CN110261445A - One kind growing nanometer In based on nonmetallic mineral electrode substrate surface in situ2O3Room temperature NO2Sensor and preparation method - Google Patents
One kind growing nanometer In based on nonmetallic mineral electrode substrate surface in situ2O3Room temperature NO2Sensor and preparation method Download PDFInfo
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- CN110261445A CN110261445A CN201910627455.9A CN201910627455A CN110261445A CN 110261445 A CN110261445 A CN 110261445A CN 201910627455 A CN201910627455 A CN 201910627455A CN 110261445 A CN110261445 A CN 110261445A
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- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
The invention discloses one kind to grow nanometer In based on nonmetallic mineral electrode substrate surface in situ2O3Room temperature NO2Sensor and preparation method belong to the gas sensor domain of metal oxide semiconductor material.The present invention sputters interdigital electrode in substrate surface using nonmetallic mineral porous ceramic electrode as substrate, using DC sputtering, and grows In in its surface in situ using hydro-thermal method2O3Nano material, the In2O3Nano material is in club shaped structure, and is uniformly densely distributed in substrate surface, a diameter of 120~200nm, length is 0.5~1 μm, which mutually accumulate by nano particle forms, and the nano particle is In2O3Cubic phase crystal structure, a diameter of 10~30nm.The gas sensor can under the conditions of working and room temperature, and UV light auxiliary restore under, to 0.1~1ppm NO2With quick response and resume speed, and there is excellent selectivity and long-time stability, there is good application prospect.
Description
Technical field
The invention belongs to the gas sensor technical fields of metal oxide semiconductor material, and in particular to one kind has room
The nanometer In of the quick response characteristic of wet2O3Gas sensor and preparation method thereof, more particularly to one kind based on nonmetallic mineral electricity
Pole substrate surface growth in situ nanometer In2O3Room temperature NO2Sensor and preparation method.
Background technique
Nitrogen dioxide (NO2) it is the toxic irritative gas given off in vehicle exhaust and industrial processes, it is to be formed
One of acid rain and the main matter of photochemical pollution, even if the NO of 1ppm2Also very big harm can be caused to human body,
Therefore for low concentration of NO2Detection it is extremely necessary.Metal-oxide semiconductor (MOS) gas sensor because its high sensitivity, can be online
Real-time monitoring, the features such as miniaturization is easily integrated, portability is strong, are widely used for the detection of toxic and harmful gas.Currently, base
In WO3、SnO2, ZnO and In2O3The gas sensor of equal metal oxide nano-materials can be to low concentration of NO2With good
Gas-sensitive property, but their operating temperature requirements are generally all at 100-400 DEG C.Long-term hot operation, not only will increase energy
Consumption can also promote nanocrystal diauxic growth or occur to reunite that its pattern is made to change, the service life of gas sensor is caused to drop
It is low.In addition, elevated operating temperature is also easy to the flammable explosive gas that ignites, to limit the application range of such gas sensor.
Therefore, the NO under the conditions of working and room temperature in recent years2Sensor is always the hot spot and difficult point of air-sensitive research field.Mesh
Before, researcher always tries to take effective ways to reduce the operating temperature of gas sensor to room temperature condition, including
Appearance of nano material regulation, surface modification, precious metal doping, graphene be compound or the methods of UV auxiliary.But for reporting at present
Most of room temperature NO in road2For gas sensitive, still complicated, the at high cost, response/recovery time in the prevalence of synthesis technology
It is too long, or even the disadvantages of can not restore completely.Therefore, needing exploitation can work at room temperature with quick response/extensive
The NO of complex velocity2Sensor.The shortcomings that in order to overcome room temperature to restore slow or do not restore, it will usually use thermal pulse or UV spoke
The method penetrated is solved.However, using thermal pulse desorption gas reach recovery method be easy material is caused it is irreversible
Influence, this can have an impact the long-time stability of gas sensor；And UV radiation nano material surface can make gas
The gas ion and hydrone of sensor surface are quickly desorbed, to generate clean nano-material surface, make gas sensor
Resistance quickly recovers to initial value, to be conducive to the long-term circulate operation of gas sensor, and improves its stability.
In2O3It is a kind of very promising gas as semiconductor material with wide forbidden band (its forbidden bandwidth is 3.6eV at room temperature)
Quick material, it is particularly possible to low concentration of NO2Show good gas-sensitive property.Therefore, the In of different morphologies2O3Nanometer air-sensitive material
Material is successfully synthesized, such as stick, line, ball, block, flower-shaped and layering porous structure.Currently, being mostly based on In2O3The gas of nano material
Body sensor all using gas sensitive is first synthesized, is then coated onto gas sensing electrode element surface and is prepared into gas sensor
The shortcomings that mode, this technique is the orderly deposition that not can control material, its pattern is caused to change, so that it is long-term to influence it
Stability.Further, since the gas sensitive and electrode loose contact of preparation, also result in reproducibility variation.
Summary of the invention
For current In2O3Relative complex, the single deficiency of preparation method existing for gas sensor, and in room temperature item
To low concentration of NO under part2The problems such as response/resume speed of gas is slow, it is former based on porous ceramic electrode that the present invention provides one kind
Position growth nanometer In2O3NO2Sensor and preparation method thereof, and radiated in gas sensor Restoration stage by UV ultraviolet lamp
Gas sensitive surface achievees the effect that fast quick-recovery.
The power of UV ultraviolet lamp of the present invention is 6W, and wavelength 365nm, light source and sample distance are 40mm.
One kind being based on nonmetallic mineral porous ceramic electrode substrate surface growth in situ nanometer In2O3Room temperature NO2Sensing
Device, the nonmetallic mineral electrode substrate are nonmetallic mineral porous ceramic electrode substrate, the NO2Sensor is by non-
The In of metalliferous mineral porous ceramic electrode substrate surface growth in situ2O3Obtained by nano material；Wherein, the In2O3Nanometer material
Club shaped structure is presented in material, and is uniformly densely grown in electrode substrate surface, which mutually accumulated by nano particle
Composition；The nano particle is In2O3Cubic phase crystal structure；Club shaped structure 120~the 200nm of diameter, length are
0.5~1 μm, the nano-particle diameter is 10~30nm.
Preferably, the material of the nonmetallic mineral porous ceramic electrode substrate is the diatomite containing aluminosilicate ingredient
Or kaolin, porous processing is carried out using pore creating material hole forming method, pore creating material is ball-type graphite or PMMA microsphere, the pore creating material
Average diameter be 10~70 μm, adding proportion be 15~50wt.%, formed using moulding sintering process, firing temperature 1000
~1200 DEG C.
Preferably, the nonmetallic mineral porous ceramic electrode substrate length is 15~20mm, and width is 5~10mm, thick
Degree is 1~2mm.
Further, the present invention also provides one kind to be based on nonmetallic mineral porous ceramic electrode substrate surface growth in situ
Nanometer In2O3Room temperature NO2The preparation method of sensor, comprises the technical steps that:
1., by the method for d.c. sputtering, being covered in covering interdigital electrode using nonmetallic mineral porous ceramic electrode as substrate
The Ni film that the electrode substrate surface of template uses plasma sputtering instrument to sputter a layer thickness as 10~20nm, then sputter a thickness
Degree is the Au film of 50~100nm；
2. by InCl3·4H2O is dissolved in deionized water, is stirred evenly at room temperature, and 0.1~0.5mL oleic acid, room is then added
Temperature adds urea after mixing evenly, and stirs 5~15min, then goes to the mixed solution in ptfe autoclave,
Wherein, InCl3·4H2The concentration of O is 0.03~0.04mol/L, In3+The molar ratio of ion and urea is 1:8~1:12；
3. 1. nonmetallic mineral porous ceramic electrode substrate that step obtains is placed on ptfe autoclave vertically
In, place it in van-type resistance furnace and be heat-treated after sealing, with 10 DEG C/min be warming up to 60~100 DEG C and keep the temperature 6~
14h；
4. after reaction, taking out electrode substrate, and electrode substrate is rinsed well with deionized water, 80 DEG C of drying 1h；
It is placed in tube type resistance furnace, is warming up to 300~500 DEG C with 2 DEG C/min and keeps the temperature 1~2h, then naturally cool to room
Temperature；Take out electrode substrate, put it into air-sensitive test macro, will after test probe contacts with interdigital electrode, it is available with
In2O3Nano material is the room temperature NO of sensitive layer2Gas sensor.
Further, in above-mentioned technical proposal, the step 1. in interdigital electrode mask plate interdigital width be 0.2~
0.5mm, interdigital spacing are 0.2~0.5mm.
The invention has the benefit that
The present invention is in nonmetallic mineral porous ceramic electrode substrate surface growth in situ In2O3Nanometer stick array, and as gas
The air-sensitive coating of body sensor.Wherein, the use of porous ceramics substrate, not only can with the high high-purity silicon source of alternative cost or
The substrate of silicon source, porosity additionally aid the In in water-heat process2O3The isomery of nano material is nucleated, and increases nucleation site,
To improve the density of product.The increase of the density of product, can be because space crowding effect promotes the direction of growth of product to become
In consistent, to form fine and close nanometer stick array, and it is formed by In2O3Nanometer rods high ratio because its meso-hole structure makes it have
Surface area, and a large amount of reactivity site is provided, therefore can be at room temperature to low concentration of NO2With good sound
Answer characteristic.The fast quick-recovery of gas sensor may be implemented by the way that UV illumination is arranged, at the same keep excellent long-time stability and
Selectivity.In addition, the synthesis technology is simple, and hydrothermal temperature is lower than 100 DEG C, can effectively reduce the production cost of material.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of nonmetallic mineral porous ceramic electrode substrate used in the embodiment of the present invention 1~3；
Fig. 2 is the X ray diffracting spectrum of prepared product in the embodiment of the present invention 1；
Fig. 3 (3-1) is porous ceramics substrate surface In in the embodiment of the present invention 12O3The low range scanning electron microscopy of product
Mirror photo, (3-2) are the moderate multiplying factor electron scanning micrographs of product, and (3-3) is that the powerful scanning electron of product is aobvious
Micro mirror photo, the upper right corner are the electron scanning micrographs being further amplified, and (3-4) is porous ceramics substrate side angle
Electron scanning micrograph；
Fig. 4 (4-1) is the low range transmission electron microscope photo of single nanometer rods in the embodiment of the present invention 1, upper right
Angle is the selective electron diffraction map of nanometer rods Blocked portion；(4-2) is high resolution transmission electron microscopy photo, and (4-3) is
High magnification transmission electron microscope photo, (4-4) are the point-like electron energy spectrum diagrams of circled in (4-3)；
Fig. 5 (5-1) is the high-resolution x-ray photoelectron spectroscopy figure of In element in prepared product in the embodiment of the present invention 1；
(5-2) is the high-resolution x-ray photoelectron spectroscopy figure to O element；
Fig. 6 (6-1) be gas sensor prepared in the embodiment of the present invention 1 at 25 DEG C of room temperature to 800ppb NO2's
Response-recovery curve graph；(6-2) gas sensor is at 25 DEG C of room temperature to 800ppb NO2Response-recovery curve graph；
Fig. 7 (7-1) be gas sensor prepared in the embodiment of the present invention 1 at 25 DEG C of room temperature to various concentration NO2
Dynamic response-recovery curve figure；(7-2) gas sensor sensitivity and NO at 25 DEG C of room temperature2Relational graph between concentration；
Fig. 8 (8-1) be gas sensor prepared in the embodiment of the present invention 1 at 25 DEG C of room temperature to 800ppb NO2's
7 round robins-recovery curve figure, (8-2) gas sensor is at 25 DEG C of room temperature to 800ppb NO2Sensitivity and test
The relational graph of number of days；
Fig. 9 be gas sensor prepared in the embodiment of the present invention 1 at 25 DEG C of room temperature to different detected gas
Sensitivity.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1
Based on nonmetallic mineral material porous ceramic electrode substrate, structural schematic diagram is as shown in Figure 1.The electricity of substrate surface
Pole is that successively sputtering Ni and Au is thin respectively on the porous ceramics substrate for be covered with interdigital electrode mask plate by DC sputtering
Film formed, the Ni film thickness be 10nm, the Au film thickness be 50nm, the interdigital width be 0.5mm, interdigital
Away from for 0.5mm.
Specific sputter step is first to sputter layer of Ni film, sputtering current 17mA, sputtering time 120s；Then again
Sputter layer of Au film, sputtering current 10mA, sputtering time 230s；Wherein, sputtering environmental condition is equal are as follows: argon flow
200sccm, vacuum degree 90mTorr, sputtering use plasma sputtering instrument (Hefei Ke Jing Materials Technology Ltd., VTC-16-
3HD)。
The material of porous ceramic electrode substrate described in above-mentioned steps be kaolin, porous processing method using
Pore creating material hole forming method, pore creating material are PMMA microsphere, and average diameter is 30 μm, adding proportion 25wt.%；Its molding mode is to adopt
With moulding sintering process, firing temperature is 1200 DEG C.
The sintering schedule of the porous ceramic electrode substrate are as follows: be sintered using gradient heating, sintering schedule is with 5
DEG C/min from room temperature rises to 250 DEG C, keep the temperature 60min；450 DEG C are warming up to 1 DEG C/min again, keeps the temperature 60min；Again with 10 DEG C/min
1200 DEG C are warming up to, 90min is kept the temperature；Room temperature is finally down to 5 DEG C/min.
Porous ceramic electrode substrate a length of 20mm, width 10mm, thickness 2mm.
One kind being based on above-mentioned porous ceramic electrode substrate growth in situ nanometer In2O3NO2The preparation method of sensor, institute
It is as follows to state method:
1., by the method for d.c. sputtering, covering interdigital electricity using nonmetallic mineral material porous ceramic electrode as substrate
The Ni film that the substrate surface of pole mask plate uses plasma sputtering instrument to sputter a layer thickness as 10nm, then sputter a layer thickness and be
The Au film of 50nm；
2. by the InCl of 0.35g3·4H2O is dissolved in 36mL deionized water, stirs 10min at room temperature；Then it is added
0.25mL oleic acid, is stirred at room temperature 10min；1g urea is added, 10min is stirred, the mixed solution is finally poured into the poly- of 100mL
In tetrafluoroethene reaction kettle；
3. 1. nonmetallic mineral porous ceramic electrode substrate that step obtains is placed on ptfe autoclave vertically
In, it places it in van-type resistance furnace and is heat-treated after sealing, be warming up to 80 DEG C with 10 DEG C/min and keep the temperature 12h；
4. after reaction, taking out electrode substrate, and electrode substrate is rinsed well with deionized water, 80 DEG C of drying 1h；
It is placed in tube type resistance furnace, is warming up to 400 DEG C with 2 DEG C/min and keeps the temperature 1h, subsequent cooled to room temperature；Take out electricity
Pole substrate is put it into air-sensitive test macro, after test probe is contacted with interdigital electrode, can be obtained with In2O3Nano material
For the room temperature NO of sensitive layer2Gas sensor.
The air-sensitive test method is tested using (GB-T 15653-1995).
It is as shown in Figure 2 in the XRD spectrum of porous ceramics substrate surface obtained product using hydrothermal synthesis method.It can from Fig. 2
To find out, the diffraction maximum of product can correspond to the In of cubic phase crystal structure2O3(JCPDS NO.88-2160), without other
The peak of impurity occurs, and can prove that product crystallinity is good, with high purity.Fig. 3-1 and Fig. 3-2 is respectively porous ceramics pore structure table
Face In2O3The low range and moderate multiplying factor electron scanning micrograph of product, it can be seen that divide with having a large amount of product even compact
Cloth is in pore structure internal and external parts.Fig. 3-3 is the high magnification stereoscan photograph of product, it can be seen that club shaped structure is presented in product,
Diameter is 120~200nm；It can be seen that club shaped structure rough surface in conjunction with the enlarged photograph in the upper right corner, be by a large amount of nanometer
Particle is mutually accumulated and is formed, and particle diameter is 10~30nm.Fig. 3-4 is that the scanning electron microscope of product side view angle is shone
Piece, it can be seen that the diameter of nanometer rods is 0.5~1 μm, and nanometer rods and substrate are closely coupled.Fig. 4-1 is single in product receives
The low range transmission electron microscope photo of rice stick, it can be seen that the diameter of nanometer rods is 170nm, and surface is by a large amount of nanometer
Particle composition, this is consistent with the result of electron scanning micrograph；Its upper right corner is the constituency electricity of nanometer rods Blocked portion
Sub- diffracting spectrum, it was demonstrated that nanometer rods are polycrystalline structures.Fig. 4-2 is that the high resolution transmission electron microscopy of the single nanometer rods shines
Piece, spacing of lattice and cubic crystal In2O3Structure matches, and further proves its crystal structure.4-3 is high magnification transmission electricity
Sub- microscope photo, it can be seen that the nano-particle diameter for forming nanometer rods is 10nm or so, with scanning electron microscope result
It is consistent.Fig. 4-4 is the point-like electron energy spectrum diagram of circled in Fig. 4-3, it can be seen that nanometer rods are made of In and O element,
The peak of middle Cu and C element is from detection device.Fig. 5-1 is the high-resolution x-ray photoelectron spectroscopy of In element in obtained product
Scheme, the peak in figure positioned at 441.16eV and 451.76eV corresponds respectively to the 3d of In element5/2And 3d3/2Spin(-)orbit peak, shows
In in sample is In3+.Fig. 5-2 is the high-resolution x-ray photoelectron spectroscopy figure of O element in obtained product, is located in figure
The peak of 529.66eV and 531.31eV corresponds respectively to In2O3Lattice Oxygen (the O of nano wireⅠ) and surface adsorbed oxygen (OⅡ), wherein table
The content of face absorption oxygen directly affects the air-sensitive performance of material.
Fig. 6-1 is for prepared gas sensor at 25 DEG C of room temperature to 800ppb NO2Response-recovery curve graph.From
In figure as can be seen that when being passed through 800ppb NO2Afterwards, the resistance of gas sensor rises rapidly and tends towards stability, Sensitirity va1ue
It is 14.9, response time 14s；As discharge NO2Afterwards, the resistance of gas sensor fails to quickly recover to initial value.However, working as
After being irradiated in gas sensor surface using UV light, by can be seen that the resistance of gas sensor can fast quick-recovery in Fig. 6-2
To initial value, recovery time 32s illustrates that the gas sensor embodies good response-recovery characteristic under UV light auxiliary.
Fig. 7-1 be the gas sensor at 25 DEG C of room temperature to 0.1~1ppm NO2Dynamic response-recovery curve figure.It can from figure
To find out, the resistance variations of gas sensor are with NO2The increase of concentration is presented raised trend, corresponding sensitivity with
NO2Relationship between concentration is as shown in Fig. 7-2, to 100,200,400,600,800 and 1000ppb NO2Sensitirity va1ue difference
It is 1.4,1.6,3.8,8.4,14.9 and 20.8.Fig. 8-1 be the gas sensor at 25 DEG C of room temperature to 800ppb NO27 times
Round robin-recovery curve figure, it can be seen that its dynamic response-recovery curve feature is essentially identical；It is passed from Fig. 8-2 gas
Sensor is at 25 DEG C of room temperature to 800ppb NO2Sensitivity and test number of days relational graph can be seen that its Sensitirity va1ue fluctuation
It is smaller, show that the gas sensor has good repeatability and long-time stability.Fig. 9 is the gas sensor at 25 DEG C of room temperature
When sensitivity to different detected gas, as can be seen from the figure the gas sensor is to 1ppm NO2Sensitivity highest,
Sensitirity va1ue is 20.8, is significantly higher than 1000ppm H2And the Sensitirity va1ue of the other gases of 100ppm, show it in room temperature condition
Under to NO2With excellent gas-selectively.
Embodiment 2
Based on nonmetallic mineral material porous ceramic electrode substrate, structural schematic diagram is as shown in Figure 1.The electricity of substrate surface
Pole is that successively sputtering Ni and Au is thin respectively on the porous ceramics substrate for be covered with interdigital electrode mask plate by DC sputtering
What film was formed, the Ni film thickness is 10nm, and the Au film thickness is 50nm, and interdigital width is 0.5mm, and interdigital spacing is
0.5mm。
Specific sputter step is first to sputter layer of Ni film, sputtering current 17mA, sputtering time 120s；Then again
Sputter layer of Au film, sputtering current 10mA, sputtering time 230s；Wherein, sputtering environmental condition is equal are as follows: argon flow is
200sccm, vacuum degree are 90mTorr, and sputtering uses plasma sputtering instrument (Hefei Ke Jing Materials Technology Ltd., VTC-
16-3HD)。
The material of porous ceramic electrode substrate described in above-mentioned steps be diatomite, porous processing method using
Pore creating material hole forming method, pore creating material are PMMA microsphere, and average diameter is 50 μm, adding proportion 15wt.%；Its molding mode is to adopt
With moulding sintering process, firing temperature is 1000 DEG C.
The sintering schedule of the porous ceramic electrode substrate are as follows: be sintered using gradient heating, sintering schedule is with 5
DEG C/min from room temperature rises to 250 DEG C, keep the temperature 60min；450 DEG C are warming up to 1 DEG C/min again, keeps the temperature 60min；Again with 10 DEG C/min
1000 DEG C are warming up to, 180min is kept the temperature；Room temperature is finally down to 5 DEG C/min.
Porous ceramic electrode substrate a length of 20mm, width 10mm, thickness 2mm.
One kind being based on above-mentioned porous ceramic electrode substrate growth in situ nanometer In2O3NO2The preparation method of sensor, institute
It is as follows to state method:
1., by the method for d.c. sputtering, covering interdigital electricity using nonmetallic mineral material porous ceramic electrode as substrate
The Ni film that the substrate surface of pole mask plate uses plasma sputtering instrument to sputter a layer thickness as 10nm, then sputter a layer thickness and be
The Au film of 50nm；
2. by the InCl of 0.35g3·4H2O is dissolved in 36mL deionized water, stirs 10min at room temperature；Then it is added
0.25mL oleic acid, is stirred at room temperature 10min；1g urea is added, 10min is stirred, the mixed solution is finally poured into the poly- of 100mL
In tetrafluoroethene reaction kettle；
3. 1. nonmetallic mineral porous ceramic electrode substrate that step obtains is placed on ptfe autoclave vertically
In, it places it in van-type resistance furnace and is heat-treated after sealing, be warming up to 80 DEG C with 10 DEG C/min and keep the temperature 12h；
4. after reaction, taking out electrode substrate, and electrode substrate is rinsed well with deionized water, 80 DEG C of drying 1h；
It is placed in tube type resistance furnace, is warming up to 400 DEG C with 2 DEG C/min and keeps the temperature 1h, subsequent cooled to room temperature；Take out electricity
Pole substrate is put it into air-sensitive test macro, after test probe is contacted with interdigital electrode, can be obtained with In2O3Nano material
For the room temperature NO of sensitive layer2Gas sensor.
The air-sensitive test method is tested using (GB-T 15653-1995).
It is manufactured in the present embodiment to be based on In through detecting2O3The gas sensor of nano material at 25 DEG C of room temperature to 0.1~
1ppm NO2With good gas-sensitive property.
Embodiment 3
Based on nonmetallic mineral material porous ceramic electrode substrate, structural schematic diagram is as shown in Figure 1.The electricity of substrate surface
Pole is that successively sputtering Ni and Au is thin respectively on the porous ceramics substrate for be covered with interdigital electrode mask plate by DC sputtering
What film was formed, the Ni film thickness is 10nm, and the Au film thickness is 50nm, interdigital width is 0.5mm, interdigital spacing
For 0.5mm.
Specific sputter step is first to sputter layer of Ni film, sputtering current 17mA, sputtering time 120s；Then again
Sputter layer of Au film, sputtering current 10mA, sputtering time 230s；Wherein, sputtering environmental condition is equal are as follows: argon flow is
200sccm, vacuum degree 90mTorr, sputtering use plasma sputtering instrument (Hefei Ke Jing Materials Technology Ltd., VTC-16-
3HD)。
The material of porous ceramic electrode substrate described in above-mentioned steps be diatomite, porous processing method using
Pore creating material hole forming method, pore creating material are ball-type graphite, and average diameter is 24 μm, adding proportion 40wt.%；Its molding mode is to adopt
With moulding sintering process, firing temperature is 1000 DEG C.
The sintering schedule of the porous ceramic electrode substrate are as follows: be sintered using gradient heating, sintering schedule is with 10
DEG C/min from room temperature rises to 500 DEG C, keep the temperature 30min；1000 DEG C are warming up to 1.5 DEG C/min again, keeps the temperature 3h；Finally with 5 DEG C/
Min is down to room temperature.
Porous ceramics substrate a length of 20mm, width 10mm, thickness 2mm.
One kind being based on above-mentioned porous ceramic electrode substrate growth in situ nanometer In2O3NO2The preparation method of sensor, institute
It is as follows to state method:
1., by the method for d.c. sputtering, covering interdigital electricity using nonmetallic mineral material porous ceramic electrode as substrate
The Ni film that the substrate surface of pole mask plate uses plasma sputtering instrument to sputter a layer thickness as 10nm, then sputter a layer thickness and be
The Au film of 50nm；
2. by the InCl of 0.35g3·4H2O is dissolved in 36mL deionized water, stirs 10min at room temperature；Then it is added
0.25mL oleic acid, is stirred at room temperature 10min；1g urea is added, 10min is stirred, the mixed solution is finally poured into the poly- of 100mL
In tetrafluoroethene reaction kettle；
3. 1. nonmetallic mineral porous ceramic electrode substrate that step obtains is placed on ptfe autoclave vertically
In, it places it in van-type resistance furnace and is heat-treated after sealing, be warming up to 80 DEG C with 10 DEG C/min and keep the temperature 12h；
4. after reaction, taking out electrode substrate, and electrode substrate is rinsed well with deionized water, 80 DEG C of drying 1h；
It is placed in tube type resistance furnace, is warming up to 400 DEG C with 2 DEG C/min and keeps the temperature 1h, subsequent cooled to room temperature；Take out electricity
Pole substrate is put it into air-sensitive test macro, after test probe is contacted with interdigital electrode, can be obtained with In2O3Nano material
For the room temperature NO of sensitive layer2Gas sensor.
The air-sensitive test method is tested using (GB-T 15653-1995).
It is manufactured in the present embodiment to be based on In through detecting2O3The gas sensor of nano material at 25 DEG C of room temperature to 0.1~
1ppm NO2With good gas-sensitive property.
Claims (5)
1. one kind grows nanometer In based on nonmetallic mineral electrode substrate surface in situ2O3Room temperature NO2Sensor and preparation side
Method, it is characterised in that: the nonmetallic mineral electrode substrate is nonmetallic mineral porous ceramic electrode substrate, the NO2Sensing
Device is by the In in nonmetallic mineral porous ceramic electrode substrate surface growth in situ2O3Obtained by nano material；Wherein, described
In2O3Club shaped structure is presented in nano material, and is uniformly densely grown in electrode substrate surface, and the club shaped structure is by receiving
Rice grain mutually accumulates composition；The nano particle is In2O3Cubic phase crystal structure；The club shaped structure diameter is
120~200nm, length are 0.5~1 μm, and the nano-particle diameter is 10~30nm.
2. room temperature NO according to claim 12Sensor, it is characterised in that: the nonmetallic mineral porous ceramic electrode lining
The material at bottom is diatomite or kaolin containing aluminosilicate ingredient, carries out porous processing using pore creating material hole forming method, makes
Hole agent is ball-type graphite or PMMA microsphere, and the average diameter of the pore creating material is 10~70 μm, adding proportion is 15~
50wt.% is formed using moulding sintering process, and firing temperature is 1000~1200 DEG C.
3. room temperature NO according to claim 12Sensor, it is characterised in that: the nonmetallic mineral porous ceramic electrode lining
The length at bottom is 15~20mm, and width is 5~10mm, with a thickness of 1~2mm.
4. room temperature NO described in claim 12The preparation method of sensor, it is characterised in that: comprise the technical steps that:
1. using nonmetallic mineral porous ceramic electrode as substrate, by the method for d.c. sputtering, in covering interdigital electrode mask plate
The electrode substrate surface Ni film that uses plasma sputtering instrument to sputter a layer thickness as 10~20nm, then sputter a layer thickness and be
The Au film of 50~100nm；
2. by InCl3·4H2O is dissolved in deionized water, is stirred evenly at room temperature, and 0.1~0.5mL oleic acid is then added, and room temperature is stirred
Urea is added after mixing uniformly, and stirs 5~15min, then goes to the mixed solution in ptfe autoclave,
In, InCl3·4H2The concentration of O is 0.03~0.04mol/L, In3+The molar ratio of ion and urea is 1:8~1:12；
3. 1. nonmetallic mineral porous ceramic electrode substrate that step obtains is placed in ptfe autoclave vertically, it is close
It is honored as a queen to place it in van-type resistance furnace and be heat-treated, be warming up to 60~100 DEG C with 10 DEG C/min and keep the temperature 6~14h；
4. after reaction, taking out electrode substrate, and electrode substrate is rinsed well with deionized water, 80 DEG C of drying 1h；By its
It is placed in tube type resistance furnace, is warming up to 300~500 DEG C with 2 DEG C/min and keeps the temperature 1~2h, subsequent cooled to room temperature；It takes
Electrode substrate out is put it into air-sensitive test macro, after test probe is contacted with interdigital electrode, can be obtained with In2O3Nanometer
Material is the room temperature NO of sensitive layer2Gas sensor.
5. the preparation method according to claim 4, it is characterised in that: the step 1. in interdigital electrode mask plate fork
Finger widths are 0.2~0.5mm, and interdigital spacing is 0.2~0.5mm.
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