CN106596654A - Three-dimensional porous graphene ultrathin film based vertical responding gas sensor and preparation method thereof - Google Patents
Three-dimensional porous graphene ultrathin film based vertical responding gas sensor and preparation method thereof Download PDFInfo
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- CN106596654A CN106596654A CN201611135425.9A CN201611135425A CN106596654A CN 106596654 A CN106596654 A CN 106596654A CN 201611135425 A CN201611135425 A CN 201611135425A CN 106596654 A CN106596654 A CN 106596654A
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Abstract
The invention discloses a three-dimensional porous graphene ultrathin film based vertical responding gas sensor and preparation method thereof. The preparation method of the gas sensor is achieved through the following four steps: a preparation of negatively charged porous graphene dispersion liquid, a preparation of positively charged porous graphene dispersion liquid, an assembly preparation of three-dimensional porous graphene ultrathin film and a preparation of three-dimensional porous graphene ultrathin film based vertical responding gas sensor. The gas sensitive sensor with porous graphene ultrathin film that prepared through the preparation method has a very high sensitivity to DMMP gas molecule. And the preparation method is simple in technology and suitable for large-scale preparation of the sensors.
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
Vertical response type gas sensor based on three-dimensional porous graphene extra-thin film and preparation method thereof.
Background technology
Gas sensor plays more and more important effect in fields such as environmental monitoring, food security, health cares.With
The development of nanometer technology, 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, has 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.The sensor that single graphene film is constituted has repeatable poor, single and breaks
The shortcomings of stability splitting and cause is not high, constructs graphene film thin film netowrk and becomes and prepare high-efficient graphite alkene sensor very
One of effective method.However, during graphene film network is constructed, due to lamella sintering action, easily causing thin
Graphene film is greatly reduced with the contact area of gas molecule in film, so as to affect the air-sensitive performance of sensor.
Typically using the structure of horizontal layout electrode, i.e. positive and negative electrode is all located at film to existing graphene film gas sensor
Plane in, when electric current is migrated in graphene planes, carrier will be subject to graphenic surface adhesion gas molecule sluggishness
Affect, so as to causing the graphene film sensor generally studied at present to there is a problem of responding and recovering slack-off.
The content of the invention
The present invention is directed to deficiencies of the prior art, there is provided 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
Graphene film direction flow, it is to avoid because Graphene causes it to carrier in the face of the adhesion of gas molecule in plane
Inhibition, so as to realize the gas sensor for making to the extremely sensitive quick response performance of gas molecule.Meanwhile, using height
Power UV irradiation and organic molecule modification electrostatic self-assembled technology or coating prepare three-dimensional porous graphene extra-thin film,
Increase the specific surface area of sensitive thin film, beneficial to the further raising of 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 following step
Suddenly：
（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 the ultraviolet process of graphene oxide dispersion, 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）During first electrode to be immersed successively the porous graphene dispersion liquid of electronegative porous graphene dispersion liquid, positively charged,
Repeat 15～200 times, be dried to obtain the first electrode with three-dimensional porous graphene extra-thin film；
（4）Second is prepared on the three-dimensional porous graphene extra-thin film surface of the first electrode with three-dimensional porous graphene extra-thin film
Electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film.
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 suction filtration cleaning, addition alcohol many of positively charged are obtained
Hole graphene dispersing solution.
In above-mentioned technical proposal, step（3）In, first electrode is placed in negatively charged porous graphene dispersion liquid and deposits one
The section time, after being dried cleaning treatment, then it is placed in deposition a period of time in positively charged porous graphene dispersion liquid, is dried cleaning treatment
Afterwards, then be placed in negatively charged porous graphene dispersion liquid deposition 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, 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；Every time the time of the porous graphene dispersion liquid of immersion positively charged is 5～30 min.
The invention also discloses a kind of system of the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film
Preparation Method, 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 the ultraviolet process of graphene oxide dispersion, obtain porous also
Former graphene oxide dispersion soln；The power of the ultraviolet process is 1500 W～4000 W, and the time is 30 s～30 min；
（2）Porous redox graphene dispersion soln is spun to into first electrode surface, dried process is obtained with three-dimensional many
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
Black alkene ultrathin membrane surface prepares second electrode, obtains based on the vertical response type gas sensing of three-dimensional porous graphene extra-thin film
Device.
In the present invention, 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 the present invention, step（1）In, liquid oxidizer adds graphene oxide water solution in aqueous oxidizing agent solution form
In, sulfate is added in graphene oxide water solution in sulfate solution form；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 proportion, nano-pore being uniformly distributed in graphene film can be realized, crossing vast scale etching will obtain non-porous broken little nanometer
Graphene film, what too small concentration was obtained is the graphene film with oxy radical.
In the present invention, step（1）In, 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, step（1）In, ultrasonically treated power is 50～100 kHz, and the time is 10 min～1 h.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, step（1）The preparation of porous graphene dispersion soln is porous graphene gas sensor of the present invention
Important step；Graphene oxide dispersion is placed in into high power ultraviolet lamp next step reduction etching reaction, reaction terminates rearmounted
In bag filter, dialyse in deionized water and obtain porous redox graphene dispersion soln；Limit the power of uviol lamp
For 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 obtain etching Graphene, creative place exactly of the invention.The present invention is adopted first
With ultraviolet process graphene oxide dispersion, ultraviolet process not only obtains porous graphene, and realizes graphene oxide
Reduction, the color of graphene solution becomes aterrimus by light gray is transparent, and nanometer sheet becomes conductive by insulation, with reducing degree
Intensification, resistance is gradually lowered, it is to avoid existing reduction treatment must be beneficial to the defect of chemical reagent, be that green chemistry is carried
For new approach；Particularly, the porous graphene for obtaining has nanoscale hole, can greatly improve the ratio table of Graphene network
Area, solves existing Graphene network due to the defect of compact structure caused by Graphene easily piling up property, and etches pore
Process is simple, can large-scale production, it is to avoid existing porous graphene needs high temperature（The temperature of carbon thermal reduction）, low yield, hole
Rate is low and uncontrollable, the problem of pore size distribution lack of homogeneity；Especially present invention achieves the graphene oxide under the conditions of oxidant
Reduction, prior art think oxidant presence cannot redox graphene, but the present invention increase UV power, limit
Fixed ultraviolet process time, at the same the oxidant and sulfate of compatibility proper ratio, and dispersion liquid acid number is limited, realize oxidation stone
The reduction of black alkene, has not only obtained the excellent Graphene of specific surface area, and has obtained the reduction-oxidation graphite of excellent electrical property
Alkene, is that bigger serface Graphene plays a crucial role for gas sensor, 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, it is prepared by the low-coat scaleization for being conducive to senser element.
In the present invention, step（1）In, the dialysis treatment time is 3 days～15 days, and molecular cut off is generally 10000
The impurity such as left and right, metal ion, hydrogen ion and hydrogen peroxide for acting as being remained in removing solution of dialysis.
In the present invention, second electrode is prepared on three-dimensional porous graphene extra-thin film surface using micro-processing technology, obtain base
In the vertical response type gas sensor of three-dimensional porous graphene extra-thin film.The first electrode of the present invention, second electrode are right respectively
Positive electrode, negative electrode or negative electrode, positive electrode are answered, the electrode vertical distribution, the three-dimensional porous Graphene of middle setting is ultra-thin
Film, is a kind of new sensor construction.
Invention additionally discloses the vertical response type gas based on three-dimensional porous graphene extra-thin film prepared by above-mentioned preparation method
Body sensor, the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film that obtains of the present invention to gas especially
It is that DMMP molecules (dimethyl methyl phosphonate) have excellent sensing capabilities.
Especially, the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film that the present invention is obtained is just
Three-dimensional porous graphene extra-thin film is set between negative electrode, vertical sandwich structure is formed, the creativeness of the present invention is just being embodied.This
Invention effectively overcomes prior art and the defect of positive and negative electrode, the vertical response of preparation can only be simultaneously arranged in sensing membrane one side
Type gas sensor has very high specific surface area, substantially increases the contact with gas molecule, effectively increases sensing
The detectability of device.
In the preparation method of the present invention, without the need for processing first electrode, direct self assembly or the three-dimensional porous Graphene of coating
Solution, in the vertical sandwich structure for ultimately forming, porous membrane good stability, without ablation phenomenon；Efficiently solve existing
Technology needs the problem for processing electrode or substrate.
Particularly, the vertical response type based on three-dimensional porous graphene extra-thin film for being prepared by the preparation method of the present invention
Gas sensor, three-dimensional porous graphene extra-thin film has respectively extraordinary interracial contact with positive and negative electrode, has both improve biography
Sensitivity of the sensor to gas increased detection accuracy again；The thickness of three-dimensional porous graphene extra-thin film is limited as 20～900
Nanometer, had both been prevented effectively from the contact of positive and negative electrode, more ultraviolet reduction etching processing under combined oxidant cause three-dimensional porous stone
Black alkene ultrathin membrane has extraordinary gas sensing effect as gas sensing 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, especially solves the problems, such as that graphene oxide cannot be reduced in the presence of oxidant, and without the need for other chemistry examinations
Agent, such as go back original reagent, the use of pore reagent, are a kind of simple and quick, environmental protection industrial methods.
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, it is excellent so as to have to gas molecule especially DMMP molecules
Sensing capabilities.
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 of preparation with huge specific surface area except also having
Excellent electric conductivity, such that it is able to prepare gas sensor of good performance.
4. the present invention prepares multi-layer three-dimension porous graphene ultrathin film using self assembly means, takes full advantage of single
Interaction force between graphene film module units is realizing ultra-thin membrane structure, such as the accurate control of graphene film number of plies etc.
System, so as to realize the accuracy controlling of ultra-thin film character, beneficial to the extensive controllable standby for optimizing device.
5. the ultraviolet reduction etching processing under combined oxidant of the present invention, prepares the sensing of certain thickness, porous
Film, solves the graphene film that prior art lamella sintering action causes and is greatly reduced with the contact area of gas molecule, so as to
Affect the problem of the air-sensitive performance of sensor.
6. the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film disclosed by the invention is adopted first
The sandwich structure of sensing membrane is set between two electrodes, the technology prejudice that prior art has to coplanar setting electrode is overcome；
The sensor for obtaining contacts very good with gas molecule, with excellent detectability.
Description of the drawings
Fig. 1 is structural representation of the present invention based on 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 based on three-dimensional porous graphene extra-thin film that obtains of embodiment one to 50ppm
DMMP molecules electrical response curve map；
Fig. 3 is the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film that obtains of embodiment three to 50ppm
DMMP molecules electrical response curve map；
Fig. 4 is the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film that obtains of embodiment eight to 50ppm
DMMP molecules electrical response curve map.
Specific embodiment
Structural representation of the accompanying drawing 1 for the present invention based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film
Figure, it includes that first electrode 1, second electrode 2 and the three-dimensional porous Graphene between first electrode and second electrode are super
Film 3.Preparation method based on the vertical response type gas sensor of 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 following step
Suddenly：
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 the mL of 5 wt% hydrogen peroxide solutions 90 to enter concentration, adds the mL of copperas solution 1 that concentration is 20 mM, 100 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 the s of reactive ion etching 40, 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. the addition mg of p-phenylenediamine 1000 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, is flowed back under water bath condition anti-
After answering 18 h, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, taken 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 ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, so repeatedly, in gold electrode surfaces
The three-dimensional porous graphene extra-thin film of 50 layers of deposition, its thickness is 70 nanometers；Then using micro-processing technology in three-dimensional porous stone
Black alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film,
Resistance is 3.5 M Ω.
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 the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including following step
Suddenly：
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 the mL of 4wt% hydrogen peroxide solutions 70 to enter concentration, adds the mL of copperas solution 1 that concentration is 15 mM, 80Hz ultrasonic disperses
40 min form graphene oxide dispersion, are subsequently adding hydrochloric acid, make pH value reach 4；
2. above-mentioned graphene oxide dispersion is placed under 2500 W uviol lamps after the s of reactive ion etching 30, 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. the addition mg of p-phenylenediamine 1000 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, is flowed back under water bath condition anti-
After answering 15 h, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, taken 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 ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, it is so repeatedly, heavy in silicon chip surface
The three-dimensional porous graphene extra-thin film of 30 layers of product, its thickness is 50 nanometers；Then using micro-processing technology in three-dimensional porous graphite
Alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film, electricity
Hinder for 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 following step
Suddenly：
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 the mL of 8wt% hydrogen peroxide solutions 80 to enter concentration, adds the mL of copperas solution 1 that concentration is 15 mM, 50Hz 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 the s of reactive ion etching 70, 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. the addition mg of p-phenylenediamine 1000 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, is flowed back under water bath condition anti-
After answering 18 h, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, taken 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 ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, it is so repeatedly, heavy in silicon chip surface
The three-dimensional porous graphene extra-thin film of 90 layers of product, its thickness is 150 nanometers；Then using micro-processing technology in three-dimensional porous graphite
Alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film, electricity
Hinder for 16.2 M Ω.
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 the vertical response type gas sensor based on three-dimensional porous graphene extra-thin film, including following step
Suddenly：
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 the mL of 5wt% hydrogen peroxide solutions 80 to enter concentration, adds the mL of copperas solution 1 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 the s of reactive ion etching 30, 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. the addition mg of p-phenylenediamine 1000 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, is flowed back under water bath condition anti-
After answering 18 h, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1.5mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 10 min, taken 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 ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 10 min, it is so repeatedly, heavy in silicon chip surface
The three-dimensional porous graphene extra-thin film of 150 layers of product, its thickness is 250 nanometers；Then using micro-processing technology in three-dimensional porous stone
Black alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film,
Resistance is 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 following step
Suddenly：
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 the mL of 7wt% hydrogen peroxide solutions 90 to enter concentration, adds the mL of copperas solution 1 that concentration is 40 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 the s of reactive ion etching 50, 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. the addition mg of p-phenylenediamine 1000 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, is flowed back under water bath condition anti-
After answering 18 h, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1.5mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, taken 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 ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, it is so repeatedly, heavy in silicon chip surface
The three-dimensional porous graphene extra-thin film of 180 layers of product, its thickness is 280 nanometers；Then using micro-processing technology in three-dimensional porous stone
Black alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film,
Resistance is 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 following step
Suddenly：
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 the mL of 6wt% hydrogen peroxide solutions 80 to enter concentration, adds the mL of copperas solution 1 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 the s of reactive ion etching 70, 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. the addition mg of p-phenylenediamine 720, the back flow reaction under water bath condition in the negatively charged mL of porous graphene dispersion liquid 100 are taken
After 18 h, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, taken out
Deionized water rinsing, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and deposits 30 min, takes out ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, it is so repeatedly, heavy in silicon chip surface
The three-dimensional porous graphene extra-thin film of 140 layers of product, its thickness is 230 nanometers；Then using micro-processing technology in three-dimensional porous stone
Black alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film,
Resistance is 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 following step
Suddenly：
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 the mL of 5wt% hydrogen peroxide solutions 80, adds the mL of copperas solution 1 that concentration is 20 mM, 80Hz ultrasounds point
Dissipate 60 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 the s of reactive ion etching 30, 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. the addition mg of p-phenylenediamine 1100 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, and 80 degree are returned under water bath condition
After stream 18 h of reaction, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 25 min, taken out
Deionized water rinsing, after nitrogen is dried up, then is placed in positively charged porous graphene dispersion liquid and deposits 10min, takes out alcohol flushing,
After nitrogen is dried up, then it is placed in negatively charged porous graphene dispersion liquid and deposits 25 min, so repeatedly, in silicon chip surface deposition
150 layers of three-dimensional porous graphene extra-thin film, its thickness is 240 nanometers；Then using micro-processing technology in three-dimensional porous graphite
Alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film, electricity
Hinder for 18.5 M Ω.
Embodiment eight
A kind of preparation method of porous graphene gas sensor, comprises the following steps：
（1）Add after the 1 mg/mL graphene oxide water solutions ultrasonic disperse that 20 mL Hummers methods are obtained is processed 3 hours
Hydrochloric acid, the pH value for making graphene oxide water solution reaches 4；It is the mL of 3 wt% hydrogen peroxide solutions 10 to be subsequently adding concentration, is added
Concentration is the mL of copperas solution 0.1 of 15 mM, 80 Hz, 10 min of ultrasound, forms graphene oxide dispersion；
（2）Above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after the s of reactive ion etching 30, in being placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid for obtaining；
（3）Gold electrode is prepared using the photoetching in micro-processing technology and lift-off technology；By porous graphene dispersion liquid（2 mg/L）
According to 0.1 mL/cm2Electrode surface is spun to, 80 DEG C of vacuum drying 1h obtain 500 nanometers of three-dimensional porous graphene extra-thin films,
Then gold electrode is prepared on three-dimensional porous graphene extra-thin film surface, so as to obtain porous graphene gas sensor, resistance rings
Should be worth for 4.0 M Ω.
Fig. 4 is electrical response curve map of the sensor to the DMMP molecules of 50 ppm, and sensor is to DMMP molecule tables
Reveal extremely sensitive response performance.
Embodiment nine
A kind of preparation method of porous graphene gas sensor, comprises the following steps：
（1）Add after the 0.5 mg/mL graphene oxide water solutions ultrasonic disperse that 20 mL Hummers methods are obtained is processed 3 hours
Enter hydrochloric acid, the pH value for making graphene oxide water solution reaches 4；It is the mL of 10 wt% hydrogen peroxide solutions 10 to be subsequently adding concentration, then is added
Enter the mL of copperas solution 0.1,80 Hz, 10 min of ultrasound that concentration is 30mM, form graphene oxide dispersion；
（2）Above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after the s of reactive ion etching 70, in being placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid for obtaining；
（3）Gold electrode is prepared using the photoetching in micro-processing technology and lift-off technology, porous graphene dispersion liquid is taken（2 mg/L）
According to 1 mL/cm2Electrode surface is spun to, 80 DEG C of vacuum drying 1h obtain 900 nanometers of three-dimensional porous graphene extra-thin films, so
Afterwards gold electrode is prepared on three-dimensional porous graphene extra-thin film surface, so as to obtain porous graphene gas sensor, resistance value is
9.5 MΩ。
Embodiment ten
A kind of preparation method of porous graphene gas sensor, comprises the following steps：
（1）In the 1mg/mL graphene oxide water solutions decentralized processing that 20 mL Hummers methods are obtained hydrochloric acid is added after 3 hours,
The pH value for making graphene oxide water solution reaches 4；It is the mL of 5 wt% hydrogen peroxide solutions 10 to be subsequently adding concentration, and adding concentration is
The mL of copperas solution 0.1 of 20 mM, 80 Hz 10 min of ultrasound, form graphene oxide dispersion；
（2）Above-mentioned graphene oxide dispersion is placed under 2500 W uviol lamps after the s of reactive ion etching 30, in being placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid for obtaining；
（3）Gold electrode is prepared using the photoetching in micro-processing technology and lift-off technology, porous graphene dispersion liquid is taken（2 mg/L）
According to 0.5 mL/cm2Electrode surface is spun to, 80 DEG C of vacuum drying 1h obtain 750 nanometers of three-dimensional porous graphene extra-thin films,
Then gold electrode is prepared on three-dimensional porous graphene extra-thin film surface, so as to obtain porous graphene gas sensor, resistance value
For 12.1 M Ω.
Embodiment 11
A kind of preparation method of porous graphene gas sensor, comprises the following steps：
（1）In the 1 mg/mL graphene oxide water solutions decentralized processing that 20 mL Hummers methods are obtained hydrochloric acid is added after 1 hour,
The pH value for making graphene oxide water solution reaches 4；It is the mL of 7 wt% hydrogen peroxide solutions 10 to be subsequently adding concentration, and adding concentration is
The mL of copperas solution 0.1 of 10 mM, 80Hz 10 min of ultrasound, form graphene oxide dispersion；
（2）Above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after the s of reactive ion etching 30, in being placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid for obtaining；
（3）Gold electrode is prepared using the photoetching in micro-processing technology and lift-off technology, porous graphene dispersion liquid is taken（2 mg/L）
According to 0.6 mL/cm2Electrode surface is spun to, 80 DEG C of vacuum drying 1h obtain 800 nanometers of three-dimensional porous graphene extra-thin films,
Then gold electrode is prepared on three-dimensional porous graphene extra-thin film surface, so as to obtain porous graphene gas sensor, resistance value
For 8.2 M Ω.
Embodiment 12
A kind of preparation method of porous graphene gas sensor, comprises the following steps：
（1）In the 1 mg/mL graphene oxide water solutions decentralized processing that 20 mL Hummers methods are obtained hydrochloric acid is added after 3 hours,
The pH value for making graphene oxide water solution reaches 4；It is the mL of 3 wt% hydrogen peroxide solutions 10 to be subsequently adding concentration, and adding concentration is
The mL of copperas solution 0.1 of 10 mM, 80Hz 10 min of ultrasound, form graphene oxide dispersion；
（2）Above-mentioned graphene oxide dispersion is placed under 3000 W uviol lamps after the s of reactive ion etching 30, in being placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid for obtaining；
（3）Gold electrode is prepared using the photoetching in micro-processing technology and lift-off technology, porous graphene dispersion liquid is taken（5 mg/L）
According to 0.5 mL/cm2Electrode surface is spun to, 80 DEG C of vacuum drying 1h obtain 850 nanometers of three-dimensional porous graphene extra-thin films,
Then gold electrode is prepared on three-dimensional porous graphene extra-thin film surface, so as to obtain porous graphene gas sensor, resistance value
For 2.4 M Ω.
Comparative example one
A kind of preparation method of porous graphene gas sensor, comprises the following steps：
（1）In the 1 mg/mL graphene oxide water solutions decentralized processing that 20 mL Hummers methods are obtained hydrochloric acid is added after 3 hours,
The pH value for making graphene oxide water solution reaches 4；It is the mL of 3 wt% hydrogen peroxide solutions 10 to be subsequently adding concentration, and adding concentration is
The mL of copperas solution 0.1 of 10 mM, 80 Hz 10 min of ultrasound, form graphene oxide dispersion；
（2）Above-mentioned graphene oxide dispersion is placed under 500 W uviol lamps after the s of reactive ion etching 400, in being placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid for obtaining；
（3）Gold electrode is prepared using the photoetching in micro-processing technology and lift-off technology, porous graphene dispersion liquid is taken（2 mg/L）
According to 0.5 mL/cm2Electrode surface is spun to, 80 DEG C of vacuum drying 1h obtain 730 nanometers of three-dimensional porous graphene extra-thin films,
Then prepare gold electrode on three-dimensional porous graphene extra-thin film surface, so as to obtain porous graphene gas sensor, resistance 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 following step
Suddenly：
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 the mL of 5wt% hydrogen peroxide solutions 10 to enter concentration, adds the mL of copperas solution 1 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 the min of reactive ion etching 5, 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. the addition mg of p-phenylenediamine 1000 in the negatively charged mL of porous graphene dispersion liquid 100 is taken, and 80 degree are returned under water bath condition
After stream 18 h of reaction, suction filtration cleaning is dissolved in after ethanol and obtains the porous graphene dispersion liquid of 1mg/mL positively chargeds；
4. gold electrode is prepared on low resistance silicon chip substrate, be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, taken 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 ethanol punching
Wash, after nitrogen is dried up, then be placed in negatively charged porous graphene dispersion liquid and deposit 15 min, it is so repeatedly, heavy in silicon chip surface
The three-dimensional porous graphene extra-thin film of 100 layers of product, its thickness is 160 nanometers；Then using micro-processing technology in three-dimensional porous stone
Black alkene ultrathin membrane surface prepares gold electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film,
Resistance is 972.6 M Ω.
As can be seen that porous redox graphene even pore distribution prepared by the present invention, with good reproducibility
Can, especially with outside high-power purple process, a step etching reduction, with while loose structure with good electric conductivity,
One layer of uniform Graphene of folder in the middle of electrode, overlap joint electrode forms galvanic circle；It is simple to operate, without the need for other reagents, can scale
Production；The porous redox graphene of preparation is prepared into after gas sensor has excellent signal conversion performance, to gas
Molecule has excellent sensing capabilities, can be used for gas detection；Achieve unexpected technique effect.
Claims (10)
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
Suddenly：
（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 the ultraviolet process of graphene oxide dispersion, 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）During first electrode to be immersed successively the porous graphene dispersion liquid of electronegative porous graphene dispersion liquid, positively charged,
Repeat 15～200 times, be dried to obtain the first electrode with three-dimensional porous graphene extra-thin film；
（4）Second is prepared on the three-dimensional porous graphene extra-thin film surface of the first electrode with three-dimensional porous graphene extra-thin film
Electrode, obtains based on the vertical response type gas sensor of three-dimensional porous graphene extra-thin film.
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
Suddenly：
（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 the ultraviolet process of graphene oxide dispersion, obtain porous also
Former graphene oxide dispersion soln；The power of the ultraviolet process is 1500 W～4000 W, and the time is 30 s～30 min；
（2）Porous redox graphene dispersion soln is spun to into first electrode surface, dried process is obtained with three-dimensional many
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
Black alkene ultrathin membrane surface prepares second electrode, obtains based on the vertical response type gas sensing of three-dimensional porous graphene extra-thin film
Device.
3. the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claims 1 or 2
Preparation method, is characterized in that：Step（1）In, liquid oxidizer adds graphene oxide water solution in aqueous oxidizing agent solution form
In, sulfate is added in graphene oxide water solution in sulfate solution form；The concentration of the graphene oxide water solution
For 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%；Oxygen
Graphite aqueous solution, aqueous oxidizing agent solution, the volume ratio of sulfate solution are（150～250）∶（50～120）∶1；It is described
Ultrasonically treated power is 50～100 kHz, and the time is 10 min～1 h.
4. the preparation side of the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claim 3
Method, is characterized in that：Step（1）In, use salt acid for adjusting pH；Liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；Adjust pH
For 4；Graphene oxide water solution, aqueous oxidizing agent solution, the volume ratio of sulfate solution are（190～210）∶（70～90）∶
1。
5. the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claims 1 or 2
Preparation method, is characterized in that：Step（1）In, the power of the ultraviolet process is 1500 W～3000 W, the time be 30 s～
70s；The dialysis treatment time is 3 days～15 days；Dialysis is carried out in deionized water.
6. the preparation side of the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claim 1
Method, is characterized in that：Step（2）In, the mass ratio of the p-phenylenediamine and electronegative porous graphene is 1:（5～20）；Return
The stream reaction time is 12～24 h；After back flow reaction terminates, suction filtration cleaning, addition alcohol obtain the porous graphene dispersion of positively charged
Liquid.
7. the preparation side of the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claim 1
Method, is characterized in that：Step（3）In, silicon chip is modified with amino silicane coupling agent；All rushed after immersion dispersion liquid every time
Wash, dried process；The concentration of the negatively charged porous graphene dispersion liquid be 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；
Every time the time of immersion positively charged porous graphene dispersion liquid is 5～30 min.
8. the preparation side of the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claim 2
Method, is characterized in that：Step（2）In, by porous redox graphene dispersion liquid revolving, concentration is formed for 1～5 mg/mL porous
Redox graphene dispersion liquid；The porous redox graphene dispersion soln is according to 0.1～1 mL/cm2It is spun to
One electrode surface；The dried process is 75～85 DEG C of vacuum drying treatments.
9. the vertical response type gas sensor of three-dimensional porous graphene extra-thin film is based on according to claims 1 or 2
The vertical response type gas sensor of three-dimensional porous graphene extra-thin film prepared by preparation method.
10. the vertical response type gas sensor of three-dimensional porous graphene extra-thin film according to claim 9, is characterized in that：
The thickness of the three-dimensional porous graphene extra-thin film is 20～900 nanometers.
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