CN104849324A - Resistance-type gas sensor based on graphene/multi-walled carbon nano-tube/zinc oxide composite material, and manufacturing method of resistance-type gas sensor - Google Patents
Resistance-type gas sensor based on graphene/multi-walled carbon nano-tube/zinc oxide composite material, and manufacturing method of resistance-type gas sensor Download PDFInfo
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Abstract
The invention discloses a graphene-based resistance-type gas sensor with room-temperature gas-sensitive response characteristics and a manufacturing method thereof, and belongs to the technical field of gas sensors. A silicon dioxide layer is generated on the surface of single crystal silicon, serving as a substrate, by using a thermal oxidation method; three to five pairs of interdigital gold electrodes are deposited on the surface of the silicon dioxide layer, a lead is connected to each interdigital gold electrode, the surfaces of the silicon dioxide layer and the interdigital gold electrodes are coated with a gas-sensitive film, the gas-sensitive film is a graphene/multi-walled carbon nano-tube/zinc oxide ternary composite material, and the thickness of the film is 10 to 50 microns; before and after the gas-sensitive film touches gas to be detected, the resistance of the gas-sensitive film is changed, and the sensitivity of the sensor can be obtained by measuring the change of the resistance between the interdigital gold electrodes. The sensor has high response sensitivity, high response recovery rate and high response reversibility at room temperature, and the problem that a zinc oxide gas sensor needs to work at high temperature generally is solved.
Description
Technical field
The invention belongs to gas sensor technical field, be specifically related to a kind of graphene-based resistor-type gas sensor with room temperature air-sensitive response characteristic and preparation method thereof, particularly relate to a kind of resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite and method for making.
Background technology
Along with the fast development of industrial or agricultural and transportation, problem of environmental pollution is more and more outstanding.Especially in recent years the discharge capacity of toxic and harmful, flammable explosive gas increases day by day, the gas in environment is carried out accurately, continuous print detect become problem demanding prompt solution, this just provides wide space for the application of gas sensor.Gas sensor is the important chemical sensor of a class, has a wide range of applications in industrial and agricultural production, process control, environmental monitoring and the field such as protection and anti-terrorism.Develop the study hotspot that the high performance gas sensor with advantages such as high sensitivity, low cost, low-power consumption, miniaturizations becomes scientific research field and industrial community.Wherein, sensitive material is the core of gas sensor, and the key improving gas sensor performance is the gas sensitive that exploitation has excellent response characteristic.At present, the conductor oxidate being representative with tin ash, zinc paste becomes a most widely used class sensitive material, it has the advantages such as easy to prepare, with low cost, wide material sources, but also come with some shortcomings simultaneously, such as, less stable, comparatively large by humidity effect, selectivity is not ideal enough.Gas sensor particularly based on metal oxide all needs to work at a higher temperature, and this makes the power consumption of element comparatively large, is difficult to prepare portable instrument.High working temperature directly affects the stability of sensor simultaneously, nor can be used for existing in the environment of flammable explosive gas, makes it apply and is subject to certain restrictions.In order to address this problem, reduce the working temperature of sensor, developing the extensive concern that the gas sensitive of working and room temperature is subject to researcher.Researchers attempt the compound substance preparing metal oxide and conducting polymer, and development can the gas sensor of working and room temperature.Although achieve room temperature to detect gas, metal oxide and conducting polymer composite material show sensitivity low, respond and recovers the problem such as slow, seriously obstruction its apply further.In recent years, the Two-dimensional Carbon based nano-material development taking Graphene as representative rapidly, becomes the focus of material circle research.The conductivity at room temperature that Graphene has and fast carrier mobility are that the gas sensitive of exploitation working and room temperature provides new thinking.Research finds that grapheme material really can realize room temperature and detect gas.In addition, Graphene and conductor oxidate compound can improve the sensitivity of graphene-based gas sensor further, improve response regeneration rate, are even expected to realize the highly sensitive gas detect under room temperature.Develop graphene-based room temperature air sensor and become one of important directions of sensor field research, develop very fast.
Summary of the invention
The object of this invention is to provide and a kind of at room temperature there is resistor-type gas sensor of the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic and preparation method thereof.
Resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite of the present invention is substrate with monocrystalline silicon, and adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 150 ~ 300nm; At silicon dioxide layer surface deposition 3 ~ 5 to interdigital gold electrode, the width of electrode is 50 ~ 100 μm, the thickness of electrode is 50 ~ 200nm, interdigital gold electrode is connected with lead-in wire, gas-sensitive film is coated with at silicon dioxide layer and interdigital gold electrode surfaces, this gas-sensitive film is Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, and the thickness of film is 10 ~ 50 μm; Before and after gas-sensitive film contact measured gas, its resistance can change, and by measuring the change of resistance between interdigital gold electrode, can obtain the sensitivity of sensor.
In described trielement composite material, the mass ratio of Graphene, multi-walled carbon nano-tubes, zinc paste is 1:0.4 ~ 20:18 ~ 900, and trielement composite material is three-dimensional porous structure, and hole dimension is 2 ~ 8nm, and BET specific surface area is 300 ~ 450m
2/ g.
The preparation method of Graphene/multi-walled carbon nano-tubes of the present invention/zinc paste trielement composite material resistor-type gas sensor, its step is as follows:
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 150 ~ 300nm; At silicon dioxide layer surface deposition 3 ~ 5 to interdigital gold electrode, the width of electrode is 50 ~ 100 μm, and the thickness of electrode is 50 ~ 200nm;
(2) be printed on the silicon dioxide of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) graphene oxide water solution is prepared, the concentration of graphene oxide water solution is 0.1mg/mL ~ 5mg/mL, then multi-walled carbon nano-tubes is added, ultrasonic disperse makes it mix fully, obtained Graphene/multi-walled carbon nano-tubes composite solution, be added in methanol solution by above-mentioned complex liquid, the weight ratio of graphene oxide and methyl alcohol is 1:4000 ~ 200000; Then add zinc nitrate and potassium hydroxide, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:0.2 ~ 10:2 ~ 100:4 ~ 200, stirs and ultrasonicly makes it be uniformly dispersed; Above-mentioned solution is put in oil bath and reacts 1 ~ 12 hour at 60 ~ 80 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution; Then, in above-mentioned system, add hydrazine hydrate, the weight ratio of graphene oxide and hydrazine hydrate is 1:0.064 ~ 3.2,80 ~ 90 DEG C of reactions 2 ~ 3 hours, thus obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution; Above-mentioned solution is carried out centrifuging, washing, oven dry, obtains Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material;
(4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), the concentration of compound substance aqueous solution is 1 ~ 10mg/mL; This solution is coated with the silica surface with interdigital gold electrode that step (2) obtains, then thermal treatment 1 ~ 4 hour at 80 ~ 130 DEG C, thus the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Gas sensor prepared by the present invention is used for NO
2room temperature response, the concentration of nitrogen dioxide is not more than 5ppm, is preferably not more than 3ppm, and its sensitivity is 1.10.
Advantage of the present invention is:
1) Graphene/multi-walled carbon nano-tubes/zinc oxide composite prepared by has three-dimensional porous structure, large specific surface area, make sensor at room temperature have very high response sensitivity, respond regeneration rate and good response reversibility fast, solving zinc paste gas sensor needs at high temperature just workable problem usually.
2) adopt wet chemistry method to prepare Graphene/multi-walled carbon nano-tubes/zinc oxide composite, method is simple, is easy to operation, with low cost.And can by controlling temperature of reaction, the experiment parameter such as ratio of reaction time and pre-reaction material realizes the regulation and control of the performance such as composition, structure of graphene-based compound substance.
3) introducing of graphene oxide and carbon nano-tube in composite material precursor, growth for zinc oxide nano-particle provides good template, by the template effect of Graphene and carbon nano-tube, the growth of controlled oxidization zinc effectively, obtains the zinc oxide nano-particle that size is less.The existence of zinc oxide nano-particle, effectively hinder the reunion of graphene oxide in reduction process, make the material obtained have larger specific surface area, be conducive to detecting the absorption of gas in sensitive material and diffusion, be conducive to the response sensitivity improving sensor.
4) introducing of Graphene in compound substance, can improve the electric conductivity of sensitive material significantly, avoids usual zinc paste because room temperature resistance is too high, and response sensitivity is extremely low and cannot realize room temperature and detect gas.
5) introducing of carbon nano-tube in compound substance, can stop the reunion of graphene sheet layer further, effectively improve the specific surface area of compound substance.The conductivity at room temperature that carbon nano-tube is good simultaneously also can improve the conductivity at room temperature of compound substance, improves the room temperature Detection results of material.
6) adopt wet chemistry method to generate zinc oxide nano-particle at Graphene and carbon nano tube compound material surface in situ, the combination of zinc paste and carbon-based material can be improved significantly, improve the conductivity at room temperature of material, be conducive to realizing room temperature and detect.The compound substance solution of preparation can adopt the methods such as spin coating film forming in interdigital electrode, and be easy to processing, can prepare gas sensor easily, solving traditional metal-oxide gas transducer needs high temperature sintering, the problem of processed complex.
Accompanying drawing explanation
Fig. 1 is the structural representation of gas sensor of the present invention.
Each several part name is called: monocrystalline silicon 1, adopt thermal oxidation method at the epontic silicon dioxide layer 2 of monocrystalline silicon 1, the multipair interdigital gold electrode 3 of deposition on silicon dioxide 2, at the gas-sensitive film 4 (Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material of the present invention) that silicon dioxide and interdigital gold electrode surfaces apply, the lead-in wire 5,6 that interdigital gold electrode connects.
Fig. 2 is the transmission electron microscope photo of the different amplification of Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Fig. 3 is that Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor is to 5ppm NO
2room temperature dynamic response recovery curve.
Fig. 4 is that Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor is to 5ppm NO
2room temperature response sensitivity (sensitivity definition is that sensor is in atmosphere with at NO
2in gas, the ratio of resistance between interdigital gold electrode) with gas concentration change curve.
Fig. 5 is that Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor is to 5ppm NO
2room temperature response repeated curve.
Fig. 6 is the selectivity analysis chart of Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor to gas with various.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment 1
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 150nm, and at silicon dioxide layer surface deposition 3 to interdigital gold electrode, the width of electrode is 50 μm, and the thickness of electrode is 50nm.
(2) be printed on the silicon dioxide layer of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) preparing 5mL concentration is the graphene oxide water solution of 0.1mg/mL, then 5mg multi-walled carbon nano-tubes is added, the weight ratio of graphene oxide and multi-walled carbon nano-tubes is 1:10, and ultrasonic disperse makes it mix fully, obtained Graphene and multi-walled carbon nano-tubes composite solution; Above-mentioned mixed liquor is added in the methanol solution of 125mL, the weight ratio of graphene oxide and methyl alcohol is 1:200000, then 0.05g zinc nitrate and 0.10g potassium hydroxide is added, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:10:100:200, stir and ultrasonicly make it be uniformly dispersed, above-mentioned solution is put in oil bath and reacts 12 hours at 60 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Then, in above-mentioned system, add 200 μ L hydrazine hydrates, graphene oxide and hydrazine hydrate weight ratio are 1:3.2.By above-mentioned solution 80 DEG C of reactions 3 hours, obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution; Above-mentioned solution is carried out centrifuging, washing, oven dry, and obtain Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, product quality is 229mg.
Graphene in the trielement composite material obtained: multi-walled carbon nano-tubes: the part by weight of zinc paste is 1:20:900, and trielement composite material is three-dimensional porous structure, and hole dimension is 2nm, and BET specific surface area is 300m
2/ g.
(4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), prepare the aqueous solution of Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, the concentration of compound substance is 1mg/mL; Above-mentioned solution is coated with the surface of silicon with interdigital gold electrode of step (2), at 80 DEG C, thermal treatment obtains sensitive material film in 4 hours, the thickness of film is 10 μm, the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Embodiment 2
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 150nm, and at silicon dioxide layer surface deposition 3 to interdigital gold electrode, the width of electrode is 50 μm, and the thickness of electrode is 50nm.
(2) be printed on the silicon dioxide layer of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) preparing 5mL concentration is the graphene oxide water solution of 0.5mg/mL, then 5mg multi-walled carbon nano-tubes is added, the weight ratio of graphene oxide and multi-walled carbon nano-tubes is 1:2, and ultrasonic disperse makes it mix fully, obtained Graphene and multi-walled carbon nano-tubes composite solution; Above-mentioned mixed liquor is added in 125mL methanol solution, the weight ratio of graphene oxide and methyl alcohol is 1:40000, then 0.5g zinc nitrate and 0.1g potassium hydroxide is added, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:2:20:40, stir and ultrasonicly make it be uniformly dispersed, above-mentioned solution is put in oil bath and reacts 8 hours at 70 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Then, in above-mentioned system, add 200 μ L hydrazine hydrates, graphene oxide and hydrazine hydrate weight ratio are 1:0.64.By above-mentioned solution 80 DEG C of reactions 2.5 hours, obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Above-mentioned solution is carried out centrifuging, washing, oven dry, obtains Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material.Product quality is 231mg.
Graphene in described trielement composite material: multi-walled carbon nano-tubes: the part by weight of zinc paste is 1:4:180, and trielement composite material is three-dimensional porous structure, and hole dimension is 4nm, and BET specific surface area is 350m
2/ g.
(4) Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3) is distributed in water the aqueous solution preparing Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, the concentration of compound substance is 4mg/mL; Above-mentioned solution is coated with the surface of silicon with interdigital gold electrode of step (2), at 90 DEG C, thermal treatment obtains sensitive material film in 3 hours, the thickness of film is 20 μm, the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Embodiment 3
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 200nm, and at silicon dioxide layer surface deposition 4 to interdigital gold electrode, the width of electrode is 80 μm, and the thickness of electrode is 100nm.
(2) be printed on the silicon dioxide layer of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) preparation 5mL, concentration are the graphene oxide water solution of 1mg/mL, then 5mg multi-walled carbon nano-tubes is added, the weight ratio of graphene oxide and multi-walled carbon nano-tubes is 1:1, and ultrasonic disperse makes it mix fully, obtained graphene oxide and multi-walled carbon nano-tubes composite solution; Above-mentioned mixed liquor is added in 125mL methanol solution, the weight ratio of graphene oxide and methyl alcohol is 1:20000, then 0.5g zinc nitrate and 0.1g potassium hydroxide is added, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:1:10:20, stir and ultrasonicly make it be uniformly dispersed, above-mentioned solution is put in oil bath and reacts 6 hours at 70 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Then, in above-mentioned system, add 200 μ L hydrazine hydrates, graphene oxide and hydrazine hydrate weight ratio are 1:0.32.By above-mentioned solution 80 DEG C of reactions 3 hours, obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Above-mentioned solution is carried out centrifuging, washing, oven dry, and obtain Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, product quality is 232mg.
Graphene in described trielement composite material: multi-walled carbon nano-tubes: the part by weight of zinc paste is 1:2:90, and trielement composite material is three-dimensional porous structure, and hole dimension is 5nm, and BET specific surface area is 380m
2/ g.
(4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), prepare the aqueous solution of Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, the concentration of compound substance is 5mg/mL; Above-mentioned solution is coated with the surface of silicon with interdigital gold electrode of step (2), at 100 DEG C, thermal treatment obtains sensitive material film in 2 hours, the thickness of film is 25 μm, the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Embodiment 4
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 200nm, and at silicon dioxide layer surface deposition 4 to interdigital gold electrode, the width of electrode is 80 μm, and the thickness of electrode is 150nm.
(2) be printed on the silicon dioxide layer of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) preparing 5mL concentration is the graphene oxide water solution of 2mg/mL, then 5mg multi-walled carbon nano-tubes is added, the weight ratio of graphene oxide and multi-walled carbon nano-tubes is 1:0.5, and ultrasonic disperse makes it mix fully, obtained Graphene and multi-walled carbon nano-tubes composite solution; Above-mentioned mixed liquor is added in 125mL methanol solution, the weight ratio of graphene oxide and methyl alcohol is 1:10000, then 0.5g zinc nitrate and 0.1g potassium hydroxide is added, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:0.5:5:10, stir and ultrasonicly make it be uniformly dispersed, above-mentioned solution is put in oil bath and reacts 8 hours at 80 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Then, in above-mentioned system, add 200 μ L hydrazine hydrates, graphene oxide and hydrazine hydrate weight ratio are 1:0.16.By above-mentioned solution 90 DEG C of reactions 3 hours, obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Above-mentioned solution is carried out centrifuging, washing, oven dry, and obtain Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, product quality is 234mg.
Graphene in described trielement composite material: multi-walled carbon nano-tubes: the part by weight of zinc paste is 1:1:45, and trielement composite material is three-dimensional porous structure, and hole dimension is 5nm, and BET specific surface area is 400m
2/ g.
(4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), prepare the aqueous solution of Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, the concentration of compound substance is 6mg/mL; Above-mentioned solution is coated with the surface of silicon with interdigital gold electrode of step (2), at 110 DEG C, thermal treatment obtains sensitive material film in 2 hours, the thickness of film is 30 μm, the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Embodiment 5
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 300nm, and at silicon dioxide layer surface deposition 5 to interdigital gold electrode, the width of electrode is 100 μm, and the thickness of electrode is 150nm.
(2) be printed on the silicon dioxide layer of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) preparing 5mL concentration is the graphene oxide water solution of 2.5mg/mL, then 5mg multi-walled carbon nano-tubes is added, the weight ratio of graphene oxide and multi-walled carbon nano-tubes is 1:0.4, and ultrasonic disperse makes it mix fully, obtained Graphene and multi-walled carbon nano-tubes composite solution; Above-mentioned mixed liquor is added in 125mL methanol solution, the weight ratio of graphene oxide and methyl alcohol is 1:8000, then 0.5g zinc nitrate and 0.1g potassium hydroxide is added, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:0.4:4:8, stir and ultrasonicly make it be uniformly dispersed, above-mentioned solution is put in oil bath and reacts 4 hours at 80 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Then, in above-mentioned system, add 200 μ L hydrazine hydrates, graphene oxide and hydrazine hydrate weight ratio are 1:0.128.By above-mentioned solution 90 DEG C of reactions 2.5 hours, obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Above-mentioned solution is carried out centrifuging, washing, oven dry, and obtain Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, product quality is 236mg.
Graphene in described trielement composite material: multi-walled carbon nano-tubes: the part by weight of zinc paste is 1:0.8:36, and trielement composite material is three-dimensional porous structure, and hole dimension is 6nm, and BET specific surface area is 420m
2/ g.
(4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), prepare the aqueous solution of Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, the concentration of compound substance is 8mg/mL; Above-mentioned solution is coated with the surface of silicon with interdigital gold electrode of step (2), at 120 DEG C, thermal treatment obtains sensitive material film in 3 hours, the thickness of film is 30 μm, the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Embodiment 6
(1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 300nm, and at silicon dioxide layer surface deposition 5 to interdigital gold electrode, the width of electrode is 100 μm, and the thickness of electrode is 200nm.
(2) be printed on the silicon dioxide layer of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
(3) preparing 5mL concentration is the graphene oxide water solution of 5mg/mL, then 5mg multi-walled carbon nano-tubes is added, the weight ratio of graphene oxide and multi-walled carbon nano-tubes is 1:0.2, and ultrasonic disperse makes it mix fully, obtained Graphene and multi-walled carbon nano-tubes composite solution; Above-mentioned mixed liquor is added in 125mL methanol solution, the weight ratio of graphene oxide and methyl alcohol is 1:4000, then 0.05g zinc nitrate and 0.1g potassium hydroxide is added, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:0.2:2:4, stir and ultrasonicly make it be uniformly dispersed, above-mentioned solution is put in oil bath and reacts 1 hour at 80 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Then, in above-mentioned system, add 200 μ L hydrazine hydrates, graphene oxide and hydrazine hydrate weight ratio are 1:0.064.By above-mentioned solution 90 DEG C of reactions 2 hours, obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution.Above-mentioned solution is carried out centrifuging, washing, oven dry, obtains Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material.Product quality is 242mg.
Graphene in described trielement composite material: multi-walled carbon nano-tubes: the part by weight of zinc paste is 1:0.4:18, and trielement composite material is three-dimensional porous structure, and hole dimension is 8nm, and BET specific surface area is 450m
2/ g.
(4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), prepare the aqueous solution of Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material, the concentration of compound substance is 10mg/mL; Above-mentioned solution is coated with the surface of silicon with interdigital gold electrode of step (2), at 130 DEG C, thermal treatment obtains sensitive material film in 1 hour, the thickness of film is 50 μm, the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material transmission electron microscope photo prepared by embodiment 1 as shown in Figure 2, as seen from Figure 2, compound substance has the lamellar structure of typical graphene-based material, and graphene sheet layer surface distributed a large amount of zinc oxide nano-particles and multi-walled carbon nano-tubes.Transmission electron microscope photo illustrates that the Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material of preparation has 3-D nano, structure, and its specific surface area is very large, reaches 300m after measured
2/ g.
Gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by embodiment 1 is at room temperature shown in Fig. 3 to the response recovery curve of variable concentrations nitrogen dioxide.Can find out, the nitrogen dioxide of graphene-based gas sensor to variable concentrations of preparation has very high, very fast response, and the response time is less than 1 minute, and sensor has good reversibility.
The response sensitivity curve of gas sensor to variable concentrations nitrogen dioxide based on Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by embodiment 1 is shown in Fig. 4.Can find out, sensor at room temperature has higher sensitivity to the nitrogen dioxide of low concentration, reaches 1.10 for 3ppm nitrogen dioxide.
Gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by embodiment 1 is at room temperature shown in Fig. 5 to the response repeatability curve of 5ppm nitrogen dioxide.Can find out, at room temperature through the multiple loop test of nitrogen dioxide-air, its response curve is almost constant, shows that this sensor has good response repeatability.
Gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by embodiment 1 is at room temperature shown in Fig. 6 for the selective response of gas with various.Can find out, sensor at room temperature has good response to nitrogen dioxide, and this sensor of surface has good selectivity.
Claims (7)
1. one kind at room temperature has the resistor-type gas sensor of the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic, it is characterized in that: be with monocrystalline silicon (1) for substrate, adopt thermal oxidation method to generate silicon dioxide layer (2) at monocrystalline silicon surface; At silicon dioxide layer (2) surface deposition 3 ~ 5 to interdigital gold electrode (3), be coated with Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material film (4) at silicon dioxide layer (2) and interdigital gold electrode (3) surface; In trielement composite material, three's mass ratio of Graphene, multi-walled carbon nano-tubes, zinc paste is 1:0.4 ~ 20:18 ~ 900.
2. a kind of resistor-type gas sensor at room temperature with the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic as claimed in claim 1, it is characterized in that: Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material is three-dimensional porous structure, hole dimension is 2 ~ 8nm, and BET specific surface area is 300 ~ 450m
2/ g.
3. a kind of resistor-type gas sensor at room temperature with the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic as claimed in claim 1, is characterized in that: the thickness of silicon dioxide layer (2) is 150 ~ 300nm; The width of interdigital gold electrode (3) is 50 ~ 100 μm, and thickness is 50 ~ 200nm; The thickness of Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material film is 10 ~ 50 μm.
4. a kind of preparation method at room temperature with the resistor-type gas sensor of the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic according to claim 3, its step is as follows:
1) take monocrystalline silicon as substrate, adopt thermal oxidation method to generate silicon dioxide layer at monocrystalline silicon surface, thickness is 150 ~ 300nm; At silicon dioxide layer surface deposition 3 ~ 5 to interdigital gold electrode, the width of electrode is 50 ~ 100 μm, and the thickness of electrode is 50 ~ 200nm;
2) be printed on the silicon dioxide of interdigital gold electrode with ethanol, water successively ultrasonic cleaning surface, dry stand-by;
3) graphene oxide water solution is prepared, the concentration of graphene oxide water solution is 0.1mg/mL ~ 5mg/mL, then multi-walled carbon nano-tubes is added, ultrasonic disperse makes it mix fully, obtained Graphene/multi-walled carbon nano-tubes composite solution, be added in methanol solution by above-mentioned complex liquid, the weight ratio of graphene oxide and methyl alcohol is 1:4000 ~ 200000; Then add zinc nitrate and potassium hydroxide, the weight ratio of graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and potassium hydroxide is 1:0.2 ~ 10:2 ~ 100:4 ~ 200, stirs and ultrasonicly makes it be uniformly dispersed; Above-mentioned solution is put in oil bath and reacts 1 ~ 12 hour at 60 ~ 80 DEG C, obtained graphene oxide/multi-walled carbon nano-tubes/zinc paste trielement composite material solution; In above-mentioned system, add hydrazine hydrate, the weight ratio of graphene oxide and hydrazine hydrate is 1:0.064 ~ 3.2,80 ~ 90 DEG C of reactions 2 ~ 3 hours, thus obtained Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material solution; Above-mentioned solution is carried out centrifuging, washing and oven dry, obtains Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material;
4) be distributed in water by Graphene/multi-walled carbon nano-tubes/zinc paste trielement composite material prepared by step (3), the concentration of compound substance aqueous solution is 1 ~ 10mg/mL; This solution is coated with step 2) the silicon dioxide layer surface with interdigital gold electrode that obtains, then thermal treatment 1 ~ 4 hour at 80 ~ 130 DEG C, thus the obtained resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite.
5. the resistor-type gas sensor at room temperature with the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic described in claim 1 or 2 or 3 is for detecting NO
2.
6. at room temperature there is the resistor-type gas sensor of the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic for detecting NO as claimed in claim 5
2, it is characterized in that: NO
2concentration be not more than 5ppm.
7. at room temperature there is the resistor-type gas sensor of the Graphene/multi-walled carbon nano-tubes/zinc oxide composite of high sensitivity gas response characteristic for detecting NO as claimed in claim 6
2, it is characterized in that: NO
2concentration be not more than 3ppm.
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