CN106248776B - A kind of sensor array of detectable multiple groups part mixed gas - Google Patents
A kind of sensor array of detectable multiple groups part mixed gas Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
Abstract
The present invention be a kind of detectable multiple groups part mixed gas sensor array, by n difference interpolars away from three electrode ionizing transducer of Jenner's metre hole film form.Sensor includes three the first, second, and third electrodes being sequentially distributed from bottom to top, and first electrode is distributed the metallic film base of Jenner's metre hole by inner surface attachment and electrode equipped with small air hole is constituted；Second electrode is made of the extraction pole that center is equipped with small fairlead；Third electrode sets slotted collector by plate face and constitutes；It is mutually isolated that three electrodes pass through insulation column respectively；N three electrode ionizing transducer first electrode of Jenner's metre hole film is produced on same pole plate；Interpolar between three electrodes is away from according to the aperture of air hole and fairlead and the setting of the side length of slot and groove depth.The present invention is not required to mixed gas to be separated, has been compared with the prior art biggish collected current and sensitivity by current detecting each component concentration away from identification different component gas by changing interpolar.
Description
Technical field
The present invention relates to gas sensing fields, are a kind of sensor arrays of detectable multiple groups part mixed gas, regardless of
From directly detecting mixed gas concentration under the conditions of mixed gas.
Background technique
With the progress and industrial development of science and technology, the requirement to the detection and analysis of multicomponent gas is continuous
It improves, but existing detection means cannot meet the needs.The equipment that can be applied to mixed gas on-line checking at present has: gas
Chromatography, sensor array, spectrum/mass spectrograph etc..Gas chromatograph uses chromatography post separation mixed gas first, then uses phase
Deserved gas sensor is detected respectively, such as the TM8 on-line computing model that Serveron company, the U.S. develops, the detection of this quasi-instrument
Process is complicated, more sensitive to environment, difficult in maintenance.Sensor array is by various pure gas sensor (such as metal oxides
Semiconductor transducer, electrochemical sensor, pyroelectric sensor, fibre optical sensor etc.) composition array detects mixed gas, and it can be with
Gas is not separated directly to be detected, but these method detection accuracy are low, stability is poor, and selectivity is bad.Spectrum/mass spectrograph
It is the instrument and equipment that can directly detect mixed gas, the Kelman TRANSFIX on-line monitoring developed such as GE company, the U.S.
Device, such detector also have the shortcomings that structure is complicated, expensive.
Carbon nanotube have big specific surface area, extremely strong adsorption ability, good electric conductivity and characteristic of semiconductor,
Excellent electronic field emission characteristic becomes the ideal gas sensitive of production gas sensor.Therefore, colleges and universities both domestic and external and
Scientific research institution has carried out numerous studies to carbon nanotube gas sensor successively.2006, Alexander etc. applied different metal
Sensor array is made in the single-walled carbon nanotube of (Pd, Pt, Rh, Au) modification, for detecting H2、CO、H2S and NH3Mixed gas,
Experiment shows the CNT sensor of Pd, Pt, Rh, Au modification respectively to H2S、H2、CO、NH3Sensitivity, but sensor array exists sternly
Retransposing interference, poor selectivity.Space etc. forms required electrode with photoresist over the carbon nanotube film in Shanghai Communications University marquis
Structure graph carries out dry etching to carbon nanotube layer with reactive ion etching method, forms small using photoresist layer as exposure mask
Away from gas gap carbon nanotube microelectrode array.Simple and effective carbon nanotube microelectrode preparation process is formd, is received for carbon
The application of mitron electronic device provides low cost, simple process, preparation method suitable for mass production.It 2013, opens brave etc.
People has developed a kind of using carbon nano-tube film as the three electrode carbon nano tube sensor of novel ionization type of cathode；Pass through three electrode knots
Structure and the design of unique electrode voltage, have drawn more cations；Experiment obtains sensor array to two component gaseous mixtures
Body NO/SO2Monodrome sensitivity characteristic (patent publication No.: 102095791A), have greater advantage in terms of detection gas.But it collects
Current value is less than normal, and sensitivity is not high enough.2014, the two electrode ionizing transducers that Saheed et al. is delivered, with CNTs's
Silicon base is as cathode, and Al plate is as anode, and the Kapton of 50.83 ± 0.05 μ m-thicks is as electrode insulation material.It is logical
The growing height for crossing control CNTs carrys out distance between control electrode.The He of various concentration, NH in air background3And N2In, experiment test
The breakdown voltages of 7 μm of pole pitch sensors obtains the relationship of sensor breakdown voltage and mixed gas concentration.With in air
Object gas He, NH3、N2The increase of concentration, the breakdown voltage monotone increasing of sensor or decline.However, operating voltage is higher,
It still has no idea to constitute practical sensor.
Researcher has found that above-mentioned three electrode sensor (patent publication No.: 102095791A) extraction hole area is larger, reversely
Field regime is limited, can only collection part cation, there are also part of cation to cathode motion bombard carbon pipe, thus make collect electricity
Stream is smaller, causes sensitivity low, affects sensor performance.
Summary of the invention
An object of the present invention provides a kind of sensor array of detectable multiple groups part mixed gas, is not separating gas
Gas concentration is measured in the case where body, obtains preferable monodrome sensitivity characteristic, and there is biggish collected current and sensitivity.Together
When, the sensor array structure is simple, at low cost.
An object of the present invention is to provide a kind of three electrode ionizing transducer of Jenner's metre hole film, sensor electrode
Aperture and interpolar optimize away from ratio, and existing three electrode sensors reversed electric field range is increased, and improve cation and draw quantity, from
And improve the ion stream drawn；Working sensor voltage is reduced, transducer sensitivity is improved.
The purpose of the present invention is what is realized by following technical proposals.
A kind of sensor array of detectable multiple groups part mixed gas includes multiple and different interpolars in array away from gold nano
Three electrode ionizing transducer of hole film；
The three electrode ionizing transducer of Jenner's metre hole film, the first electricity being sequentially distributed from bottom to top including three
Pole, second electrode and third electrode, the first electrode by inner surface attachment be distributed the metallic film base of Jenner's metre hole with
And the electrode equipped with small air hole is constituted；The second electrode is made of the extraction pole that center is equipped with small fairlead；The third
Electrode sets reeded collector by plate face and constitutes；It is mutually isolated that three electrodes pass through insulation column respectively；
Jenner's metre hole thin-film material is grown using evaporation deposition method in the first electrode inner surface metallic film base；
The aperture of the small air hole is 0.8~4mm, and the aperture of small fairlead is 1.2~6mm, and the side length of groove is 1.2
× 1.2~6 × 8mm, groove depth are 200 μm；
Interpolar between three electrodes is away from according to the setting of small air hole, the side length in the aperture of small fairlead and groove and groove depth.
The sensor array is according to multiple three electrode ionizing transducers of Jenner's metre hole film and column distribution, all sensings
The first electrode of device is produced on same pole plate, between adjacent sensors second electrode pole plate, between third electrode pad according to
Setting is spaced apart.
Further, it is spaced between the sensor array adjacent sensors second electrode pole plate, between third electrode pad
It is 3~8mm.
Further, the aperture of the small air hole be 0.8~4mm when, between first electrode and second electrode interpolar away from
The ratio between aperture of small air hole is 3/200~3/20.
Further, the aperture of the small fairlead be 1.2~6mm when, between first electrode and second electrode interpolar away from
The ratio between aperture of small fairlead is 1/100~1/10, and interpolar is away from the aperture with small fairlead between second electrode and third electrode
The ratio between be 1/100~1/10.
Further, when the side length and groove depth of the groove are respectively 1.2 × 1.2~6 × 8mm and 200 μm, second electrode with
Interpolar is away from being 3/10~3/5 with the ratio between groove depth between third electrode.
Further, the small air hole of the electrode surface of the first electrode is equipped with 1~20；
The small fairlead of the second electrode extraction pole has 1~20；
The groove of the third electrode collector is equipped with 1.
Correspondingly, the present invention gives a kind of Jenner's metre hole preparation of three electrode ionizing transducer of Jenner's metre hole film
To the method for metallic film base, include the following steps:
1) it is pre-processed before plated film: the silicon wafer for being etched with air hole being selected to pre-process as matrix and before carrying out plated film；
2) it sputters: successively sputtering titanium film, nickel film and golden film on three substrates respectively under vacuum conditions, three-layer thin-film is thick
Degree is respectively 50nm, 400nm and 125nm；
3) it anneals: sputtering is had to silicon base 30~80s of short annealing of titanium nickel gold thin film, annealing temperature is 400~500
℃；
4) prepared by gold nano Porous materials: being 3 × 10 in vacuum degree-3Pa has in Ti/Ni/Au film silicon base in sputtering, uses
Evaporation deposition method grows Jenner's metre hole thin-film material, and it is highly 1.8 μm that the average-size of Jenner's metre hole, which is 350nm,；
5) microscopic appearance detection is carried out, completes the growth course of metallic film base Jenner metre hole thin-film material since then.
Further, in step 2), sputtering condition are as follows: vacuum degree is 2.5 × 10-3Pa, sputter temperature are 30~40 DEG C, successively
Sputtering titanium film, nickel film and golden film sputtering time is respectively 7min, 50min and 13min.
Further, in step 4), it is 1.5nm/s that evaporation deposition method, which grows Jenner's metre hole thin-film material deposition rate, when deposition
Between be 20min.
The present invention has following technical effect that
The present invention can detect the sensor array of multiple groups part mixed gas, be mixed by n different interpolars away from detectable multiple groups part
The sensor for closing gas forms sensor array, measures mixed gas each component concentration to be measured respectively；It is supplied by sensor voltage source
Electricity；It is exported by pA grades of current measurement system detection sensors；Electrode spacing is adjusted, electrode voltage is adjusted, it is sensitive special to obtain monodrome
Property.The sensor array of detectable multiple groups part mixed gas obtains the sensitive spy of preferable monodrome not separating mixed gas
Property, there is biggish collected current and sensitivity.And desired hardware configuration is simple, and it is at low cost, various mixed gases can be applicable in,
High sensitivity, accuracy are high, while laying a good foundation for multicomponent gas detection.
Detailed description of the invention
Fig. 1 is the schematic perspective view of detectable multiple groups part hybrid gas sensor.
Fig. 2 is detectable multiple groups part hybrid gas sensor array three-dimensional display diagram.
Fig. 3 is detectable multiple groups part hybrid gas sensor array, detects mixed gas CH4The monodrome sensitivity characteristic of/CO
Figure.
Fig. 4 is the sensitivity characteristic figure of 1 Jenner's metre hole film of embodiment, three electrode ionization type CO sensor.
Fig. 5 is 1 Jenner's metre hole film of embodiment, three electrode ionization type CH4The sensitivity characteristic figure of sensor.
Fig. 6 is the schematic perspective view of carbon nano tube sensor.
Fig. 7 is the schematic perspective view of gold-plated carbon nano tube sensor.
Fig. 8 is the schematic perspective view of gold nano hole sensor.
Fig. 9 is the simulated current density of carbon nano tube sensor, gold-plated carbon nano tube sensor and gold nano hole sensor.
In Fig. 6~8: 1, first electrode；Small air hole on 1-1, first electrode；2, second electrode；2-1, second electrode
On small fairlead；3, third electrode；3-1, groove；4, the electrode equipped with small air hole；5, metallic film base；6, carbon nanotube
Film；7, Jenner's metre hole film；8, insulation column；9, gold-plated carbon nano-tube film.
Specific embodiment
With reference to the accompanying drawing and specific embodiment the present invention will be further described.
The schematic perspective view of detectable multiple groups part hybrid gas sensor as shown in Figure 1.Sensor array according to
Multiple three electrode ionizing transducers of Jenner's metre hole film and column distribution, the first electrode of all the sensors are produced on same pole plate
On, between sensor array adjacent second electrode pole plate between be divided into 3mm, between adjacent third electrode pad between be divided into 3mm.
Three electrode ionizing transducer of monomeric gold nano-pore has the following structure: being sequentially distributed from bottom to top including three
First electrode 1, second electrode 2 and third electrode 3, first electrode 1 are distributed the gold of Jenner's metre hole film 7 by inner surface attachment
Belong to film substrate 5 and the electrode 4 equipped with small air hole is constituted；Second electrode 2 is equipped with the extraction pole structure of small fairlead 2-1 by center
At；Third electrode 3 is made of plate face equipped with the collector of groove 3-1；It is mutually isolated that three electrodes pass through insulation column respectively,
Insulation column 8 is separately positioned between the metallic film base 5 and second electrode 2 for being dispersed with Jenner's metre hole film, second electrode 2 with
Between third electrode 3, i.e. the surface two sides and the third electrode 3 that are distributed in second electrode 2 face first electrode 1 of insulation column 8
The two sides on inside golden film surface.
As shown in Fig. 2, the interpolar of n adjacent electrode may be selected away from according to small air hole, the aperture of small fairlead and slot
Side length and groove depth setting three electrode ionization transducer of Jenner's metre hole form sensor array.Wherein, n three electricity of Jenner's metre hole film
Pole ionizing transducer first electrode is produced on same pole plate, between adjacent sensors second electrode, adjacent sensors third
Interval is 3~8mm between electrode.The quantity of second pole plate and third pole plate is determined by parameter to be measured.
Wherein, the aperture of small air hole 1-1 is set in 0.8~4mm, the aperture of small fairlead 2-1 is 1.2~6mm, groove
The side length and groove depth of 3-1 is respectively 1.2 × 1.2~6 × 8mm and 200 μm.When the aperture of small air hole is 0.8~4mm, the
One interpolar is 3/200~3/20 away from the ratio between the aperture with small air hole away from interpolar between the second pole；When the aperture of small fairlead
When for 1.2~6mm, away from the second interpolar, the interpolar away between away from the ratio between the aperture with small fairlead is 1/100~1/ to the first interpolar
10, the second interpolar is 1/100~1/10 away from the ratio between the aperture with small fairlead away from interpolar between third pole；When slot side length and
When groove depth is respectively 1.2 × 1.2~6 × 8mm and 200 μm, the second interpolar is away from interpolar between third pole away from being with the ratio between groove depth
3/10~3/5.
In this configuration, the small air hole of the electrode surface of first electrode has 1~20, and small ventilative hole shape can be circle
Shape；The small fairlead of second electrode extraction pole is equipped with 1~20, and small fairlead shape can be circular；Third electrode is received
The groove of collector is equipped with 1, and groove shapes can be rectangle.
The electrode plate face that the present invention is equipped with air hole is made of silicon sheet material；Metallic film base is using titanium, nickel, three kinds of gold
Metal material production；Jenner's metre hole film uses Jin Yuan, growth production Jenner's metre hole film in metallic film base；Second electrode
Silicon wafer to manufacture is all made of with third electrode.The two sides of first electrode and third electrode medial surface, second electrode are equipped with metal
Film.
Jenner's metre hole of three electrode ionizing transducer of the present embodiment Jenner's metre hole film is prepared into the step of metallic film base
It is rapid as follows:
1) it is pre-processed before plated film: the silicon wafer for being etched with air hole being selected to pre-process as matrix and before carrying out plated film；
2) it sputters: being 2.5 × 10 in vacuum degree-3Pa successively sputters titanium film, nickel on three substrates respectively at 30~40 DEG C
Film and golden film, sputtering time are respectively 10min, 40min and 20min, three-layer thin-film thickness be respectively 50nm, 400nm and
125nm；
3) it anneals: sputtering is had to silicon base 30~80s of short annealing of titanium nickel gold thin film, annealing temperature is 400~500
℃；
4) prepared by gold nano Porous materials: being 3 × 10 in vacuum degree-3Pa has in Ti/Ni/Au film silicon base in sputtering, uses
Evaporation deposition method grows Jenner's metre hole thin-film material, deposition 1.5nm/s, sedimentation time 20min, and Jenner's metre hole is averaged
It is highly 1.8mm having a size of 350nm；
5) microscopic appearance detection is carried out.
The three electrode ionizing transducer collected current of Jenner's metre hole film is high, and operating voltage is low, detection gas sensitivity
Height, at low cost, the service life is long.
With reference to the accompanying drawing and specific embodiment the present invention will be further described.
Embodiment 1
The present embodiment can detect the sensor array (structure is as shown in Figure 1 and Figure 2) of multiple groups part mixed gas, by two gold
Three electrode ionizing transducer of nano-porous thin film composition.The cathode of two sensors is produced on same pole plate, two extractions
Pole and collector structure having the same, two sensors have different interpolars away from.The first electrode of one of sensor
Electrode surface have the round air hole of 2 Φ 3mm, interpolar is away from the ratio between with air hole aperture between first electrode and second electrode
It is 1/40；Second electrode center be equipped with 9 Φ 1.2mm round fairlead, between first electrode and second electrode interpolar away from
The ratio between fairlead aperture is 1/16, and interpolar between second electrode and third electrode is away from being 1/16；The setting of third electrode collector
1 length and width is 6 × 8mm, 200 μm of deep trouth is corresponding with the fairlead of second electrode, second electrode and third electrode interpolar
Away from being 3/8 with the ratio between deep trouth groove depth.Insulation column is separately positioned on the metallic film base and second for being dispersed with Jenner's metre hole film
Between electrode, between second electrode and third electrode, i.e. the insulation column surface two that is distributed in second electrode face first electrode
The both ends on end and the inside golden film surface of third electrode.First three electrode ionizing transducer of Jenner's metre hole film is for detecting
The concentration of CO.
The structure of another sensor is identical as the structure of first sensor, interpolar between first electrode and second electrode
Away from being respectively 19/600 and 19/240 with small air hole and small fairlead diameter ratio；Interpolar between second electrode and third electrode
It is respectively 19/240 and 19/40 away from the ratio between the hole depth with small fairlead diameter and collector deep trouth.Second Jenner's metre hole film
Three electrode ionizing transducers are for detecting CH4Concentration.
The first electrode of two three electrode ionizing transducers of Jenner's metre hole film is produced on same pole in sensor array
On plate, between adjacent second electrode between be divided into 3mm, between adjacent third electrode between be divided into 3mm.
4 plate face of electrode that the present invention is equipped with air hole is made of silicon sheet material；Jenner's metre hole film substrate 5 is metal film
Substrate；Jenner's metre hole film 7, using evaporation deposition method, growth production Jenner's metre hole film 7 in metallic film base 5.The
Two electrodes 2 and third electrode 3 are all made of silicon wafer to manufacture.3 medial surface of first electrode 1 and third electrode equipped with air hole, second
The equal metal-plated membrane in the two sides of electrode 2.
Jenner's metre hole of the present embodiment production three electrode ionizing transducer of Jenner's metre hole is prepared into metallic film base step
It is as follows:
The silicon wafer for being etched with air hole is selected to pre-process as matrix and before carrying out plated film；It is 2.5 × 10 in vacuum degree- 3Pa, successively sputters titanium film, nickel film and golden film at 30 DEG C on three substrates respectively, sputtering time be respectively 10min, 40min and
20min, three-layer thin-film thickness are respectively 50nm, 400nm and 125nm；Sputtering is had to the silicon base short annealing of titanium nickel gold thin film
30s, annealing temperature are 500 DEG C；The preparation of gold nano Porous materials: being 3 × 10 in vacuum degree-3Pa has Ti/Ni/Au film silicon in sputtering
In substrate, Jenner's metre hole thin-film material, deposition 1.5nm/s, sedimentation time 20min, gold are grown using evaporation deposition method
The average-size of nano-pore is 350nm, is highly 1.8 μm.
Below by a specific example, inventive sensor array detection mixed gas concentration is described further.
Using three electrode ionizing transducer array of Jenner's metre hole film, experiment obtains methane CH4With carbon monoxide CO
The monodrome gas-sensitive property of multiple groups part mixed gas can measure carbon monoxide and methane multiple groups part mixed gas concentration value.
There are 2 small air holes on electrode in its three electrode ionizing transducer first electrode 1 of Jenner's metre hole film, is convenient for
Gas to be detected enters electrode gap；Metallic film base has conductive capability, and is firmly attached to one side surface of first electrode；The
Two electrodes 2 are equipped with the small fairlead of cation stream；3 collector of third electrode passes through the small fairlead of second electrode 2, collects gas
The cation stream that volume ionization generates.Pass through between first electrode 1 and second electrode 2, between second electrode 2 and third electrode 3 exhausted
Edge pillar 8 is mutually isolated；Tested gas is entered between the two neighboring electrode of sensor by the interelectrode gap of sensor perimeter
In gap.
The present invention takes the three electrode ionizing transducer of Jenner's metre hole film of above structure when measuring gas concentration, the
Two electrode potentials are higher than first electrode current potential, and third electrode potential is lower than second electrode current potential and is higher than first electrode current potential.The
It is leading circuit that two electrodes and first electrode, which are formed with electron stream, and it is leading that third electrode and first electrode, which are formed with ion stream,
Circuit, operating voltage reduce, draw the reduction in aperture so that reversed electric field range increase, increase the energy of collection of ions stream
Power improves transducer sensitivity.The collected current and gas concentration of three electrode ionizing transducer of Jenner's metre hole film output,
On the basis of second electrode applies certain voltage, monodrome gas concentration sensitive relations are presented.
In embodiment, experimental situation condition is temperature 50 C, relative humidity 25.2%RH, atmospheric pressure 101KPa.Two
1 cathode voltage of first electrode for measuring multiple groups part mixed gas concentration sensor is 0V, and 2 extraction pole of second electrode loads electricity
Press 250V, the equal on-load voltage 1V of 3 collector of third electrode.In CH4In 0~1000ppm of gas concentration range and CO gas 0~
In the concentration range of 5000ppm, 36 groups of experimental datas are obtained, CH is obtained4With the monodrome sensitivity characteristic of CO, can regardless of
From detection gas under the conditions of mixed gas.As shown in figure 3, experiment obtains sensor array to two component mixed gas CH4/CO
Monodrome sensitivity characteristic.With CH4With the raising of CO gas concentration, the collector of two measurement multicomponent gas concentration sensors
The ion stream being collected into reduces, and ion stream increases the relationship that monodrome is presented and declines with multicomponent gas concentration.Fig. 4 and Fig. 5 institute
Show, illustrates the single valued relation schematic diagram of sensor array detection carbon monoxide and methane multiple groups part mixed gas concentration respectively.
This sensor array for inventing detectable multiple groups part mixed gas is listed in cathode surface and is dispersed with Jenner's metre hole film,
The effect for changing cathode conductive characteristic has been not only acted as, field emission characteristic has been changed simultaneously；Although the quantity in extraction pole increase hole
But it reduces aperture and changes field distribution.Sensor electrode aperture and interpolar optimize away from ratio, enhance Particle diffusion effect,
More cations can be collected, increase collected current is reached, improve the effect of sensitivity.
In nitrogen gas, simulation calculation carbon nano tube sensor, gold-plated carbon nano tube sensor and above-mentioned electrode structure
Gold nano hole sensor collector average current density.In simulation calculation, carbon nano tube sensor (structure is as shown in Figure 6)
Including three first electrodes being sequentially distributed from top to bottom, second electrode and third electrode, the first electrode is glued by inner surface
It is connected to the substrate for being dispersed with carbon nano-tube film and the electrode equipped with the ventilative circular hole of 2 diameter 4mm is constituted；Second electrode is in
The heart is equipped with the extraction pole composition that 1 diameter 6mm draws circular hole；Third electrode is equipped with 16 × 8mm, 200 μm of deep trouths by plate face
Collector is constituted；It is mutually isolated that three electrodes pass through insulation column respectively.In simulation calculation, gold-plated carbon nano tube sensor
(structure is as shown in Figure 7) includes three first electrodes being sequentially distributed from top to bottom, second electrode and third electrode, and described first
Electrode is bonded with the substrate for being dispersed with gold-plated carbon nano-tube film by inner surface and equipped with the ventilative semicircle orifice of 2 diameter 5mm
Electrode is constituted；Second electrode is made of the extraction pole that center is equipped with 6 diameter 2mm extraction circular holes；Third electrode is smooth by plate face
Collector constitute；It is mutually isolated that three electrodes pass through insulation column respectively.In simulation calculation, carbon nano tube sensor, plating
The gold nano hole sensor structure of golden carbon nano tube sensor and above-mentioned electrode structure is as shown in Figure 8.
The collector average current density of simulation calculation is as shown in Figure 9.The average collected current of gold nano hole sensor is close
Degree is 2.26 × 10-5A/m2, the average collected current density of gold-plated carbon nano tube sensor is 2.07 × 10-6A/m2, carbon nanometer
The average collected current density of pipe is 1.96 × 10-7A/m2.It can be seen from the figure that the average collection electricity of gold nano hole sensor
Current density is greater than the average collected current density of gold-plated carbon nano tube sensor, the average collection electricity of gold-plated carbon nano tube sensor
Current density is greater than the average collected current density of carbon nanotube.The larger reason of gold nano hole sensor collected current density it
One, it is that sensor plate distributed quantity is more, the lesser aperture in aperture.Simulation result explanation, gold nano hole sensor structure have
Conducive to the extraction of cation, collected current is improved.
The present invention can detect sensor array, gold-plated carbon nano pipe array and the carbon nanotube sensing of multiple groups part mixed gas
The collected current of device array (patent publication No.: 102095791A) detection mixed gas and the comparison of sensitivity are as shown in table 1.Table
In 1, multiple groups part hybrid gas sensor array sensitivity of the present invention is the sensitivity of methane transducer；Gold-plated carbon nanotube sensing
The sensitivity of device array method for detecting concentration of mixed gas is the sensitivity of methane transducer；The mixing of carbon nano tube sensor array
The sensitivity of gas concentration detection method is the sensitivity of nitric oxide sensor.The present invention can detect multiple groups part mixed gas
The collected current of sensor array compares gold-plated carbon nano pipe array and improves an order of magnitude, and sensitivity improves a quantity
Grade；The collected current comparison carbon nano tube sensor array of the sensor array of detectable multiple groups part mixed gas improves three
The order of magnitude, sensitivity improve two orders of magnitude.Experimental result and simulation result illustrate that the present invention can detect multiple groups part gaseous mixture
The sensor array collected current of body is big, and high sensitivity has very strong advantage compared with existing detection technique.
Embodiment 2
The present embodiment basic structure is with embodiment 1, in the sensor array embodiments that can detect multiple groups part mixed gas, two
A sensor has an identical structure, different interpolars away from.Pole in the sensor array of detectable multiple groups part mixed gas
Spacing is set according to air hole, the side length in the aperture of fairlead and groove and groove depth.A kind of detectable multiple groups part mixed gas
In sensor array, the electrode surface of one of three electrode ionizing transducer first electrode of Jenner's metre hole film has 20 small
Air hole, aperture 0.8mm.There are 20 small fairleads, aperture 1.2mm in second electrode center.Third electrode has 1 length and width to be
6 × 8mm, 200 μm of deep trouth.At this point, between first electrode and second electrode interpolar away from small air hole and small fairlead diameter
The ratio between be respectively 3/20 and 1/10；Between second electrode and third electrode interpolar away from small fairlead diameter and collector deep trouth
The ratio between hole depth is respectively 1/10 and 3/5.
The electrode surface of another sensor first electrode has 20 small air holes, aperture 0.8mm.Second electrode center
There are 20 small fairleads, aperture 1.2mm.It is 6 × 8mm, 200 μm of deep trouth that third electrode, which has 1 length and width,.At this point, the first electricity
Interpolar is away from being respectively 3/20 and 1/10 with small air hole and small fairlead diameter ratio between pole and second electrode；Second electrode with
Interpolar is respectively 1/10 and 3/5 away from the ratio between the hole depth with small fairlead diameter and collector deep trouth between third electrode.
Interval is between two sensor array adjacent second electrode pole plates, between adjacent sensors third electrode pad
4mm。
It is as described in Example 1 that the present embodiment Jenner's metre hole is prepared into metallic film base step.
Embodiment 2 is identical as 1 experiment condition of embodiment, it can be reasonably determined that the sensor using embodiment 2 can obtain
Identical experiment effect, meets the requirements.
Embodiment 3
The present embodiment basic structure is with embodiment 1, in the sensor array embodiments that can detect multiple groups part mixed gas, two
A sensor has an identical structure, different interpolars away from.Interpolar in the sensor array of detectable multiple groups part mixed gas
Away from according to the aperture of air hole, fairlead and the setting of the side length of slot and groove depth.A kind of sensing of detectable multiple groups part mixed gas
In device array, the electrode surface of one of three electrode ionizing transducer first electrode of Jenner's metre hole film has 1 small ventilative
Hole, aperture 4mm.There are 1 small fairlead, aperture 6mm in second electrode center.Third electrode have 1 length and width be 6 × 8mm,
200 μm of deep trouth.At this point, between first electrode and second electrode interpolar away from small air hole and small fairlead diameter ratio difference
For 3/200 and 1/100；Between second electrode and third electrode interpolar away from the hole depth with small fairlead diameter and collector deep trouth it
Than being respectively 1/100 and 3/10.
The electrode surface of another sensor first electrode has 1 small air hole, aperture 4mm.Second electrode center has 1
A small fairlead, aperture 6mm.It is 6 × 8mm, 200 μm of deep trouth that third electrode, which has 1 length and width,.At this point, first electrode and the
Interpolar is away from being respectively 3/20 and 1/10 with small air hole and small fairlead diameter ratio between two electrodes；Second electrode and third electricity
Interpolar is respectively 1/10 and 3/5 away from the ratio between the hole depth with small fairlead diameter and collector deep trouth between pole.
Interval is between two sensor array adjacent second electrode pole plates, between adjacent sensors third electrode pad
8mm。
It is as described in Example 1 that the present embodiment Jenner's metre hole is prepared into metallic film base step.
Embodiment 3 is identical as 1 experiment condition of embodiment, it can be reasonably determined that the sensor using embodiment 3 can obtain
Identical experiment effect, meets the requirements.
Embodiment 4
The present embodiment can detect the sensor array (structure is as shown in Figure 1 and Figure 2) of multiple groups part mixed gas, by three gold
Three electrode ionizing transducer of nano-pore composition.The cathode of three sensors is produced on same pole plate, three extraction poles and
Collector structure having the same, three sensors have different interpolars away from.The sensor array of the present embodiment is without separation
Mixed gas can directly detect H2/C2H2/C2H4Concentration.Three sensors have an identical structure, different interpolars away from.This can
The interpolar in the sensor array of multiple groups part mixed gas is detected away from according to the aperture of air hole, fairlead and the side length of slot and slot
Deep setting.
In a kind of sensor array of detectable multiple groups part mixed gas, first three electrode ionization type of Jenner's metre hole film
The electrode surface of sensor first electrode has 2 small air holes, aperture 3mm.There are 9 small fairleads, hole in second electrode center
When diameter is 2mm.It is 1.2 × 1.2mm, 200 μm of deep trouth that third electrode, which has 1 length and width,.At this point, first electrode and second electrode it
Between interpolar away from being respectively 1/40 and 1/16 with small air hole and small fairlead diameter ratio；Pole between second electrode and third electrode
The ratio between spacing and the hole depth of small fairlead diameter and collector deep trouth are respectively 1/16 and 3/8.First Jenner's metre hole film three
Electrode ionizing transducer is for detecting C2H2Concentration.
The electrode surface of second three electrode ionizing transducer first electrode of Jenner's metre hole film has 2 small air holes,
Aperture is 3mm.There are 9 small fairleads at second electrode center, when aperture is 2mm.Third electrode have 1 length and width be 1.2 ×
1.2mm, 200 μm of deep trouth.At this point, between first electrode and second electrode interpolar away from small air hole and small fairlead diameter it
Than being respectively 3/100 and 3/40；Between second electrode and third electrode interpolar away from small fairlead diameter and collector deep trouth
The ratio between hole depth is respectively 3/40 and 9/20.Second three electrode ionizing transducer of Jenner's metre hole film is for detecting C2H4It is dense
Degree.
The electrode surface of three electrode ionizing transducer first electrode of third Jenner's metre hole film has 2 small air holes,
Aperture is 3mm.There are 9 small fairleads at second electrode center, when aperture is 2mm.Third electrode have 1 length and width be 1.2 ×
1.2mm, 200 μm of deep trouth.At this point, between first electrode and second electrode interpolar away from small air hole and small fairlead diameter it
Than being respectively 1/25 and 1/10；Interpolar is away from the hole with small fairlead diameter and collector deep trouth between second electrode and third electrode
The ratio between deep is respectively 1/10 and 3/5.Three electrode ionizing transducer of third Jenner's metre hole film is for detecting H2Concentration.
Interval is between three sensor array adjacent second electrode pole plates, between adjacent sensors third electrode pad
7mm。
It is as described in Example 1 that the present embodiment Jenner's metre hole is prepared into metallic film base step.
Embodiment 4 is identical as 1 experiment condition of embodiment, it can be reasonably determined that using the sensor of embodiment 4 without separation
Mixed gas can directly detect H2/C2H2/C2H4Concentration, meet the requirements.
The sensor array that the present invention can detect multiple groups part mixed gas is listed in cathode surface and is dispersed with Jenner's metre hole film, no
Only play the role of changing cathode conductive characteristic, has changed simultaneously field emission characteristic；Although extraction pole increases the quantity in hole but
It reduces aperture and changes field distribution, enhance Particle diffusion effect, more cations can be collected, reach increase and collect
Electric current improves the effect of sensitivity.A kind of sensor array of detectable multiple groups part mixed gas is listed in material, structure, preparation side
There is biggish improvement in method.
Following table 1 gives inventive sensor array detection multiple groups part hybrid gas sensor array, gold-plated carbon nanometer
When pipe array and carbon nano tube sensor array detection mixed gas, the comparison of collected current and sensitivity.
The wherein calculating formula of peak response:
(in formula: i-gas with various concentration point serial number, i >=2；Ii- sensor collection current average；- gas concentration
Value.)
Table 1
As can be seen from the above Table 1, the sensor array that the present invention detects multiple groups part mixed gas solves existing sensing
The problem of device collected current is smaller, causes sensitivity low, affects the performance of sensor.Collected current of the invention reaches
188.50nA, average sensitivity is up to 1.7 × 10-1NA/ppm, peak response reach 265.7nA/ppm.
Although the present invention is made that detailed description to the present invention with above-mentioned preferred embodiment, above-described embodiment is not
For limiting the present invention.In the case where not departing from technical characteristic given by technical solution of the present invention and range of structures, to skill
Increase made by art feature, deform or with the replacement of the same content in this field, protection scope of the present invention should all be belonged to.
Claims (6)
1. a kind of sensor array of detectable multiple groups part mixed gas, which is characterized in that include multiple and different interpolars in array
Away from three electrode ionizing transducer of Jenner's metre hole film；
The three electrode ionizing transducer of Jenner's metre hole film, including three first electrodes being sequentially distributed from bottom to top,
Two electrodes and third electrode, the first electrode are distributed the metallic film base of Jenner's metre hole by inner surface attachment and are equipped with
The electrode of small air hole is constituted；The second electrode is made of the small extraction pole that center is equipped with fairlead；The third electrode by
Plate face sets reeded collector and constitutes；It is mutually isolated that three electrodes pass through insulation column respectively；
Jenner's metre hole thin-film material is prepared using evaporation deposition method in the first electrode inner surface metallic film base；
Interpolar between three electrodes is away from according to the setting of small air hole, the side length in the aperture of small fairlead and groove and groove depth；
The aperture of the small air hole is 0.8~4mm, between corresponding first electrode and second electrode interpolar away from small air hole
The ratio between aperture is 3/200~3/20；The aperture of small fairlead is 1.2~6mm, interpolar between corresponding first electrode and second electrode
Be 1/100~1/10 away from the ratio between aperture with small fairlead, between second electrode and third electrode interpolar away from small fairlead
The ratio between aperture is 1/100~1/10；The side length of groove is 1.2 × 1.2~6 × 8mm, and groove depth is 200 μm, corresponding second electrode with
Interpolar is away from being 3/10~3/5 with the ratio between groove depth between third electrode；
The sensor array according to multiple three electrode ionizing transducers of Jenner's metre hole film and column distribution, all the sensors
First electrode is produced on same pole plate, between adjacent sensors second electrode pole plate, between third electrode pad according to setting
It is spaced apart.
2. the sensor array of detectable multiple groups part mixed gas according to claim 1, which is characterized in that the sensing
Interval is 3~8mm between device array adjacent sensors second electrode pole plate, between third electrode pad.
3. the sensor array of detectable multiple groups part mixed gas according to claim 1, which is characterized in that described first
The small air hole of the electrode surface of electrode is equipped with 1~20；
The small fairlead of the second electrode extraction pole 1~20；
The groove of the third electrode collector is equipped with 1.
4. a kind of gold of the three electrode ionizing transducer of Jenner's metre hole film of any one of claim 1-3 sensor array
The method that nano-pore is prepared into metallic film base, which is characterized in that include the following steps:
1) it is pre-processed before plated film: the silicon wafer for being etched with air hole being selected to pre-process as matrix and before carrying out plated film；
2) it sputters: successively sputtering titanium film, nickel film and golden film, three-layer thin-film thickness point on three substrates respectively under vacuum conditions
It Wei not 50nm, 400nm and 125nm；
3) it anneals: sputtering is had to silicon base 30~80s of short annealing of titanium nickel gold thin film, annealing temperature is 400~500 DEG C；
4) prepared by gold nano Porous materials: being 3 × 10 in vacuum degree-3Pa has in Ti/Ni/Au film silicon base in sputtering, using evaporation
Sedimentation grows Jenner's metre hole thin-film material, and it is highly 1.8 μm that the average-size of Jenner's metre hole, which is 350nm,；
5) microscopic appearance detection is carried out, completes the growth course of metallic film base Jenner metre hole thin-film material since then.
5. according to the method described in claim 4, it is characterized in that, in step 2), sputtering condition are as follows: vacuum degree is 2.5 × 10- 3Pa, sputter temperature are 30~40 DEG C, successively sputter titanium film, nickel film and golden film sputtering time be respectively 7min, 50min and
13min。
6. according to the method described in claim 4, it is characterized in that, evaporation deposition method grows Jenner's metre hole film in step 4)
Rate of material deposition is 1.5nm/s, sedimentation time 20min.
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| CN110243807B (en) * | 2019-07-10 | 2021-08-24 | 浙江农林大学 | Multifunctional gas sensor |
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