makes it whole dissolvings, dropwise adds watery hydrochloric acid, until no longer produce precipitation, subsequently, heated solution to 40 ℃, and drip 2ml H
2o
2enter solution, continue to stir, it is the seed solution of 0.2M yellow transparent that precipitation is dissolved formation concentration;
(3) prepare Seed Layer
Adopt spin-coating method to be coated in the aluminium oxide sensor base that is covered with interdigital electrode prepared by step (1) the sodium tungstate seed solution of preparation in step (2), then be placed in annealing furnace air atmosphere annealing in process, 500 ℃ of annealing temperatures, temperature retention time 2h, 2 ℃/min of heating rate;
(4) prepare hydro-thermal reaction solution
The sodium tungstate solution of preparation 0.06M, sodium tungstate is dissolved in deionized water, magnetic agitation is to all dissolving, add 0.08M potassium chloride, adding template P123 is triblock copolymer (polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer) again, forms the colloidal solution of homogeneous, dropwise adds watery hydrochloric acid, make the pH of solution be controlled at 2.1, form the sodium tungstate sol solution of milky homogeneous;
(5) prepare tungstic acid multi-level nano-structure
There is the aluminium oxide of sodium tungstate Seed Layer sensor base to be placed in the stainless steel hydrothermal reaction kettle that liner is teflon by covering in step (3), the sodium tungstate solution of simultaneously being prepared by step (4) is also transferred in reactor, sealing, then at the temperature of 160 ℃, adopt hydro-thermal method at the directly synthetic tungstic acid multi-stage nano material in aluminium oxide sensor base surface, the hydro-thermal reaction time is 12h, react complete, make reactor naturally cool to room temperature;
(6) rinse water thermal response rear oxidation aluminium sensor substrate
By the aluminium oxide sensor base after hydro-thermal reaction in step (5), repeatedly clean through deionized water and soaked in absolute ethyl alcohol, dry in the vacuum drying chamber of 60 ℃, make the nitrogen dioxide gas sensor element based on tungstic acid multi-level nano-structure.
The electron microscopic analysis result of the surface topography in embodiment 1 step (3) after the annealing of sodium tungstate Seed Layer as shown in Figure 1, can in aluminium oxide sensor base, form equally distributed diameter is 100nm～1 μ m, length is the little crystal grain of 1～5 μ m, in aluminium oxide sensor base, preparing tungstic acid multi-level nano-structure for next step provides growth in situ point, is the indispensable experimental section of the present invention.
The electron microscopic analysis result that embodiment 1 prepares gained tungsten trioxide nano material surface pattern as shown in Figure 2, can be clear that and in aluminium oxide sensor base, form equally distributed loose shape tungsten oxide reticulated film, and these mesh are to be made up of nano wire, nanobelt.
The difference of the present embodiment and embodiment 1 is: in step (1), sputtering time is 9min; In step (2), seed solution concentration is 0.3M; Adopt in step (3) infusion process to apply seed solution, and at 550 ℃ air atmosphere annealing 2.5h; In step (4), controlling potassium chloride concentration is 0.10M solution; Hydrothermal temperature in step (5) in hydro-thermal reaction solution is 180 ℃, makes tungstic acid multi-level nano-structure gas sensitive.
The scanning electron microscope analysis result of the surface topography of the present embodiment as shown in Figure 3, there are a large amount of class featheriness nanometer hierarchical structures of two-way growth dispersedly, in this multilevel hierarchy, nano wire is reunited with contacting and is formed nanometer bundle, the growth of the nano-chip arrays formula that the nanometer bundle at two ends is vertical and middle, and can be clear that a lot of gaps between nano wire, there is larger specific surface area, freely " turnover " of nitrogen dioxide gas be can make, thereby higher sensitivity, dynamic response faster made it have.
The difference of the present embodiment and embodiment 1 is: sputtering power 85W in step (1), and the thickness of interdigital platinum electrode is 100nm; In step (2), seed solution concentration is 0.4M; The aluminium oxide sensor base heating rate in annealing process that is coated with seed solution in step (3) is 3 ℃/min; In step (4), pH value of solution control is 2.3; Hydrothermal temperature in step (5) in hydro-thermal reaction solution is 200 ℃, makes the gas sensitive of tungstic acid micron bar structure.
The scanning electron microscope analysis result of the surface topography of the present embodiment as shown in Figure 4, due to the increase of temperature of reaction, obtains material and does enough energy in growth course, preferential growth in the specific direction of growth, the micron bar of formation monocrystal material.
The difference of the present embodiment and embodiment 1 is: sputtering time 10min in step (1), and the thickness of interdigital platinum electrode is 120nm; Adopt in step (3) drop-coating to apply seed solution, and at 600 ℃ air atmosphere annealing 3h; In step (4), controlling concentration of sodium tungstate is 0.08M, and potassium chloride concentration is 0.14M; Hydrothermal temperature in step (5) in hydro-thermal reaction solution is 180 ℃, and the hydro-thermal reaction time becomes 9h, makes tungstic acid multi-level nano-structure gas sensitive.
The scanning electron microscope analysis result of the surface topography of the present embodiment as shown in Figure 5, this product also presents the penniform nanometer hierarchical structure of class of partial array growth, but can significantly observe, with reaction conditions be 180 ℃, the product pattern of 12h is compared, and does not start polymerization, still the state in being separated from each other between nano wire, identical is that nano wire is all grown perpendicular to nanometer sheet with it, forms the penniform nanometer hierarchical structure of class.With respect to the nanometer bundle of reuniting, nano wire can provide more gas absorption point, and more loose " turnover " that is more conducive to nitrogen dioxide gas of structure, and these make to show aspect its sensitivity at gas-sensitive property and response speed more superior.Fig. 7-9 further reaction its to nitrogen dioxide gas the ultrafast response speed when the room temperature, and high sensitivity and selectivity characteristic.
The difference of the present embodiment and embodiment 1 is: sputtering power 90W in step (1), and the thickness of interdigital platinum electrode is 120nm; In step (2), seed solution concentration is 0.5M; Adopt in step (3) spraying process to apply seed solution, and at 600 ℃ air atmosphere annealing 2.5h, heating rate is 2.5 ℃/min; In step (4), controlling concentration of sodium tungstate is 0.10M, and potassium chloride concentration is 0.15M, and pH value of solution is 2.5; Hydrothermal temperature in step (5) in hydro-thermal reaction solution is 180 ℃, and the hydro-thermal reaction time becomes 6h, makes tungstic acid multi-stage nano network gas sensitive.
The scanning electron microscope analysis result of the surface topography of the present embodiment as shown in Figure 6, its pattern with at 160 ℃, under the reaction conditions of 12h, products therefrom is similar, and this is mainly because both reaction conditionss all can not provide enough energy to form nanometer hierarchical structure: temperature is too low or the reaction time is too short.
The present invention adopts static distribution method in 300 ℃ of temperature ranges, to measure the sensitivity characteristic of tungstic acid multi-level nano-structure sensor element to nitrogen dioxide gas in room temperature (20 ℃), sensitivity S=the Rg/Ra of definition gas sensor, wherein Rg, Ra are respectively element in the resistance value detecting in gas and dry air.
In measuring process, the nitrogen dioxide gas sensor of preparing gained is connected in circuit, by the resistance variations between two platinum electrode pins of the direct survey sensor of general-purpose ohmmeter, multimeter is directly connected with computing machine and can be stored measuring the data obtained.Whole circuit is placed in the container of a sealing, adjusts the concentration value of nitrogen dioxide in container by inject the nitrogen dioxide gas of different volumes in container.
Tungstic acid is a kind of typical N-shaped semiconductor, when oxidizing gas is (as NO
2) be adsorbed onto trioxide when surface, oxidizing gas molecule is combined with the scission of link of semiconductor surface, conduction charge carrier hole in oxidizing gas and the conduction carrier electrons of tungstic acid are compound, therefore make semi-conductive resistance change in the front and back of contact detection gas, the test of sensitivity is exactly this principle of based semiconductor resistance variations, and resistance variations more sensitivity is higher.
Claims (6)
1. the preparation method with the nitrogen dioxide gas sensor element of super fast response characteristic, has following steps:
(1) prepare the interdigital platinum electrode of sensor
Aluminium oxide sensor base is successively cleaned and thoroughly dried and be placed in the vacuum chamber of ultrahigh vacuum facing-target magnetron sputtering system equipment in acetone solvent, absolute ethyl alcohol, deionized water for ultrasonic, using high pure metal platinum as target, using argon gas as working gas, sputter operating pressure is 2.0Pa, sputtering power 80～90W, sputtering time 8～10min, base reservoir temperature is room temperature, forms interdigital platinum electrode at alumina surface;
(2) prepare seed solution
Sodium tungstate is dissolved in the deionized water of 15ml, magnetic agitation makes it whole dissolvings, dropwise adds watery hydrochloric acid, until no longer produce precipitation, subsequently, heated solution to 40 ℃, and drip 2ml H
2o
2enter solution, continue to stir, it is the sodium tungstate seed solution of 0.2M～0.5M yellow transparent that precipitation is dissolved formation concentration;
(3) prepare Seed Layer
Sodium tungstate seed solution prepared by step (2) is coated in the aluminium oxide sensor base that is covered with interdigital electrode prepared by step (1), then be placed in annealing furnace, annealing in process under air atmosphere, annealing temperature is 500～600 ℃, temperature retention time 2～3h, heating rate is 2-3 ℃/min;
(4) prepare hydro-thermal reaction solution
The sodium tungstate solution of preparation 0.06M～0.1M, sodium tungstate is dissolved in deionized water, magnetic agitation is to all dissolving, add 0.08M～0.15M potassium chloride, adding template P123 is triblock copolymer again, forms the colloidal solution of homogeneous, dropwise adds watery hydrochloric acid, make the pH of solution be controlled at 2.1～2.5, form the sodium tungstate solution of milky homogeneous;
(5) prepare tungstic acid multi-level nano-structure
There is the aluminium oxide of sodium tungstate Seed Layer sensor base to be placed in the stainless steel hydrothermal reaction kettle that liner is teflon by covering in step (3), the sodium tungstate solution of simultaneously being prepared by step (4) is also transferred in reactor, sealing, then at 160～200 ℃ of temperature, adopt hydro-thermal method at the directly synthetic tungstic acid multi-stage nano material in aluminium oxide sensor base surface, the hydro-thermal reaction time is 6～12 hours, react complete, make reactor naturally cool to room temperature;
(6) rinse water thermal response rear oxidation aluminium sensor substrate
By the aluminium oxide sensor base after hydro-thermal reaction in step (5), repeatedly clean through deionized water and soaked in absolute ethyl alcohol, dry in the vacuum drying chamber of 60 ℃, make the nitrogen dioxide gas sensor element with super fast response characteristic based on tungstic acid multi-level nano-structure.
2. according to the preparation method of the nitrogen dioxide gas sensor element with super fast response characteristic of claim 1, it is characterized in that the metal platinum that the quality purity of the high pure metal platinum target of described step (1) is 99.95%.
3. according to the preparation method of the nitrogen dioxide gas sensor element with super fast response characteristic of claim 1, it is characterized in that, the quality purity of the working gas argon gas of described step (1) is 99.999%.
4. according to the preparation method of the nitrogen dioxide gas sensor element with super fast response characteristic of claim 1, it is characterized in that, the Platinum Electrode Thickness that described step (1) adopts radio-frequency magnetron sputter method to prepare is 80～120nm.
5. according to the preparation method of the nitrogen dioxide gas sensor element with super fast response characteristic of claim 1, it is characterized in that, the seed solution of described step (3) adopts spin-coating method, dipping, spraying or drips the methods such as painting and is coated in the aluminium oxide sensor base that is covered with interdigital electrode.
6. according to the preparation method of the nitrogen dioxide gas sensor element with super fast response characteristic of claim 1, it is characterized in that, after the Seed Layer annealing of described step (3), in aluminium oxide sensor base, forming equally distributed diameter is 100nm～1 μ m, and length is the little crystal grain of 1～5 μ m.
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| CN104237325A (en) * | 2014-10-09 | 2014-12-24 | 扬州大学 | Preparation method of nitrogen dioxide sensing membrane based on dye-sensitized semiconductor |
| CN105092659A (en) * | 2015-08-28 | 2015-11-25 | 云南大学 | Pt-doped SnO2 mesoporous thin film-based gas sensor preparation method |
| CN108572196A (en) * | 2017-03-08 | 2018-09-25 | 天津大学 | Gas sensor and its preparation method and application based on silicon-tungsten oxide nano heterojunction structure |
| CN109632893A (en) * | 2019-01-11 | 2019-04-16 | 东北大学 | One kind being based on p-n heterojunction structure NiO-In2O3The gas sensor of composite Nano ball |
| CN110357606A (en) * | 2019-08-01 | 2019-10-22 | 东北大学 | A kind of In based on zeolite substrate2O3Nano material preparation and its application |
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| CN104237325A (en) * | 2014-10-09 | 2014-12-24 | 扬州大学 | Preparation method of nitrogen dioxide sensing membrane based on dye-sensitized semiconductor |
| CN105092659A (en) * | 2015-08-28 | 2015-11-25 | 云南大学 | Pt-doped SnO2 mesoporous thin film-based gas sensor preparation method |
| CN105092659B (en) * | 2015-08-28 | 2017-11-03 | 云南大学 | Gas sensor preparation method based on the Pt doping order mesoporous films of SnO2 |
| CN108572196A (en) * | 2017-03-08 | 2018-09-25 | 天津大学 | Gas sensor and its preparation method and application based on silicon-tungsten oxide nano heterojunction structure |
| CN109632893A (en) * | 2019-01-11 | 2019-04-16 | 东北大学 | One kind being based on p-n heterojunction structure NiO-In2O3The gas sensor of composite Nano ball |
| CN109632893B (en) * | 2019-01-11 | 2022-02-25 | 东北大学 | NiO-In based on p-n heterojunction structure2O3Composite nanosphere gas sensor |
| CN110357606A (en) * | 2019-08-01 | 2019-10-22 | 东北大学 | A kind of In based on zeolite substrate2O3Nano material preparation and its application |
| CN111747431A (en) * | 2020-07-06 | 2020-10-09 | 复旦大学 | Functionalized JANUS thin film device and super-assembly preparation method thereof |
| CN111747431B (en) * | 2020-07-06 | 2022-06-14 | 复旦大学 | Functionalized JANUS thin film device and super-assembly preparation method thereof |
| CN114235903A (en) * | 2020-09-09 | 2022-03-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gas sensor and manufacturing method thereof |
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Application publication date: 20140611 |