CN106596654B - Vertical response type gas sensor based on three-dimensional porous graphene extra-thin film and preparation method thereof - Google Patents
Vertical response type gas sensor based on three-dimensional porous graphene extra-thin film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of vertical response type gas sensor and preparation method thereof based on three-dimensional porous graphene extra-thin film, the preparation of preparation, positively charged porous graphene dispersion liquid through negatively charged porous graphene dispersion liquid, the assembling preparation of three-dimensional porous graphene extra-thin film, vertical response type gas sensor based on three-dimensional porous graphene extra-thin film four steps of preparation realize the preparation of sensor.The obtained porous graphene ultrathin membrane gas sensor of the present invention has high sensitivity to DMMP gas molecule；This preparation method simple process is suitable for a large amount of preparations of sensor.
Description
Technical field
The invention belongs to sensor technical field, it is related to a kind of nano-sensor and preparation method thereof, and in particular to a kind of
Vertical response type gas sensor based on three-dimensional porous graphene extra-thin film and preparation method thereof.
Background technique
Gas sensor plays increasingly important role in fields such as environmental monitoring, food safety, health cares.With
The development of nanotechnology, all using metal-oxide semiconductor (MOS) nano particle, carbon nanomaterial and two-dimensional nano-film etc.
It is used as sensitive material and constitutes gas sensor, there is more excellent detection performance compared with traditional sensors.Wherein,
Graphene has caused extensive concern since 2004 are found.Due to its unique bi-dimensional cellular structure, graphene tool
There are many irreplaceable advantages of conventional sensors material, therefore, as sensing material biology, chemistry, machinery, aviation,
Military affairs etc. have extensive development prospect.The sensor that single graphene film is constituted has repeatability poor, single and breaks
Split and caused by stability it is not high the disadvantages of, construct graphene film thin film netowrk become prepare high-efficient graphite alkene sensor very
One of effective method.However, due to lamella sintering action, being be easy to cause thin during constructing graphene film network
The contact area of graphene film and gas molecule is greatly reduced in film, to influence the air-sensitive performance of sensor.
Existing graphene film gas sensor generally uses the structure of horizontal layout electrode, i.e. positive and negative electrode is all located at film
Plane in, when electric current migrates in graphene planes, carrier is by the sluggishness of the gas molecule adhered to by graphene surface
It influences, there is a problem of responding so as to cause the graphene film sensor generally studied at present and restores slack-off.
Summary of the invention
The present invention In view of the above shortcomings of the prior art, provides a kind of hanging down based on three-dimensional porous graphene extra-thin film
Straight response type gas sensor and preparation method thereof, transport response from plane unlike, in the structure electric current with perpendicular to
The flowing of graphene film direction, avoids in plane since graphene face causes it to carrier the adherency of gas molecule
Inhibition, to realize the gas sensor of production to the extremely sensitive quick response performance of gas molecule.Meanwhile using height
Three-dimensional porous graphene extra-thin film is prepared in power UV irradiation and organic molecule modification electrostatic self-assembled technology or coating,
Increase the specific surface area of sensitive thin film, conducive to further increasing for response performance.
The present invention is achieved by the following technical solutions:
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, being adjusted with acid pH is 1~4；Then
Ultrasonic treatment forms graphene oxide dispersion；Dialysis treatment will be carried out after the ultraviolet processing of graphene oxide dispersion, obtains band
Negative electricity porous graphene disperses solution；The power of the ultraviolet processing is the W of 1500 W~4000, and the time is the min of 30 s~30；
(2) p-phenylenediamine is added in negatively charged porous graphene dispersion solution, back flow reaction obtains positively charged porous
Graphene dispersing solution；
(3) first electrode is successively immersed to electronegative porous graphene dispersion liquid, positively charged porous graphene dispersion
In liquid, repeats 15~200 times, be dried to obtain the first electrode with three-dimensional porous graphene extra-thin film；
(4) it is prepared on the three-dimensional porous graphene extra-thin film surface of the first electrode with three-dimensional porous graphene extra-thin film
Second electrode obtains the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film.
In above-mentioned technical proposal, in step (2), the mass ratio of the p-phenylenediamine and electronegative porous graphene is 1:
(5~20)；Reflux time is 12~24 h；After back flow reaction, filter cleaning, be added in alcohol obtain it is positively charged more
Hole graphene dispersing solution.
In above-mentioned technical proposal, in step (3), first electrode is placed in negatively charged porous graphene dispersion liquid and deposits one
The section time after dry cleaning treatment, then is placed in positively charged porous graphene dispersion liquid and deposits a period of time, dry cleaning treatment
Afterwards, then be placed in negatively charged porous graphene dispersion liquid and deposit a period of time, be deposited on repeatedly first electrode surface obtain 15~
200 layers of three-dimensional porous graphene ultrathin film.
In above-mentioned technical proposal, in step (3), the concentration of the negatively charged porous graphene dispersion liquid is 0.1~2 mg/
mL；The concentration of the positively charged porous graphene dispersion liquid is 0.1~2 mg/mL；Electronegative porous graphene is immersed every time
The time of dispersion liquid is 5~30 min；The time for immersing positively charged porous graphene dispersion liquid every time is 5~30 min.
The system of the invention also discloses a kind of vertical response type gas sensor based on three-dimensional porous graphene extra-thin film
Preparation Method, comprising the following steps:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, being adjusted with acid pH is 1~4；Then
Ultrasonic treatment forms graphene oxide dispersion；Dialysis treatment will be carried out after the ultraviolet processing of graphene oxide dispersion, obtained more
Hole redox graphene disperses solution；The power of the ultraviolet processing is the W of 1500 W~4000, and the time is 30 s~30
min；
(2) porous redox graphene dispersion solution is spun to first electrode surface, is dried, obtains with three
Tie up the first electrode of porous graphene ultrathin membrane；Then more in the three-dimensional of the first electrode with three-dimensional porous graphene extra-thin film
Hole graphene extra-thin film surface prepares second electrode, obtains the vertical response type gas based on three-dimensional porous graphene extra-thin film and passes
Sensor.
In the present invention, step (1) described graphene oxide can by Hummers method, Brodie method or
Staudenmaier method is prepared；It is preferred that first by graphene oxide water solution point before liquid oxidizer and sulfate is added
Processing 1~5 hour is dissipated, avoids gathering conducive to graphene oxide dispersion, and good with liquid oxidizer and sulfate formation
Reaction interface.
In the present invention, in step (1), graphene oxide water solution is added in liquid oxidizer in the form of aqueous oxidizing agent solution
In, sulfate is added in graphene oxide water solution in the form of sulfate solution；The concentration of the graphene oxide water solution
For 0.2~5 mg/mL, preferably 0.5~3 mg/mL；The concentration of sulfate solution be 10~50 mM, preferably 15~30
mM；The concentration of aqueous oxidizing agent solution is 4~10 wt%, preferably 5~8 wt%；Graphene oxide water solution, aqueous oxidizing agent solution,
The volume ratio of sulfate solution is (150~250): (50~120): 1, preferably (190~210): (70~90): 1, at this
In proportional region, it is able to achieve nano-pore being uniformly distributed in graphene film, non-porous broken small nanometer will be obtained by crossing large scale etching
Graphene film, too small concentration obtain being the graphene film with oxygen-containing group.
In the present invention, in step (1), liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；Acid is hydrochloric acid.Mixing
Solution realizes that the etching of graphene oxide sheet and reduction provide media environment for a step.
In the present invention, in step (1), the power of ultrasonic treatment is 50~100 kHz, and the time is the h of 10 min~1.Oxidation
Graphite is placed in mixed solution, can be attracted each other between particle, causes dispersion stability poor, and ultrasonic disperse can reduce particle
Between concentration effect, provide good basis to form uniform graphene.
In the present invention, the preparation that step (1) porous graphene disperses solution is porous graphene gas sensor of the present invention
Important step；Graphene oxide dispersion is placed in high power ultraviolet lamp reduction etching reaction in next step, is set after reaction
In bag filter, dialyses obtain porous redox graphene dispersion solution in deionized water；Limit the power of ultraviolet lamp
For the W of 1500 W~4000, the preferably W of 1500 W~3000, the ultraviolet processing time is the min of 30 s~30, preferably 30 s~70s,
Can not only redox graphene, and obtain etching graphene, it is exactly of the invention it is creative where.The present invention adopts for the first time
With ultraviolet processing graphene oxide dispersion, ultraviolet processing not only obtains porous graphene, but also realizes graphene oxide
The color of reduction, graphene solution becomes aterrimus by light gray is transparent, and nanometer sheet becomes conductive by insulating, with reducing degree
Intensification, resistance gradually decreases, and avoids the defect that existing reduction treatment must be conducive to chemical reagent, mention for green chemistry
For new approach；Particularly, the porous graphene obtained has nanoscale hole, can greatly improve the ratio table of graphene network
Area solves the defect of existing graphene network compact structure as caused by graphene easily piling up property, and etches pore
Process is simple, can large-scale production, avoid existing porous graphene and need high temperature (temperature of carbon thermal reduction), low yield, hole
Rate is low and uncontrollable, pore size distribution uniformity difference problem；Especially the present invention realizes the graphene oxide under the conditions of oxidant
Reduction, the prior art think oxidant presence can not redox graphene, but the present invention increase UV power, limit
Fixed ultraviolet processing time, while the oxidant and sulfate of compatibility proper ratio, and dispersion liquid acid value is limited, realize oxidation stone
The reduction of black alkene has not only obtained the excellent graphene of specific surface area, but also has obtained the reduction-oxidation graphite of excellent electrical property
Alkene plays a crucial role for gas sensor for bigger serface graphene, achieves unexpected technical effect.
The present invention uses the ultraviolet means of high power, and one step of energy realizes the etching and reduction of graphene oxide sheet, this is existing
Technology institute under oxidant hydrogen peroxide environment is inaccessiable.It is double due to containing oxidant in graphene solution under the prior art
The etching of graphene oxide only occurs for oxygen water, solution, and the drastic reduction of graphene oxide sheet cannot occur, obtained porous oxidation
Graphene film is insulation, cannot achieve its electric conductivity.Therefore, high power ultraviolet irradiation processing of the present invention has significantly simplified porous
The preparation step of graphene film, and speed is fast, is conducive to the low-coat scaleization preparation of senser element.
In the present invention, in step (1), the dialysis treatment time is 3 days~15 days, and molecular cut off is generally 10000
Left and right, the effect of dialysis are to remove the impurity such as remaining metal ion, hydrogen ion and hydrogen peroxide in solution.
In the present invention, second electrode is prepared on three-dimensional porous graphene extra-thin film surface using micro-processing technology, obtains base
In the vertical response type gas sensor of three-dimensional porous graphene extra-thin film.First electrode of the invention, second electrode are right respectively
Positive electrode, negative electrode or negative electrode, positive electrode are answered, the electrode vertical distribution, it is ultra-thin that three-dimensional porous graphene is arranged in centre
Film is a kind of new sensor structure.
Invention additionally discloses the vertical response type gas based on three-dimensional porous graphene extra-thin film of above-mentioned preparation method preparation
Body sensor, the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film that the present invention obtains to gas especially
It is that DMMP molecule (dimethyl methyl phosphonate) has excellent sensing capabilities.
Especially, the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film that the present invention obtains is just
Three-dimensional porous graphene extra-thin film is set between negative electrode, forms vertical interlayer structure, is just embodying creativeness of the invention.This
Invention, which effectively overcomes the prior art, in sensing membrane one side while the defect of positive and negative electrode is arranged, the vertical response of preparation
Type gas sensor has very high specific surface area, substantially increases the contact with gas molecule, effectively increases sensing
The detectability of device.
In preparation method of the invention, without handling first electrode, direct self assembly or the three-dimensional porous graphene of coating
Solution, in finally formed vertical interlayer structure, porous membrane stability is good, no ablation phenomenon；It efficiently solves existing
Technology needs to handle the problem of electrode or substrate.
Particularly, the vertical response type based on three-dimensional porous graphene extra-thin film of preparation method preparation through the invention
Gas sensor, three-dimensional porous graphene extra-thin film have extraordinary interfacial contact with positive and negative electrode respectively, have both improved biography
Sensor increases detection accuracy to the sensitivity of gas again；Limit three-dimensional porous graphene extra-thin film with a thickness of 20~900
Nanometer, both effectively avoids the contact of positive and negative electrode, more ultraviolet reduction etching processing under combined oxidant make three-dimensional porous stone
Black alkene ultrathin membrane has extraordinary gas sensing effect as gas sensing film.
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
1. first passage high-power purple of the present invention handles graphene oxide outside and one-step method obtains porous reduction-oxidation graphite
Alkene not only restores surface of graphene oxide oxygen-containing group, but also equally distributed hole is prepared in graphene film, and collection is carved
Erosion reduction one, graphene oxide can not restore in the presence of especially solving the problems, such as oxidant, and without other chemistry
Reagent, such as the use of go back original reagent, pore reagent are a kind of simple and quick, environmentally protective industrial methods.
2. then being handled outside high-power purple the method comprises the steps of firstly, preparing the graphene oxide dispersion of stably dispersing, at dialysis
Reason obtains negatively charged porous graphene dispersion liquid, adds p-phenylenediamine and prepares positively charged porous graphene dispersion liquid；Then more
Secondary deposition is self-assembly of three-dimensional porous graphene film, finally prepares electrode and obtains gas sensor, the electric conductivity of graphene,
Excellent in stability, it is especially good with semiconductor material Ohmic contact, to have to gas molecule especially DMMP molecule excellent
Sensing capabilities.
3. high power ultraviolet irradiation processing disclosed by the invention has significantly simplified the preparation step of porous graphene piece, have
Conducive to the low-coat scaleization preparation for realizing high performance device；The graphene of preparation with huge specific surface area in addition to also having
Excellent electric conductivity, so as to which gas sensor of good performance is prepared.
4. the present invention prepares multi-layer three-dimension porous graphene ultrathin film using self assembly means, take full advantage of single
Interaction force between graphene film assembling unit, to realize the accurate control of ultra-thin membrane structure, such as the graphene film number of plies etc.
System, so that the accuracy controlling of ultra-thin film character is realized, conducive to the extensive controllable preparation for optimizing device.
5. the ultraviolet reduction etching processing under combined oxidant of the present invention, is prepared certain thickness, porous sensing
Film, the contact area for solving graphene film caused by prior art lamella sintering action and gas molecule are greatly reduced, thus
The problem of influencing the air-sensitive performance of sensor.
6. the vertical response type gas sensor disclosed by the invention based on three-dimensional porous graphene extra-thin film uses for the first time
The interlayer structure of sensing membrane is set between two electrodes, overcomes the technology prejudice that the prior art has to coplanar setting electrode；
It is very good that obtained sensor is contacted with gas molecule, has excellent detectability.
Detailed description of the invention
Fig. 1 is that the present invention is based on the structural representations of the vertical response type gas sensor of three-dimensional porous graphene extra-thin film
Figure；
Wherein, 1, first electrode, 2, second electrode, 3, three-dimensional porous graphene extra-thin film；
Fig. 2 is the vertical response type gas sensor pair based on three-dimensional porous graphene extra-thin film that embodiment one obtains
The electrical response curve graph of the DMMP molecule of 50ppm；
Fig. 3 is the vertical response type gas sensor pair based on three-dimensional porous graphene extra-thin film that embodiment three obtains
The electrical response curve graph of the DMMP molecule of 50ppm；
Fig. 4 is the vertical response type gas sensor pair based on three-dimensional porous graphene extra-thin film that embodiment eight obtains
The electrical response curve graph of the DMMP molecule of 50ppm.
Specific embodiment
Attached drawing 1 is that the present invention is based on the structural representations of the vertical response type gas sensor of three-dimensional porous graphene extra-thin film
Figure comprising first electrode 1, second electrode 2 and the three-dimensional porous graphene between first electrode and second electrode surpass
Film 3.The preparation method of vertical response type gas sensor based on three-dimensional porous graphene extra-thin film is disclosed in detail below.
Embodiment one
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 1 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 5 wt% hydrogen peroxide solution, 90 mL, adds ferrous sulfate solution 1 mL, 100 Hz that concentration is 20 mM
30 min of ultrasonic disperse forms graphene oxide dispersion, and hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W ultraviolet lamps after 40 s of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. take in negatively charged 100 mL of porous graphene dispersion liquid addition 1000 mg of p-phenylenediamine, water bath condition next time
After 18 h of stream reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, repeatedly, in gold electrode table
Face deposits 50 layers of three-dimensional porous graphene extra-thin film, with a thickness of 70 nanometers；Then using micro-processing technology three-dimensional porous
Graphene extra-thin film surface prepares gold electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device, resistance are 3.5 M Ω.
Fig. 2 is response curve of the sensor to the DMMP molecule of 50 ppm, and sensor goes out extremely DMMP molecule displays
Sensitive response performance.
Embodiment two
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 2 mg/mL graphene oxide water solution ultrasonic disperses that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 70 mL of 4wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 80Hz ultrasound that concentration is 15 mM
Disperse 40 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2500 W ultraviolet lamps after 30 s of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. take in negatively charged 100 mL of porous graphene dispersion liquid addition 1000 mg of p-phenylenediamine, water bath condition next time
After 15 h of stream reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 30 layers of deposition, with a thickness of 50 nanometers；Then using micro-processing technology in three-dimensional porous stone
The black ultra-thin film surface of alkene prepares gold electrode, obtains the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film,
Resistance is 7.7 M Ω.
Embodiment three
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 1 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 80 mL of 8wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 50Hz ultrasound that concentration is 15 mM
Disperse 30 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 3000 W ultraviolet lamps after 70 s of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. take in negatively charged 100 mL of porous graphene dispersion liquid addition 1000 mg of p-phenylenediamine, water bath condition next time
After 18 h of stream reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 90 layers of deposition, with a thickness of 150 nanometers；Then using micro-processing technology in three-dimensional porous stone
The black ultra-thin film surface of alkene prepares gold electrode, obtains the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film,
Resistance is 16.2 M Ω.
Fig. 3 is response curve of the sensor to the DMMP molecule of 50 ppm, and sensor goes out extremely DMMP molecule displays
Sensitive response performance.
Example IV
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 2 hours in the 1 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 80 mL of 5wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 80Hz ultrasound that concentration is 20 mM
Disperse 30 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W ultraviolet lamps after 30 s of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 0.5 mg/mL；
3. take in negatively charged 100 mL of porous graphene dispersion liquid addition 1000 mg of p-phenylenediamine, water bath condition next time
After 18 h of stream reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1.5mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 10 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 10 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 150 layers of deposition, with a thickness of 250 nanometers；Then using micro-processing technology three-dimensional porous
Graphene extra-thin film surface prepares gold electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device, resistance are 20.1 M Ω.
Embodiment five
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 1 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 90 mL of 7wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 80Hz ultrasound that concentration is 40 mM
Disperse 30 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W ultraviolet lamps after 50 s of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. take in negatively charged 100 mL of porous graphene dispersion liquid addition 1000 mg of p-phenylenediamine, water bath condition next time
After 18 h of stream reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1.5mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 180 layers of deposition, with a thickness of 280 nanometers；Then using micro-processing technology three-dimensional porous
Graphene extra-thin film surface prepares gold electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device, resistance are 23.4 M Ω.
Embodiment six
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 1 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 80 mL of 6wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 80Hz ultrasound that concentration is 20 mM
Disperse 30 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 3；
2. above-mentioned graphene oxide dispersion is placed under 2500 W ultraviolet lamps after 70 s of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. taking addition 720 mg of p-phenylenediamine in negatively charged 100 mL of porous graphene dispersion liquid, flow back under water bath condition
After reacting 18 h, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 30 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 140 layers of deposition, with a thickness of 230 nanometers；Then using micro-processing technology three-dimensional porous
Graphene extra-thin film surface prepares gold electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device, resistance are 15.9 M Ω.
Embodiment seven
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 0.5 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 80 mL of 5wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 80Hz ultrasound that concentration is 20 mM
Disperse 60 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 1500 W ultraviolet lamps after 30 s of reactive ion etching, it is placed in bag filter
In (molecular cut off 10000) after dialysis 15 days, negatively charged porous graphene dispersion liquid is obtained, is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. addition 1100 mg of p-phenylenediamine in negatively charged 100 mL of porous graphene dispersion liquid is taken, 80 under water bath condition
After spending 18 h of back flow reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 25 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 10min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 25 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 150 layers of deposition, with a thickness of 240 nanometers；Then using micro-processing technology three-dimensional porous
Graphene extra-thin film surface prepares gold electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device, resistance are 18.5 M Ω.
Embodiment eight
A kind of preparation method of porous graphene gas sensor, comprising the following steps:
(1) after the 1 mg/mL graphene oxide water solution ultrasonic disperse that 20 mL Hummers methods obtain is handled 3 hours
Hydrochloric acid is added, the pH value of graphene oxide water solution is made to reach 4；Then it is 3 wt% hydrogen peroxide solution, 10 mL that concentration, which is added, then
Ferrous sulfate solution 0.1 mL, 80 Hz 10 min of ultrasound that concentration is 15 mM are added, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W ultraviolet lamps after 30 s of reactive ion etching, is placed in bag filter
Middle deionized water dialysis is after 7 days, obtained porous graphene dispersion liquid；
(3) photoetching and lift-off technology in micro-processing technology is used to prepare gold electrode；By porous graphene dispersion liquid (2
Mg/L) according to 0.1 mL/cm2It is spun to electrode surface, it is super to obtain 500 nanometers of three-dimensional porous graphenes by 80 DEG C of vacuum drying 1h
Then film prepares gold electrode on three-dimensional porous graphene extra-thin film surface, so that porous graphene gas sensor is obtained, electricity
Resistance response is 4.0 M Ω.
Fig. 4 is the sensor to the electrical response curve graph of the DMMP molecule of 50 ppm, and sensor is to DMMP molecule table
Reveal extremely sensitive response performance.
Embodiment nine
A kind of preparation method of porous graphene gas sensor, comprising the following steps:
(1) it is handled 3 hours in the 0.5 mg/mL graphene oxide water solution ultrasonic disperse that 20 mL Hummers methods obtain
After hydrochloric acid is added, so that the pH value of graphene oxide water solution is reached 4；Then it is 10 wt% hydrogen peroxide solution, 10 mL that concentration, which is added,
Ferrous sulfate solution 0.1 mL, 80 Hz 10 min of ultrasound that concentration is 30mM are added, graphene oxide dispersion is formed；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W ultraviolet lamps after 70 s of reactive ion etching, is placed in bag filter
Middle deionized water dialysis is after 7 days, obtained porous graphene dispersion liquid；
(3) it uses photoetching and lift-off technology in micro-processing technology to prepare gold electrode, takes porous graphene dispersion liquid (2
Mg/L) according to 1 mL/cm2It is spun to electrode surface, it is ultra-thin to obtain 900 nanometers of three-dimensional porous graphenes by 80 DEG C of vacuum drying 1h
Then film prepares gold electrode on three-dimensional porous graphene extra-thin film surface, to obtain porous graphene gas sensor, resistance
Value is 9.5 M Ω.
Embodiment ten
A kind of preparation method of porous graphene gas sensor, comprising the following steps:
(1) salt is added after the 1mg/mL graphene oxide water solution decentralized processing that 20 mL Hummers methods obtain 3 hours
Acid makes the pH value of graphene oxide water solution reach 4；Then it is 5 wt% hydrogen peroxide solution, 10 mL that concentration, which is added, is added dense
Degree is ferrous sulfate solution 0.1 mL, 80 Hz 10 min of ultrasound of 20 mM, forms graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 2500 W ultraviolet lamps after 30 s of reactive ion etching, is placed in bag filter
Middle deionized water dialysis is after 7 days, obtained porous graphene dispersion liquid；
(3) it uses photoetching and lift-off technology in micro-processing technology to prepare gold electrode, takes porous graphene dispersion liquid (2
Mg/L) according to 0.5 mL/cm2It is spun to electrode surface, it is super to obtain 750 nanometers of three-dimensional porous graphenes by 80 DEG C of vacuum drying 1h
Then film prepares gold electrode on three-dimensional porous graphene extra-thin film surface, so that porous graphene gas sensor is obtained, electricity
Resistance value is 12.1 M Ω.
Embodiment 11
A kind of preparation method of porous graphene gas sensor, comprising the following steps:
(1) it is added after the 1 mg/mL graphene oxide water solution decentralized processing that 20 mL Hummers methods obtain 1 hour
Hydrochloric acid makes the pH value of graphene oxide water solution reach 4；Then it is 7 wt% hydrogen peroxide solution, 10 mL that concentration, which is added, is added
Concentration is ferrous sulfate solution 0.1 mL, 80Hz 10 min of ultrasound of 10 mM, forms graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 2000 W ultraviolet lamps after 30 s of reactive ion etching, is placed in bag filter
Middle deionized water dialysis is after 7 days, obtained porous graphene dispersion liquid；
(3) it uses photoetching and lift-off technology in micro-processing technology to prepare gold electrode, takes porous graphene dispersion liquid (2
Mg/L) according to 0.6 mL/cm2It is spun to electrode surface, it is super to obtain 800 nanometers of three-dimensional porous graphenes by 80 DEG C of vacuum drying 1h
Then film prepares gold electrode on three-dimensional porous graphene extra-thin film surface, so that porous graphene gas sensor is obtained, electricity
Resistance value is 8.2 M Ω.
Embodiment 12
A kind of preparation method of porous graphene gas sensor, comprising the following steps:
(1) it is added after the 1 mg/mL graphene oxide water solution decentralized processing that 20 mL Hummers methods obtain 3 hours
Hydrochloric acid makes the pH value of graphene oxide water solution reach 4；Then it is 3 wt% hydrogen peroxide solution, 10 mL that concentration, which is added, is added
Concentration is ferrous sulfate solution 0.1 mL, 80Hz 10 min of ultrasound of 10 mM, forms graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 3000 W ultraviolet lamps after 30 s of reactive ion etching, is placed in bag filter
Middle deionized water dialysis is after 7 days, obtained porous graphene dispersion liquid；
(3) it uses photoetching and lift-off technology in micro-processing technology to prepare gold electrode, takes porous graphene dispersion liquid (5
Mg/L) according to 0.5 mL/cm2It is spun to electrode surface, it is super to obtain 850 nanometers of three-dimensional porous graphenes by 80 DEG C of vacuum drying 1h
Then film prepares gold electrode on three-dimensional porous graphene extra-thin film surface, so that porous graphene gas sensor is obtained, electricity
Resistance value is 2.4 M Ω.
Comparative example one
A kind of preparation method of porous graphene gas sensor, comprising the following steps:
(1) it is added after the 1 mg/mL graphene oxide water solution decentralized processing that 20 mL Hummers methods obtain 3 hours
Hydrochloric acid makes the pH value of graphene oxide water solution reach 4；Then it is 3 wt% hydrogen peroxide solution, 10 mL that concentration, which is added, is added
Concentration is ferrous sulfate solution 0.1 mL, 80 Hz 10 min of ultrasound of 10 mM, forms graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 500 W ultraviolet lamps after 400 s of reactive ion etching, is placed in bag filter
Middle deionized water dialysis is after 7 days, obtained porous graphene dispersion liquid；
(3) it uses photoetching and lift-off technology in micro-processing technology to prepare gold electrode, takes porous graphene dispersion liquid (2
Mg/L) according to 0.5 mL/cm2It is spun to electrode surface, it is super to obtain 730 nanometers of three-dimensional porous graphenes by 80 DEG C of vacuum drying 1h
Then film prepares gold electrode on three-dimensional porous graphene extra-thin film surface, so that porous graphene gas sensor is obtained, electricity
Resistance is without response.
Comparative example two
A kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including it is following
Step:
1. being handled 5 hours in the 1 mg/mL graphene oxide water solution ultrasonic disperse that 200 mL Hummers methods obtain
Afterwards；Addition concentration is 10 mL of 5wt% hydrogen peroxide solution, adds ferrous sulfate solution 1 mL, the 80Hz ultrasound that concentration is 20 mM
Disperse 30 min and form graphene oxide dispersion, hydrochloric acid is then added, pH value is made to reach 4；
2. above-mentioned graphene oxide dispersion is placed under 500 W ultraviolet lamps after 5 min of reactive ion etching, it is placed in bag filter
Dialysis after a week, obtains negatively charged porous graphene dispersion liquid in (molecular cut off 10000), is incited somebody to action by Rotary Evaporators
To negatively charged porous graphene dispersion liquid be condensed into 1mg/mL；
3. addition 1000 mg of p-phenylenediamine in negatively charged 100 mL of porous graphene dispersion liquid is taken, 80 under water bath condition
After spending 18 h of back flow reaction, cleaning is filtered, obtains the positively charged porous graphene dispersion liquid of 1mg/mL after being dissolved in ethyl alcohol；
4. preparing gold electrode on low resistance silicon chip substrate, it is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
It takes out deionized water to rinse, after being dried with nitrogen, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, take out ethyl alcohol
It rinses, after being dried with nitrogen, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 100 layers of deposition, with a thickness of 160 nanometers；Then using micro-processing technology three-dimensional porous
Graphene extra-thin film surface prepares gold electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device, resistance are 972.6 M Ω.
It can be seen that porous redox graphene even pore distribution prepared by the present invention, there is good reproducibility
Can, it being handled especially with outside high-power purple, step etching reduction has good electric conductivity while with porous structure,
One layer of uniform graphene is pressed from both sides among electrode, overlap joint electrode forms galvanic circle；It is easy to operate, other reagents are not necessarily to, it can scale
Production；The porous redox graphene of preparation has excellent signal conversion performance after being prepared into gas sensor, to gas
Molecule has excellent sensing capabilities, can be used for gas detection；Achieve unexpected technical effect.
Claims (8)
1. a kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including following step
It is rapid:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, being adjusted with acid pH is 1~4；Then ultrasonic
Processing forms graphene oxide dispersion；Dialysis treatment will be carried out after the ultraviolet processing of graphene oxide dispersion, obtained negatively charged
Porous graphene disperses solution；The power of the ultraviolet processing is the W of 1500 W~4000, and the time is the min of 30 s~30；
(2) p-phenylenediamine is added in negatively charged porous graphene dispersion solution, back flow reaction obtains positively charged porous graphite
Alkene dispersion liquid；
(3) first electrode is successively immersed to electronegative porous graphene dispersion liquid, in positively charged porous graphene dispersion liquid,
It repeats 15~200 times, is dried to obtain the first electrode with three-dimensional porous graphene extra-thin film；
(4) in the three-dimensional porous graphene extra-thin film surface of the first electrode with three-dimensional porous graphene extra-thin film preparation second
Electrode obtains the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film；
In step (1), liquid oxidizer is added in graphene oxide water solution in the form of aqueous oxidizing agent solution, and sulfate is with sulfuric acid
Saline solution form is added in graphene oxide water solution；The concentration of the graphene oxide water solution is 0.2~5 mg/mL,
The concentration of sulfate solution is 10~50 mM, and the concentration of aqueous oxidizing agent solution is 4~10 wt%；Graphene oxide water solution,
Aqueous oxidizing agent solution, sulfate solution volume ratio be (150~250): (50~120): 1；The power of the ultrasonic treatment
For 50~100 kHz, the time is the h of 10 min~1；The power of the ultraviolet processing is the W of 1500 W~3000, and the time is 30 s
~70s；The dialysis treatment time is 3 days~15 days；Dialysis carries out in deionized water.
2. a kind of preparation method of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including following step
It is rapid:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, being adjusted with acid pH is 1~4；Then ultrasonic
Processing forms graphene oxide dispersion；Dialysis treatment will be carried out after the ultraviolet processing of graphene oxide dispersion, obtains porous go back
Former graphene oxide disperses solution；The power of the ultraviolet processing is the W of 1500 W~4000, and the time is the min of 30 s~30；
(2) porous redox graphene dispersion solution is spun to first electrode surface, be dried, obtained with three-dimensional more
The first electrode of hole graphene extra-thin film；Then in the three-dimensional porous stone of the first electrode with three-dimensional porous graphene extra-thin film
The black ultra-thin film surface of alkene prepares second electrode, obtains the vertical response type gas sensing based on three-dimensional porous graphene extra-thin film
Device；
In step (1), liquid oxidizer is added in graphene oxide water solution in the form of aqueous oxidizing agent solution, and sulfate is with sulfuric acid
Saline solution form is added in graphene oxide water solution；The concentration of the graphene oxide water solution is 0.2~5 mg/mL,
The concentration of sulfate solution is 10~50 mM, and the concentration of aqueous oxidizing agent solution is 4~10 wt%；Graphene oxide water solution,
Aqueous oxidizing agent solution, sulfate solution volume ratio be (150~250): (50~120): 1；The power of the ultrasonic treatment
For 50~100 kHz, the time is the h of 10 min~1；The power of the ultraviolet processing is the W of 1500 W~3000, and the time is 30 s
~70s；The dialysis treatment time is 3 days~15 days；Dialysis carries out in deionized water.
3. according to claim 1 or 2 vertical response type gas sensors based on three-dimensional porous graphene extra-thin film
Preparation method, it is characterized in that: in step (1), with salt acid for adjusting pH；Liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；
Adjusting pH is 4；Graphene oxide water solution, aqueous oxidizing agent solution, sulfate solution volume ratio be (190~210): (70
~90): 1.
4. the preparation side of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film according to claim 1
Method, it is characterized in that: the mass ratio of the p-phenylenediamine and electronegative porous graphene is 1: (5~20) in step (2)；It returns
The stream reaction time is 12~24 h；After back flow reaction, cleaning is filtered, addition alcohol obtains positively charged porous graphene dispersion
Liquid.
5. the preparation side of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film according to claim 1
Method, it is characterized in that: being modified with amino silicane coupling agent silicon wafer in step (3)；It is all rushed after immersing dispersion liquid every time
It washes, be dried；The concentration of the negatively charged porous graphene dispersion liquid is 0.1~2 mg/mL, the positively charged porous graphite
The concentration of alkene dispersion liquid is 0.1~2 mg/mL；The time for immersing negatively charged porous graphene dispersion liquid every time is 5~30 min；
The time for immersing positively charged porous graphene dispersion liquid every time is 5~30 min.
6. the preparation side of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film according to claim 2
Method, it is characterized in that: rotating porous redox graphene dispersion liquid in step (2), forming concentration is that 1~5 mg/mL is porous
Redox graphene dispersion liquid；The porous redox graphene dispersion solution is according to 0.1~1 mL/cm2It is spun to
One electrode surface；Described be dried is 75~85 DEG C of vacuum drying treatments.
7. according to claim 1 or 2 vertical response type gas sensors based on three-dimensional porous graphene extra-thin film
The vertical response type gas sensor of the three-dimensional porous graphene extra-thin film of preparation method preparation.
8. according to the vertical response type gas sensor for requiring the 1 or 2 three-dimensional porous graphene extra-thin films, it is characterized in that:
The three-dimensional porous graphene extra-thin film with a thickness of 20~900 nanometers.
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