CN104849324B - A kind of resistor-type gas sensor and preparation method based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite - Google Patents
A kind of resistor-type gas sensor and preparation method based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite Download PDFInfo
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Abstract
A kind of graphene-based resistor-type gas sensor with room temperature air-sensitive response characteristic and preparation method thereof, belongs to gas sensor technical field.It is, with monocrystalline silicon as substrate, silicon dioxide layer to be generated in monocrystalline silicon surface using thermal oxidation method；3~5 pairs of interdigital gold electrodes are deposited in silica layer surface, connect leaded on interdigital gold electrode, gas-sensitive film is coated with silicon dioxide layer and interdigital gold electrode surfaces, the gas-sensitive film is Graphene/multi-walled carbon nano-tubes/zinc oxide 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, by measuring interdigital gold electrode between resistance change, the sensitivity of sensor can be obtained.Sensor has response sensitivity very high, quickly response regeneration rate and good response invertibity at room temperature, and solving zinc oxide gas sensor generally needs at high temperature just workable problem.
Description
Technical field
The invention belongs to gas sensor technical field, and in particular to a kind of Graphene with room temperature air-sensitive response characteristic
Based resistance type gas sensor and preparation method thereof, it is more particularly to a kind of multiple based on Graphene/multi-walled carbon nano-tubes/zinc oxide
The resistor-type gas sensor and preparation method of condensation material.
Background technology
With industrial or agricultural and the fast development of transportation, problem of environmental pollution is increasingly protruded.Especially in recent years
Toxic and harmful, the discharge capacity of flammable explosive gas increasingly increase, and accurate, continuous detection into is carried out to the gas in environment
It is problem demanding prompt solution, this is just for the application of gas sensor provides wide space.Gas sensor is that a class is important
Chemical sensor, had a wide range of applications in industrial and agricultural production, process control, environmental monitoring and protection and the field such as anti-terrorism.
Development has the advantages that high sensitivity, low cost, low-power consumption, the high performance gas sensor of miniaturization turn into scientific research field and product
The study hotspot of industry.Wherein, sensitive material is the core of gas sensor, and the key for improving gas sensor performance is exploitation
Gas sensitive with excellent response characteristic.At present, the conductor oxidate with tin ash, zinc oxide as representative turns into and uses
Most commonly used class sensitive material, it has the advantages that to prepare convenient, with low cost, wide material sources, but there is also one simultaneously
It is a little not enough, for example, less stable, is influenceed larger by humidity, and selectivity is not ideal enough etc..It is based particularly on metal oxide
Gas sensor is required for working at a higher temperature, and this causes that the power consumption of element is larger, it is difficult to prepare portable instrument.Together
When operating temperature high directly affect the stability of sensor, nor can be used in the environment for exist flammable explosive gas,
It is subject to certain restrictions its application.In order to solve this problem, operating temperature, the gas of exploitation working and room temperature of sensor are reduced
Quick material is subject to the extensive concern of researcher.Researchers' trial prepares the composite of metal oxide and conducting polymer,
Develop can working and room temperature gas sensor.Although realizing room temperature detection gas, metal oxide and conducting polymer
Composite material exhibits go out the problems such as sensitivity is low, response recovers slow, seriously hinder it further to apply.In recent years, with Graphene
For the two-dimentional c-based nanomaterial for representing quickly grows, the focus as the research of material circle.The conductivity at room temperature that Graphene has
With fast carrier mobility new thinking is provided to develop the gas sensitive of working and room temperature.Research finds that grapheme material is true
Can realize that room temperature detects gas in fact.Additionally, Graphene is compound with conductor oxidate can further to improve graphene-based
The sensitivity of gas sensor, improves response regeneration rate, or even be expected to realize highly sensitive gas detection at room temperature.Exploitation stone
Mertenyl room temperature air sensor turns into one of important directions of sensor field research, develops very fast.
The content of the invention
It is an object of the invention to provide a kind of Graphene/many wall carbon with high sensitivity gas response characteristic at room temperature
Resistor-type gas sensor of nanotube/zinc oxide composite and preparation method thereof.
Resistor-type gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite of the invention, with list
Crystal silicon is substrate, and silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, and thickness is 150~300nm；In silica
Layer surface deposits 3~5 pairs of interdigital gold electrodes, and the width of electrode is 50~100 μm, and the thickness of electrode is 50~200nm, interdigital
Connect leaded on gold electrode, be coated with gas-sensitive film in silicon dioxide layer and interdigital gold electrode surfaces, the gas sensitization
Film is Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, and the thickness of film is 10~50 μm；Gas sensitization is thin
Before and after film contact measured gas, its resistance can change, by measuring interdigital gold electrode between resistance change, can be passed
The sensitivity of sensor.
In the trielement composite material, Graphene, multi-walled carbon nano-tubes, the mass ratio of zinc oxide are 1：0.4~20：18~
900, trielement composite material is three-dimensional porous structure, and hole size is 2~8nm, and BET specific surface area is 300~450m2/g。
Graphene/multi-walled carbon nano-tubes of the present invention/zinc oxide trielement composite material resistor-type gas sensor
Preparation method, its step is as follows：
(1) with monocrystalline silicon as substrate, using thermal oxidation method monocrystalline silicon surface generate silicon dioxide layer, thickness be 150~
300nm；3~5 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 50~100 μm, and the thickness of electrode is
50~200nm；
(2) it is cleaned by ultrasonic the silica that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) graphene oxide water solution is prepared, the concentration of graphene oxide water solution is 0.1mg/mL~5mg/mL, then
Adding multi-walled carbon nano-tubes, ultrasonic disperse makes its mixing abundant, Graphene/multi-walled carbon nano-tubes composite solution is obtained, will be above-mentioned
Complex liquid is added in methanol solution, and graphene oxide is 1 with the weight ratio of methyl alcohol：4000~200000；It is subsequently adding 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, stirring and ultrasound make it be uniformly dispersed；Above-mentioned solution is put into oil bath the reaction 1~12 at 60~80 DEG C small
When, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained；Then, to adding water in above-mentioned system
Hydrazine is closed, graphene oxide is 1 with the weight ratio of hydrazine hydrate：0.064~3.2, reacted 2~3 hours at 80~90 DEG C, so as to be obtained
Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution；Above-mentioned solution is centrifuged, washes, is dried,
Obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material；
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, it is multiple
The concentration of the condensation material aqueous solution is 1~10mg/mL；The solution is coated with step (2) is obtained with interdigital gold electrode two
Silicon oxide surface, is then heat-treated 1~4 hour at 80~130 DEG C, so as to be obtained be based on Graphene/multi-walled carbon nano-tubes/oxygen
Change the resistor-type gas sensor of zinc composite.
Gas sensor prepared by the present invention is used for NO2Room temperature response, the concentration of nitrogen dioxide is not more than 5ppm, excellent
Choosing is not more than 3ppm, and its sensitivity is 1.10.
It is an advantage of the invention that：
1) Graphene/multi-walled carbon nano-tubes/zinc oxide composite prepared by has three-dimensional porous structure, big ratio table
Area so that sensor has response sensitivity very high at room temperature, quickly response regeneration rate and good response can
Inverse property, solving zinc oxide gas sensor generally needs at high temperature just workable problem.
2) Graphene/multi-walled carbon nano-tubes/zinc oxide composite is prepared using wet chemistry method, method is simple, it is easy to grasp
Make, it is with low cost.And can be by the experiment parameter reality such as ratio of controlling reaction temperature, reaction time and pre-reaction material
The regulation and control of the performances such as composition, the structure of existing graphene-based composite.
3) in composite material precursor graphene oxide and CNT introducing, be that the growth of zinc oxide nano-particle is carried
Good template has been supplied, by Graphene and the template effect of CNT, the growth of zinc oxide has been efficiently controlled, chi has been obtained
Very little less zinc oxide nano-particle.The presence of zinc oxide nano-particle, effectively obstruction graphene oxide is in reduction process
Reunion so that the material of acquisition has larger specific surface area, is conducive to detecting absorption and expansion of the gas in sensitive material
Dissipate, be conducive to improving the response sensitivity of sensor.
4) in composite Graphene introducing, the electric conductivity of sensitive material can be significantly increased, it is to avoid generally oxidation
Zinc because room temperature resistance it is too high, response sensitivity it is extremely low and cannot realize room temperature detect gas.
5) in composite CNT introducing, can further prevent the reunion of graphene sheet layer, effectively carry
The specific surface area of composite high.The good conductivity at room temperature of CNT can also improve the conductivity at room temperature of composite simultaneously
Property, improve the room temperature Detection results of material.
6) using wet chemistry method in Graphene and carbon nano tube compound material surface in situ generation zinc oxide nano-particle, can
Significantly to improve the combination of zinc oxide and carbon-based material, the conductivity at room temperature of material is improved, be advantageously implemented room temperature detection.System
Standby composite solution can be using method film forming in interdigital electrode such as spin coatings, it is easy to processes, can easily prepare gas
Body sensor, solving traditional metal-oxide gas transducer needs high temperature sintering, the problem of processed complex.
Brief description of the drawings
Fig. 1 is the structural representation of gas sensor of the invention.
Each several part is entitled：Monocrystalline silicon 1, using thermal oxidation method the superficial growth of monocrystalline silicon 1 silicon dioxide layer 2, two
The multipair interdigital gold electrode 3 deposited on silica 2, in the gas-sensitive film 4 that silica and interdigital gold electrode surfaces are coated
(Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material of the present invention), the lead connected on interdigital gold electrode
5、6。
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 Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor to 5ppm NO2Room temperature dynamic
Response recovery curve.
Fig. 4 is Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor to 5ppm NO2Room temperature response
(sensitivity definition is sensor in atmosphere and in NO for sensitivity2In gas, the ratio of resistance between interdigital gold electrode) with gas
Concentration curve.
Fig. 5 is Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor to 5ppm NO2Room temperature response
Repetition linearity curve.
Fig. 6 is selectivity point of the Graphene/multi-walled carbon nano-tubes/zinc oxide composite gas sensor to gas with various
Analysis figure.
Specific embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
Embodiment 1
(1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 150nm,
3 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 50 μm, the thickness of electrode is 50nm.
(2) it is cleaned by ultrasonic the silicon dioxide layer that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) it is the graphene oxide water solution of 0.1mg/mL to prepare 5mL concentration, is subsequently adding 5mg multi-walled carbon nano-tubes, oxygen
The weight ratio of graphite alkene and multi-walled carbon nano-tubes is 1：10, ultrasonic disperse makes its mixing abundant, and Graphene and many wall carbon are obtained
Nanotube composite solution；Above-mentioned mixed liquor is added in the methanol solution of 125mL, graphene oxide is 1 with the weight ratio of methyl alcohol：
200000, it is subsequently adding 0.05g zinc nitrates and 0.10g potassium hydroxide, graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and hydrogen
The weight ratio of potassium oxide is 1：10：100：200, stirring and ultrasound make it be uniformly dispersed, and above-mentioned solution is put into oil bath 60
Reacted 12 hours at DEG C, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Then, to above-mentioned
200 μ L hydrazine hydrates are added in system, graphene oxide is 1 with hydrazine hydrate weight ratio：3.2.Above-mentioned solution is small in 80 DEG C of reactions 3
When, Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained；Above-mentioned solution is centrifuged, water
Wash, dry, obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, product quality is 229mg.
Graphene in resulting trielement composite material：Multi-walled carbon nano-tubes：The part by weight of zinc oxide is 1：20：900,
Trielement composite material is three-dimensional porous structure, and hole size is 2nm, and BET specific surface area is 300m2/g。
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, is made
The aqueous solution of standby Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, the concentration of composite is 1mg/mL；Will be upper
The surface of silicon with interdigital gold electrode that solution is coated with step (2) is stated, is heat-treated at 80 DEG C and is obtained within 4 hours sensitive material
Material film, the thickness of film is 10 μm, and the resistor-type gas based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite is obtained
Body sensor.
Embodiment 2
(1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 150nm,
3 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 50 μm, the thickness of electrode is 50nm.
(2) it is cleaned by ultrasonic the silicon dioxide layer that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) it is the graphene oxide water solution of 0.5mg/mL to prepare 5mL concentration, is subsequently adding 5mg multi-walled carbon nano-tubes, oxygen
The weight ratio of graphite alkene and multi-walled carbon nano-tubes is 1：2, ultrasonic disperse makes its mixing abundant, Graphene is obtained and is received with many wall carbon
Mitron composite solution；Above-mentioned mixed liquor is added in 125mL methanol solutions, graphene oxide is 1 with the weight ratio of methyl alcohol：
40000, it is subsequently adding 0.5g zinc nitrates and 0.1g potassium hydroxide, graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and hydroxide
The weight ratio of potassium is 1：2：20：40, stirring and ultrasound make it be uniformly dispersed, and above-mentioned solution is put into oil bath and is reacted at 70 DEG C
8 hours, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Then, add in above-mentioned system
Enter 200 μ L hydrazine hydrates, graphene oxide is 1 with hydrazine hydrate weight ratio：0.64.Above-mentioned solution is reacted 2.5 hours at 80 DEG C, system
Obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution.Above-mentioned solution is centrifuged, washes, is dried
It is dry, obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material.Product quality is 231mg.
Graphene in the trielement composite material：Multi-walled carbon nano-tubes：The part by weight of zinc oxide is 1：4：180, ternary
Composite is three-dimensional porous structure, and hole size is 4nm, and BET specific surface area is 350m2/g。
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water and is made
The aqueous solution of standby Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, the concentration of composite is 4mg/mL；Will be upper
The surface of silicon with interdigital gold electrode that solution is coated with step (2) is stated, is heat-treated at 90 DEG C and is obtained within 3 hours sensitive material
Material film, the thickness of film is 20 μm, and the resistor-type gas based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite is obtained
Body sensor.
Embodiment 3
(1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 200nm,
4 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 80 μm, the thickness of electrode is 100nm.
(2) it is cleaned by ultrasonic the silicon dioxide layer that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) it is the graphene oxide water solution of 1mg/mL to prepare 5mL, concentration, is subsequently adding 5mg multi-walled carbon nano-tubes, oxygen
The weight ratio of graphite alkene and multi-walled carbon nano-tubes is 1：1, ultrasonic disperse makes its mixing abundant, and graphene oxide and many walls are obtained
CNT composite solution；Above-mentioned mixed liquor is added in 125mL methanol solutions, graphene oxide is 1 with the weight ratio of methyl alcohol：
20000, it is subsequently adding 0.5g zinc nitrates and 0.1g potassium hydroxide, graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and hydroxide
The weight ratio of potassium is 1：1：10：20, stirring and ultrasound make it be uniformly dispersed, and above-mentioned solution is put into oil bath and is reacted at 70 DEG C
6 hours, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Then, add in above-mentioned system
Enter 200 μ L hydrazine hydrates, graphene oxide is 1 with hydrazine hydrate weight ratio：0.32.Above-mentioned solution is reacted 3 hours at 80 DEG C, is obtained
Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution.Above-mentioned solution is centrifuged, washes, is dried,
Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material is obtained, product quality is 232mg.
Graphene in the trielement composite material：Multi-walled carbon nano-tubes：The part by weight of zinc oxide is 1：2：90, ternary is multiple
Condensation material is three-dimensional porous structure, and hole size is 5nm, and BET specific surface area is 380m2/g。
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, is made
The aqueous solution of standby Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, the concentration of composite is 5mg/mL；Will be upper
The surface of silicon with interdigital gold electrode that solution is coated with step (2) is stated, is heat-treated at 100 DEG C and is obtained within 2 hours sensitive
Material film, the thickness of film is 25 μm, and the resistor-type based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite is obtained
Gas sensor.
Embodiment 4
(1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 200nm,
4 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 80 μm, the thickness of electrode is 150nm.
(2) it is cleaned by ultrasonic the silicon dioxide layer that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) it is the graphene oxide water solution of 2mg/mL to prepare 5mL concentration, is subsequently adding 5mg multi-walled carbon nano-tubes, is aoxidized
The weight ratio of Graphene and multi-walled carbon nano-tubes is 1：0.5, ultrasonic disperse makes its mixing abundant, Graphene is obtained and is received with many wall carbon
Mitron composite solution；Above-mentioned mixed liquor is added in 125mL methanol solutions, graphene oxide is 1 with the weight ratio of methyl alcohol：
10000, it is subsequently adding 0.5g zinc nitrates and 0.1g potassium hydroxide, graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and hydroxide
The weight ratio of potassium is 1：0.5：5：10, stirring and ultrasound make it be uniformly dispersed, and above-mentioned solution are put into oil bath anti-at 80 DEG C
Answer 8 hours, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Then, in above-mentioned system
200 μ L hydrazine hydrates are added, graphene oxide is 1 with hydrazine hydrate weight ratio：0.16.Above-mentioned solution is reacted 3 hours at 90 DEG C, system
Obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution.Above-mentioned solution is centrifuged, washes, is dried
It is dry, Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material is obtained, product quality is 234mg.
Graphene in the trielement composite material：Multi-walled carbon nano-tubes：The part by weight of zinc oxide is 1：1：45, ternary is multiple
Condensation material is three-dimensional porous structure, and hole size is 5nm, and BET specific surface area is 400m2/g。
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, is made
The aqueous solution of standby Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, the concentration of composite is 6mg/mL；Will be upper
The surface of silicon with interdigital gold electrode that solution is coated with step (2) is stated, is heat-treated at 110 DEG C and is obtained within 2 hours sensitive
Material film, the thickness of film is 30 μm, and the resistor-type based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite is obtained
Gas sensor.
Embodiment 5
(1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 300nm,
5 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 100 μm, the thickness of electrode is 150nm.
(2) it is cleaned by ultrasonic the silicon dioxide layer that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) it is the graphene oxide water solution of 2.5mg/mL to prepare 5mL concentration, is subsequently adding 5mg multi-walled carbon nano-tubes, oxygen
The weight ratio of graphite alkene and multi-walled carbon nano-tubes is 1：0.4, ultrasonic disperse makes its mixing abundant, and Graphene and many wall carbon are obtained
Nanotube composite solution；Above-mentioned mixed liquor is added in 125mL methanol solutions, graphene oxide is 1 with the weight ratio of methyl alcohol：
8000, it is subsequently adding 0.5g zinc nitrates and 0.1g potassium hydroxide, graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and hydroxide
The weight ratio of potassium is 1：0.4：4：8, stirring and ultrasound make it be uniformly dispersed, and above-mentioned solution is put into oil bath and is reacted at 80 DEG C
4 hours, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Then, add in above-mentioned system
Enter 200 μ L hydrazine hydrates, graphene oxide is 1 with hydrazine hydrate weight ratio：0.128.Above-mentioned solution is reacted 2.5 hours at 90 DEG C,
Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Above-mentioned solution is centrifuged, washes, is dried
It is dry, Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material is obtained, product quality is 236mg.
Graphene in the trielement composite material：Multi-walled carbon nano-tubes：The part by weight of zinc oxide is 1：0.8：36, ternary
Composite is three-dimensional porous structure, and hole size is 6nm, and BET specific surface area is 420m2/g。
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, is made
The aqueous solution of standby Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, the concentration of composite is 8mg/mL；Will be upper
The surface of silicon with interdigital gold electrode that solution is coated with step (2) is stated, is heat-treated at 120 DEG C and is obtained within 3 hours sensitive
Material film, the thickness of film is 30 μm, and the resistor-type based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite is obtained
Gas sensor.
Embodiment 6
(1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 300nm,
5 pairs of interdigital gold electrodes are deposited in silica layer surface, the width of electrode is 100 μm, the thickness of electrode is 200nm.
(2) it is cleaned by ultrasonic the silicon dioxide layer that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
(3) it is the graphene oxide water solution of 5mg/mL to prepare 5mL concentration, is subsequently adding 5mg multi-walled carbon nano-tubes, is aoxidized
The weight ratio of Graphene and multi-walled carbon nano-tubes is 1：0.2, ultrasonic disperse makes its mixing abundant, Graphene is obtained and is received with many wall carbon
Mitron composite solution；Above-mentioned mixed liquor is added in 125mL methanol solutions, graphene oxide is 1 with the weight ratio of methyl alcohol：
4000, it is subsequently adding 0.05g zinc nitrates and 0.1g potassium hydroxide, graphene oxide, multi-walled carbon nano-tubes, zinc nitrate and hydroxide
The weight ratio of potassium is 1：0.2：2：4, stirring and ultrasound make it be uniformly dispersed, and above-mentioned solution is put into oil bath and is reacted at 80 DEG C
1 hour, graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution is obtained.Then, add in above-mentioned system
Enter 200 μ L hydrazine hydrates, graphene oxide is 1 with hydrazine hydrate weight ratio：0.064.Above-mentioned solution is reacted 2 hours at 90 DEG C, system
Obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution.Above-mentioned solution is centrifuged, washes, is dried
It is dry, obtain Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material.Product quality is 242mg.
Graphene in the trielement composite material：Multi-walled carbon nano-tubes：The part by weight of zinc oxide is 1：0.4：18, ternary
Composite is three-dimensional porous structure, and hole size is 8nm, and BET specific surface area is 450m2/g。
(4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, is made
The aqueous solution of standby Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material, the concentration of composite is 10mg/mL；Will be upper
The surface of silicon with interdigital gold electrode that solution is coated with step (2) is stated, is heat-treated at 130 DEG C and is obtained within 1 hour sensitive
Material film, the thickness of film is 50 μm, and the resistor-type based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite is obtained
Gas sensor.
Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material transmission electron microscope photo such as Fig. 2 prepared by embodiment 1
Shown, as seen from Figure 2, composite has the lamellar structure of typical graphene-based material, graphene film layer surface point
Cloth substantial amounts of zinc oxide nano-particle and multi-walled carbon nano-tubes.Graphene/many wall carbon prepared by transmission electron microscope photo explanation are received
Mitron/zinc oxide trielement composite material has 3-D nano, structure, and its specific surface area is very big, and 300m is reached after measured2/g。
Gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by embodiment 1 exists
The response recovery curve to various concentrations nitrogen dioxide is shown in Fig. 3 at room temperature.As can be seen that the graphene-based gas sensor for preparing
There is response very high, quickly to the nitrogen dioxide of various concentrations, the response time is less than 1 minute, and sensor has very well
Invertibity.
Gas sensor pair based on Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by embodiment 1
The response sensitivity curve of various concentrations nitrogen dioxide is shown in Fig. 4.As can be seen that sensor is at room temperature to the titanium dioxide of low concentration
Nitrogen has sensitivity higher, and 1.10 are reached for 3ppm nitrogen dioxide.
Gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by embodiment 1 exists
The response repetition linearity curve to 5ppm nitrogen dioxide is shown in Fig. 5 at room temperature.As can be seen that at room temperature by nitrogen dioxide-air
Multiple loop tests, its response curve is almost unchanged, shows that the sensor has good response repeatability.
Gas sensor based on Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by embodiment 1 exists
The selective response for gas with various is shown in Fig. 6 at room temperature.As can be seen that sensor has very well to nitrogen dioxide at room temperature
Response, the surface sensor has good selectivity.
Claims (3)
1. it is a kind of at room temperature with high sensitivity gas response characteristic Graphene/multi-walled carbon nano-tubes/zinc oxide composite wood
The preparation method of the resistor-type gas sensor of material, its step is as follows：
1) with monocrystalline silicon as substrate, silicon dioxide layer is generated in monocrystalline silicon surface using thermal oxidation method, thickness is 150~300nm；
Deposit 3~5 pairs of interdigital gold electrodes in silica layer surface, the width of electrode is 50~100 μm, the thickness of electrode for 50~
200nm；
2) it is cleaned by ultrasonic the silica that surface is printed on interdigital gold electrode successively with ethanol, water, dries stand-by；
3) graphene oxide water solution is prepared, the concentration of graphene oxide water solution is 0.1mg/mL~5mg/mL, is subsequently adding
Multi-walled carbon nano-tubes, ultrasonic disperse makes its mixing abundant, and Graphene/multi-walled carbon nano-tubes composite solution is obtained, will be above-mentioned compound
Liquid is added in methanol solution, and graphene oxide is 1 with the weight ratio of methyl alcohol：4000~200000；It is subsequently adding zinc nitrate and hydrogen
Potassium oxide, 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, stirring and ultrasound make it be uniformly dispersed；Above-mentioned solution is put into oil bath and is reacted 1~12 hour at 60~80 DEG C, be obtained
Graphene oxide/multi-walled carbon nano-tubes/zinc oxide trielement composite material solution；To hydrazine hydrate is added in above-mentioned system, stone is aoxidized
Black alkene is 1 with the weight ratio of hydrazine hydrate：0.064~3.2, reacted 2~3 hours at 80~90 DEG C, so as to Graphene/many walls are obtained
CNT/zinc oxide trielement composite material solution；Above-mentioned solution is centrifuged, washed and dried, acquisition Graphene/
Multi-walled carbon nano-tubes/zinc oxide trielement composite material；
4) Graphene/multi-walled carbon nano-tubes/zinc oxide trielement composite material prepared by step (3) is distributed in water, composite wood
The concentration for expecting the aqueous solution is 1~10mg/mL；The solution is coated with step 2) silica with interdigital gold electrode that obtains
Layer surface, is then heat-treated 1~4 hour, at 80~130 DEG C so as to be obtained for detecting NO2Based on Graphene/many wall carbon
The resistor-type gas sensor of nanotube/zinc oxide composite.
2. a kind of Graphene/many wall carbon with high sensitivity gas response characteristic at room temperature as claimed in claim 1 are received
The preparation method of the resistor-type gas sensor of mitron/zinc oxide composite, it is characterised in that：Graphene/multi-wall carbon nano-tube
Pipe/zinc oxide trielement composite material is three-dimensional porous structure, and hole size is 2~8nm, and BET specific surface area is 300~450m2/g。
3. a kind of Graphene/many wall carbon with high sensitivity gas response characteristic at room temperature as claimed in claim 1 are received
The preparation method of the resistor-type gas sensor of mitron/zinc oxide composite, it is characterised in that：The thickness of silicon dioxide layer is
150~300nm；The width of interdigital gold electrode is 50~100 μm, and thickness is 50~200nm；Graphene/multi-walled carbon nano-tubes/oxygen
The thickness for changing zinc trielement composite material film is 10~50 μm.
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