CN106556677A - A kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof - Google Patents
A kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0054—Specially adapted to detect a particular component for ammonia
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0047—Specially adapted to detect a particular component for organic compounds
Abstract
The invention discloses a kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof, prepared by the preparation of the negatively charged porous graphene dispersion liquids of Jing, the preparation of positively charged porous graphene dispersion liquid, the assembling of three-dimensional porous graphene extra-thin film, four steps of preparation of three-dimensional porous graphene extra-thin film gas sensor realize the preparation of sensor.Porous graphene ultrathin membrane gas sensor obtained by the present invention has high sensitivity to DMMP gas molecules.This preparation method process is simple, is suitable for a large amount of preparations of sensor.
Description
Technical field
The invention belongs to sensor technical field, is related to a kind of nano-sensor and preparation method thereof, and in particular to a kind of
Three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof.
Background technology
Gas sensor plays more and more important effect in fields such as environmental monitoring, food safety, health cares.With
The development of nanotechnology, using metal-oxide semiconductor (MOS) nano-particle, carbon nanomaterial and two-dimensional nano-film etc. all
Jing is used as sensitive material and constitutes gas sensor, with 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
Have the irreplaceable advantage of many conventional sensors materials, therefore, its as sensing material biology, chemistry, machinery, aviation,
The aspects such as military affairs have extensive development prospect.
Various methods（Such as stripping method, chemical vapor infiltration, epitaxial growth method, chemistry or thermal reduction graphite oxide method
Deng）The Graphene of preparation shows good response performance to gas molecule.Wherein, electronation graphene oxide is relative
Graphene prepared by additive method has the advantages that simple preparation method, low cost, modifiability are strong, therefore becomes making gas
The very efficient method of sensing material.In view of repeatable poor, the single rupture of sensor that single graphene film is constituted
And the stability that causes it is not high the shortcomings of, constructing graphene film network becomes that to prepare high-efficient graphite alkene sensor very effective
One of method.However, during Graphene network is constructed, due to lamella sintering action, easily causing graphene film and gas
The contact area of body molecule is greatly reduced, so as to affect the air-sensitive performance of sensor.
The content of the invention
The present invention is directed to deficiencies of the prior art, there is provided a kind of three-dimensional porous graphene extra-thin film gas sensing
Device and preparation method thereof, is prepared with plus-minus electric porous reduction-oxidation graphite using high power ultraviolet irradiation and organic molecule modification
Alkene, and three-dimensional porous graphene extra-thin film is obtained using electrostatic self-assembled technology, with the gas sensor pair of this ultra-thin film production
Ammonia shows extremely sensitive response performance.
The present invention is achieved by the following technical solutions：
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
（1）Liquid oxidizer and sulfate are added in graphene oxide water solution, is 1～4 with acid for adjusting pH；Then it is ultrasonic
Process forms graphene oxide dispersion；Dialysis treatment will be carried out after graphene oxide dispersion ultraviolet process, obtain negatively charged
Porous graphene dispersion soln；The power of the ultraviolet process is 1500 W～4000 W, and the time is 30 s～30 min；
（2）P-phenylenediamine is added in negatively charged porous graphene dispersion soln, back flow reaction obtains the porous graphite of positively charged
Alkene dispersion liquid；
（3）Silicon chip after will be amido modified immerses electronegative porous graphene dispersion liquid, the porous graphite of positively charged successively
In alkene dispersion liquid, repeat 1～60 time, be dried to obtain three-dimensional porous graphene extra-thin film；
（4）Electrode is prepared on three-dimensional porous graphene extra-thin film surface, three-dimensional porous graphene extra-thin film gas sensor is obtained.
In above-mentioned technical proposal, step（1）The graphene oxide can by Hummers methods, Brodie methods or
Staudenmaier methods are prepared from；It is preferred that first by graphene oxide water solution point before liquid oxidizer and sulfate is added
Dissipate and process 1～5 hour, avoid gathering beneficial to graphene oxide dispersion, and it is good with liquid oxidizer and sulfate formation
Reaction interface.
In above-mentioned technical proposal, step（1）In, liquid oxidizer adds graphene oxide water with aqueous oxidizing agent solution form
In solution, sulfate is added in graphene oxide water solution with sulfate solution form；The graphene oxide water solution
Concentration is 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
Liquid, the volume ratio of sulfate solution are（150～250）∶（50～120）: 1, preferably（190～210）∶（70～90）: 1,
In the proportion, nano-pore being uniformly distributed in graphene film can be realized, cross vast scale etching and will obtain non-porous broken little
Nano-graphene piece, what too small concentration was obtained are the graphene film with oxy radical.
In above-mentioned technical proposal, step（1）In, liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；Acid is salt
Acid.For a step, mixed solution realizes that the etching of graphene oxide sheet and reduction provide media environment.
In above-mentioned technical proposal, step（1）In, the power of supersound process is 50～100 kHz, and the time is 10 min～1
h.Graphite oxide is placed in mixed solution, can be attracted each other between particle, causes dispersion stability poor, and ultrasonic disperse can drop
Low interparticle concentration effect, provides good basis to form uniform Graphene.
In above-mentioned technical proposal, step（1）The preparation of negatively charged porous graphene dispersion soln is porous graphite of the present invention
The important step of alkene gas sensor；The preparation of negatively charged porous graphene dispersion soln is referred to puts graphene oxide dispersion
Etching reaction is reduced in high power ultraviolet lamp next step, reaction is placed in bag filter after terminating, and is dialysed in deionized water and is obtained
To porous redox graphene dispersion liquid；The power of uviol lamp is limited as 1500 W～4000 W, preferably 1500 W～3000
W, ultraviolet process time is 30 s～30 min, preferably 30 s～70s, can not only redox graphene, and carved
Erosion Graphene, creative place exactly of the invention.The present invention adopts ultraviolet process graphene oxide dispersion, ultraviolet place first
Manage and not only obtain porous graphene, and realize the reduction of graphene oxide, the color of graphene solution is by the transparent change of light gray
Into atrouss, and nanometer sheet becomes conductive by insulation, with the intensification of reducing degree, resistance is gradually lowered, it is to avoid it is existing also
Original place reason must be beneficial to the defect of chemical reagent, provide new approach for green chemistry；Particularly, the porous graphite for obtaining
Alkene has nanoscale hole, can greatly improve the specific surface area of Graphene network, solves existing Graphene network due to stone
The defect of compact structure caused by black alkene easily piling up property, and it is simple to etch pore process, can large-scale production, it is to avoid existing many
Hole Graphene needs high temperature（The temperature of carbon thermal reduction）, low yield, porosity are low and uncontrollable, pore size distribution lack of homogeneity ask
Topic；Especially present invention achieves the graphene oxide under the conditions of oxidant is reduced, prior art thinks that the presence of oxidant is
Cannot redox graphene, but the present invention increases UV power, limits ultraviolet process time, while compatibility proper ratio
Oxidant and sulfate, and limit dispersion liquid acid number, realize the reduction of graphene oxide, not only obtained specific surface area excellent
Different Graphene, and the redox graphene of excellent electrical property has been obtained, it is that bigger serface Graphene is passed for air-sensitive
Sensor plays a crucial role, and achieves unexpected technique effect.
The present invention adopts the ultraviolet means of high power, one step of energy to realize etching and the reduction of graphene oxide sheet, and this is existing
Technology institute under oxidant hydrogen peroxide environment is inaccessiable.Under prior art, due to double containing oxidant in graphene solution
Only there is the etching of graphene oxide in oxygen water, solution, it is impossible to which the drastic reduction of graphene oxide sheet occurs, the porous oxidation for obtaining
Graphene film is insulation, it is impossible to realize its electric conductivity.Therefore, high power ultraviolet irradiation of the present invention is processed and significantly simplifies porous
The preparation process of graphene film, and speed is fast, is conducive to the low-coat scaleization of senser element to prepare.
In above-mentioned technical proposal, step（1）In, the dialysis treatment time is 3 days～15 days, and molecular cut off is generally
10000 or so, the acting as of dialysis removes the impurity such as metal ion, hydrion and hydrogen peroxide for remaining in solution.
In above-mentioned technical proposal, step（2）In, 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 terminates, in sucking filtration cleaning, addition alcohol, many of positively charged are obtained
Hole graphene dispersing solution.
In above-mentioned technical proposal, step（3）In, by silicon chip substrate Jing after amido modified dose of modification, it is placed in negatively charged porous
Deposition a period of time in graphene dispersing solution, after being dried cleaning treatment, then it is placed in deposition in positively charged porous graphene dispersion liquid
For a period of time, after being dried cleaning treatment, then it is placed in deposition a period of time in negatively charged porous graphene dispersion liquid, deposits repeatedly
To 1～60 layer of three-dimensional porous Graphene ultrathin film.Described amido modified dose is triethoxy amino silicone, trimethoxy
The amino silicane coupling agents such as amino silicone；The present invention solves the problems, such as that existing silicon chip is poor with Graphene cementability, increases
Ohm contact performance.
In above-mentioned technical proposal, step（3）In, 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 of the porous graphene dispersion liquid of immersion positively charged is 5～30 min every time.
The present invention prepares multi-layer three-dimension porous graphene ultrathin film using self assembly means, takes full advantage of single graphite
Interaction force between alkene piece module unitss, realizes ultra-thin membrane structure, the such as precise control of graphene film number of plies etc., from
And the accuracy controlling of ultra-thin film character is realized, beneficial to the extensive controllable standby of optimization device.
In above-mentioned technical proposal, step（4）In, using micro- photoetching added in technology and lift-off technology in three-dimensional porous stone
Black alkene ultrathin membrane surface prepares electrode, obtains three-dimensional porous graphene extra-thin film gas sensor；The spacing of the electrode is 50
～500 μm, the spacing of adjacent electrode is 3～30 μm.
Invention additionally discloses three-dimensional porous graphene extra-thin film gas sensor prepared by above-mentioned preparation method, of the invention
The three-dimensional porous graphene extra-thin film gas sensor for arriving is to DMMP molecules (dimethyl methyl phosphonate) with excellent sensitivities
Energy.
The present invention further discloses a kind of preparation method of three-dimensional porous graphene extra-thin film, comprises the following steps：
（1）Liquid oxidizer and sulfate are added in graphene oxide water solution, is 1～4 with acid for adjusting pH；Then it is ultrasonic
Process forms graphene oxide dispersion；Dialysis treatment will be carried out after graphene oxide dispersion ultraviolet process, obtain negatively charged
Porous graphene dispersion soln；The power of the ultraviolet process is 1500 W～4000 W, and the time is 30 s～30 min；
（2）P-phenylenediamine is added in negatively charged porous graphene dispersion soln, back flow reaction obtains the porous graphite of positively charged
Alkene dispersion liquid；
（3）Silicon chip after will be amido modified immerses electronegative porous graphene dispersion liquid, the porous graphite of positively charged successively
In alkene dispersion liquid, repeat 1～60 time, be dried to obtain three-dimensional porous graphene extra-thin film.
Due to the utilization of above-mentioned technical proposal, the present invention compared with prior art, has the advantage that：
1. outside first passage high-power purple of the present invention process graphene oxide and one-step method obtains porous redox graphene,
Not only surface of graphene oxide oxy radical is reduced, and equally distributed hole is prepared in graphene film, collection etching
Reduction one, in the presence of especially solving the problems, such as oxidant, graphene oxide cannot be reduced, and without the need for other chemistry examinations
Agent, such as go back original reagent, the use of pore reagent, are a kind of industrial methods of simple and quick, environmental protection.
2., the method comprises the steps of firstly, preparing the graphene oxide dispersion of stably dispersing, then process outside high-power purple, at dialysis
Reason obtains negatively charged porous graphene dispersion liquid, adds p-phenylenediamine and prepares positively charged porous graphene dispersion liquid；Then it is many
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 semi-conducting material Ohmic contact, so as to there are excellent sensing capabilities to ammonia molecule.
3. high power ultraviolet irradiation disclosed by the invention processes the preparation process for significantly simplifying porous graphene piece, has
Prepare beneficial to the low-coat scaleization for realizing high performance device；The graphene film of preparation is nanoscale, except with huge
Specific surface area also has excellent electric conductivity, such that it is able to prepare gas sensor of good performance.
Description of the drawings
Fig. 1 is the three-dimensional porous graphene extra-thin film gas sensor scanning electron microscope (SEM) photograph that embodiment one is obtained；
Fig. 2 is resistance of the three-dimensional porous graphene extra-thin film gas sensor that obtains of embodiment one to the DMMP molecules of 50ppm
Response curve.
Fig. 3 is DMMP molecule of the three-dimensional porous graphene extra-thin film gas sensor that obtains of embodiment three to 50ppm
Electrical response curve chart；
Fig. 4 is resistance of the three-dimensional porous graphene extra-thin film gas sensor that obtains of embodiment nine to the DMMP molecules of 50ppm
Response curve.
Specific embodiment
Embodiment one
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 5 wt% hydrogen peroxide solutions, 80 mL to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80 Hz ultrasounds point
Dissipate 30 min and form graphene oxide dispersion, be subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15
Min, takes out deionized water rinsing, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and deposits 15 min, takes out
Alcohol flushing, after nitrogen is dried up, then is placed in negatively charged porous graphene dispersion liquid and deposits 15 min, so repeatedly, in silicon chip
Surface deposits 20 layers of three-dimensional porous graphene extra-thin film；
5. electrode is prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology, electricity
The spacing of pole is 200 μm, and the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, resistance
For 8.9 M Ω.
Electrode stereoscan photograph figures of the Fig. 1 for the sensor, it can be seen that redox graphene shape between electrode
Into one layer of nanoscale ultrathin membrane, the network structure of composition is overlapped between interdigital electrode and forms galvanic circle.
Fig. 2 is response curve of the sensor to the DMMP molecules of 50 ppm, and sensor goes out extremely to DMMP molecule displays
Sensitive response performance.
Embodiment two
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 2 mg/mL graphene oxide water solutions ultrasonic disperses that 200 mL Hummers methods are obtained are processed 5 hours；Plus
It is 80 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 20 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
11.2 MΩ。
Embodiment three
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 80 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 3000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 20 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
16.1 MΩ。
Fig. 3 is response curve of the sensor to the DMMP molecules of 50 ppm, and sensor goes out extremely to DMMP molecule displays
Sensitive response performance.
Example IV
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 2 hours；Plus
It is 80 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 0.5 mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 20 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
18.2 MΩ。
Embodiment five
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 80 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1.5mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 20 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
3.9 MΩ。
Embodiment six
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 80 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 10 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
28.3 MΩ。
Embodiment seven
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 90 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1.5mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 30 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 400 μm, the spacing of adjacent electrode is 25 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
19.3 MΩ。
Embodiment eight
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 80 mL of 6wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 3；
2. above-mentioned graphene oxide dispersion is placed under 2500 W uviol lamps after 70 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 700 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, 80 degree of backflows under water bath condition
After reacting 18 h, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 40 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
17.1 MΩ。
Embodiment nine
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 0.5 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；
Addition concentration is 80 mL of 5wt% hydrogen peroxide solutions, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasounds point
Dissipate 30 min and form graphene oxide dispersion, be subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis 3 days, negatively charged porous graphene dispersion liquid is obtained, by Rotary Evaporators by the band for obtaining
Negative electricity porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 50 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
12.7 MΩ。
Fig. 4 is response curve of the sensor to the DMMP molecules of 50 ppm, and sensor goes out extremely to DMMP molecule displays
Sensitive response performance.
Embodiment ten
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 2 mg/mL graphene oxide water solutions ultrasonic disperses that 200 mL Hummers methods are obtained are processed 5 hours；Plus
It is 80 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after 30 s of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis 15 days, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1800 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 100 degree are returned
After stream 24 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 25 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 20 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 100 μm, the spacing of adjacent electrode is 15 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
6.5 MΩ。
Comparative example one
A kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
1. after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 200 mL Hummers methods are obtained is processed 5 hours；Plus
It is 10 mL of 5wt% hydrogen peroxide solutions to enter concentration, adds 1 mL of copperas solution that concentration is 20 mM, 80Hz ultrasonic disperses
30 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 500 W uviol lamps after 10 min of reactive ion etching, is placed in bag filter（Retention
Molecular weight is 10000）After middle dialysis one week, negatively charged porous graphene dispersion liquid is obtained, will be obtained by Rotary Evaporators
Negatively charged porous graphene dispersion liquid is condensed into 1mg/mL；
3. 1000 mg of p-phenylenediamine is added in taking negatively charged 100 mL of porous graphene dispersion liquid, and under water bath condition, 80 degree are returned
After stream 18 h of reaction, sucking filtration cleaning obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds after being dissolved in ethanol；
4. low resistance silicon chip substrate Jing after the modification of APS dressing agents is placed in negatively charged porous graphene dispersion liquid and deposits 15 min,
Deionized water rinsing is taken out, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and is deposited 15 min, take out ethanol
Rinse, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in silicon chip surface
The three-dimensional porous graphene extra-thin film of 30 layers of deposition；
5. electrode, electrode are prepared on three-dimensional porous graphene extra-thin film surface using micro- photoetching added in technology and lift-off technology
Spacing be 200 μm, the spacing of adjacent electrode is 5 μm, obtains three-dimensional porous graphene extra-thin film gas sensor, and resistance is
789.2MΩ。
Claims (10)
1. a kind of preparation method of three-dimensional porous graphene extra-thin film gas sensor, comprises the following steps：
（1）Liquid oxidizer and sulfate are added in graphene oxide water solution, is 1～4 with acid for adjusting pH；Then it is ultrasonic
Process forms graphene oxide dispersion；Dialysis treatment will be carried out after graphene oxide dispersion ultraviolet process, obtain negatively charged
Porous graphene dispersion soln；The power of the ultraviolet process is 1500 W～4000 W, and the time is 30 s～30 min；
（2）P-phenylenediamine is added in negatively charged porous graphene dispersion soln, back flow reaction obtains the porous graphite of positively charged
Alkene dispersion liquid；
（3）Silicon chip after will be amido modified immerses electronegative porous graphene dispersion liquid, the porous graphite of positively charged successively
In alkene dispersion liquid, repeat 1～60 time, be dried to obtain three-dimensional porous graphene extra-thin film；
（4）Electrode is prepared on three-dimensional porous graphene extra-thin film surface, three-dimensional porous graphene extra-thin film gas sensor is obtained.
2. the preparation method of three-dimensional porous graphene extra-thin film gas sensor according to claim 1, is characterized in that：Step
（1）In, liquid oxidizer is added in graphene oxide water solution with aqueous oxidizing agent solution form, and sulfate is with sulfate solution
During form adds graphene oxide water solution；The concentration of the graphene oxide water solution be 0.2～5 mg/mL, sulphuric acid saline
The concentration of solution is 10～50 mM, and the concentration of aqueous oxidizing agent solution is 4～10 wt%；Graphene oxide water solution, oxidant water
Solution, the volume ratio of sulfate solution are（150～250）∶（50～120）∶1；The power of the supersound process is 50～100
KHz, time are 10 min～1 h.
3. the preparation method of three-dimensional porous graphene extra-thin film gas sensor according to claim 2, is characterized in that：Step
（1）In, use salt acid for adjusting pH；Liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；It is 4 to adjust pH；Graphene oxide water
Solution, aqueous oxidizing agent solution, the volume ratio of sulfate solution are（190～210）∶（70～90）∶1.
4. the preparation method of three-dimensional porous graphene extra-thin film gas sensor according to claim 1, is characterized in that：Step
（1）In, the power of the ultraviolet process is 1500 W～3000 W, and the time is 30 s～70s；The dialysis treatment time is 3
My god～15 days；Dialysis is carried out in deionized water.
5. the preparation method of three-dimensional porous graphene extra-thin film gas sensor according to claim 1, is characterized in that：Step
（2）In, the mass ratio of the p-phenylenediamine and electronegative porous graphene is 1:（5～20）；Reflux time be 12～
24 h；After back flow reaction terminates, sucking filtration cleaning, addition alcohol obtain the porous graphene dispersion liquid of positively charged.
6. the preparation method of three-dimensional porous graphene extra-thin film gas sensor according to claim 1, is characterized in that：Step
（3）In, silicon chip is modified with amino silicane coupling agent；All be rinsed after immersion dispersion liquid every time, dried.
7. the preparation method of three-dimensional porous graphene extra-thin film gas sensor according to claim 1, is characterized in that：Step
（3）In, the concentration of the negatively charged porous graphene dispersion liquid is 0.1～2 mg/mL, the positively charged porous graphene dispersion
The concentration of liquid is 0.1～2 mg/mL；The time for immersing negatively charged porous graphene dispersion liquid every time is 5～30 min；Soak every time
The time for entering positively charged porous graphene dispersion liquid is 5～30 min.
8. a kind of preparation method of three-dimensional porous graphene extra-thin film, comprises the following steps：
（1）Liquid oxidizer and sulfate are added in graphene oxide water solution, is 1～4 with acid for adjusting pH；Then it is ultrasonic
Process forms graphene oxide dispersion；Dialysis treatment will be carried out after graphene oxide dispersion ultraviolet process, obtain negatively charged
Porous graphene dispersion soln；The power of the ultraviolet process is 1500 W～4000 W, and the time is 30 s～30 min；
（2）P-phenylenediamine is added in negatively charged porous graphene dispersion soln, back flow reaction obtains the porous graphite of positively charged
Alkene dispersion liquid；
（3）Silicon chip after will be amido modified immerses electronegative porous graphene dispersion liquid, the porous graphite of positively charged successively
In alkene dispersion liquid, repeat 1～60 time, be dried to obtain three-dimensional porous graphene extra-thin film.
9. the three-dimensional porous Graphene that according to claim 8 prepared by the preparation method of three-dimensional porous graphene extra-thin film is ultra-thin
Film.
10. three-dimensional porous graphene extra-thin film described in claim 9 is preparing three-dimensional porous graphene extra-thin film gas sensor
In application.
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