CN107817279B - A kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor - Google Patents
A kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor Download PDFInfo
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- CN107817279B CN107817279B CN201710897155.3A CN201710897155A CN107817279B CN 107817279 B CN107817279 B CN 107817279B CN 201710897155 A CN201710897155 A CN 201710897155A CN 107817279 B CN107817279 B CN 107817279B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- 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
Abstract
Invention is related to a kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor and preparation method thereof belongs to the gas sensor technical field of one-dimensional metal oxide semiconductor material.A kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor, the sensor are made of electrode member and uniform growth in situ in the NiO film of electrode element surface, wherein the NiO film is made of NiO crystal grain, and the NiO crystal grain is face-centered cubic phase crystal structure, and diameter is 20~30nm.The gas sensor is obtained when operating temperature is 150 DEG C to NO2Peak response, response and recovery time are short, and selectivity is high, and long-time stability are good, the deficiencies of INVENTIONConventional metal-oxide semiconductor-type gas sensor preparation process flow is complicated, selectivity is poor with long-time stability is efficiently solved, is the NO with good development prospect2Gas sensor.
Description
Technical field
The present invention relates to a kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor and preparation method thereof,
Belong to the gas sensor technical field of one-dimensional metal oxide semiconductor material.
Background technique
With the development of society and the progress of science and technology, people's lives quality has occurred revolutionary variation, but with
The various negative issues of bring also constantly highlight simultaneously for this.In recent years, haze, greenhouse effects, acid rain etc. threaten people's body strong
The phenomenon that health, constantly aggravates, and gas leak, gas explosion, gassing etc. threaten the accident of people's life security to occur again and again,
So that people constantly promote the demand of pollution, danger, the detection and alarm of pernicious gas, to sense to high performance gas
The development of device proposes the more urgently requirement with harshness.
There are many type of gas sensor at present, can be divided into semiconductor-type gas sensing according to gas sensitive and action effect
Device, electrochemical gas sensor, solid electrolyte formula gas sensor, catalytic combustion type gas sensor, optical type gas
Sensor, high score minor gas sensor etc..Wherein, metal-oxide semiconductor (MOS) formula gas sensor is due to response speed
Fastly, high sensitivity, the advantages that detection gas concentration limit is low, all solid state, small in size, are a kind of gas being most widely used at present
Body sensor.The working environment of gas sensor is complicated, usually contains a variety of toxic and harmful gas, metal oxide is partly led
For body gas sensor, poor gas-selectively is always to restrict an important factor for it further develops.
NiO is a kind of p-type broad stopband metal oxide semiconductor material, and forbidden bandwidth is in 3.6~4.0eV or so.
NiO material has very excellent electronic transmission performance and chemical stability, in electrochromism, catalysis, magnetic material, battery, gas
The fields such as sensor have all shown good application prospect.Due to its gas sensitivity with higher, low cost, with it is various
The advantages that nanometer technique is preferably compatible, had once been considered as one of the best candidate of gas sensitive.Gas sensitive element at present
The preparation method of part is substantially the gas sensitive that will be prepared in advance and is manually applied on electrode, so that gas sensitive and base
Hardened resultant force is poor, poor so as to cause the long-time stability of gas sensor.
Summary of the invention
For current metal-oxide semiconductor (MOS) formula gas sensor in terms of gas-selectively and long-time stability not
Foot, the present invention provide a kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor and preparation method thereof.Purpose
It is to lift coating method by sol-gel to go out in electrode surface growth in situ that surface topography is uniform, property is stable, loose porous
NiO nano thin-film, and it is prepared into the NO with highly selective, excellent long-time stability2Sensor, to overcome existing sensor to select
The deficiencies of selecting property is not high, long-time stability are poor.
A kind of NO2Sensor, the sensor by electrode member and uniform growth in situ electrode element surface NiO
Film composition,
Wherein, the NiO film is made of NiO crystal grain, and the NiO crystal grain is face-centered cubic phase crystal knot
Structure, diameter are 20~30nm.
NO of the present invention2Sensor, the NiO nano thin-film are detection NO2The gas sensitive of gas.
In above-mentioned technical proposal, the NiO nano thin-film architectural characteristic uniform, loose porous with surface topography.
In above-mentioned technical proposal, the material of the preferably described electrode member is Al2O3Ceramic material or gold.
In above-mentioned technical proposal, the shape of the preferably described electrode member is tubulose or plane.
Further, the most preferably described electrode member is tubular ceramic element or plane gold dollar part.
In above-mentioned technical proposal, the preferably described sensor is by electrode element surface growth in situ NiO nano thin-film
Gained.
Further, the method for the growth in situ NiO nano thin-film are as follows: using lifting coating method in electrode element surface
NiO colloidal sol is coated, it is dry；The electrode member that surface is coated with NiO colloidal sol is heat-treated, condition are as follows: with 3 DEG C/min's
Heating rate is heated to 500 DEG C and keeps 1h；Aging for 24 hours, both obtained at 250~300 DEG C.
Further, the NiO colloidal sol is made as follows: at room temperature, second two being added into nickel acetate tetrahydrate
Alcohol methyl ether, stirring, is completely dissolved in nickel acetate tetrahydrate among ethylene glycol monomethyl ether；Solution will be formed by 60 DEG C of stirring 2h,
And the ammonium hydroxide of 25~28wt.% is added dropwise dropwise into solution；Sealing is aged for 24 hours at room temperature, and filtering obtains NiO colloidal sol,
Wherein, nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio be 5~7:5~7:100.
In above-mentioned technical proposal, the nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio in ammonium hydroxide amount with ammonia
Solute meter in water.
Further, the lifting film carries out in pulling coating machine, is dried after film, the lifting film
Parameter is arranged in machine are as follows: stroke 6cm, decrease speed 300~500 μm/s, 30~60s of quiescent time, 300~400 μ of the rate of climb
m/s；If you need to increase the film number of plies, then repeat the above steps.
Compared with prior art, the features of the present invention and excellent effect are:
The present invention provides one kind based on electrode surface growth in situ, preparation method is simple, selectivity is high, long-time stability
The NiO nano thin-film NO of the advantages that good2Sensor and preparation method thereof.From preparation method, the present invention passes through colloidal sol-first
Gel method has gone out layer of Ni O nano thin-film in electrode surface growth in situ, is then prepared into gas sensor by aging process.
The gas sensor is obtained when operating temperature is 150 DEG C to NO2Peak response, response and recovery time it is short, selectivity
Height, long-time stability are good, efficiently solve INVENTIONConventional metal-oxide semiconductor-type gas sensor preparation process flow complexity, choosing
The deficiencies of selecting property and long-time stability are poor, is the NO with good development prospect2Gas sensor.
Detailed description of the invention
Fig. 1 is the NO based on tubular ceramic electrode surface growth in situ NiO nano thin-film in embodiment 1 and embodiment 22
The structural schematic diagram of sensor.Wherein, 1:Al2O3Ceramic tube；2:NiO air-sensitive coating；3: resistive heater；4: gold electrode；5: platinum
Gold wire.
Fig. 2 is the X ray diffracting spectrum of NiO nano thin-film prepared by the present invention；
Fig. 3 is (a) low range and (b) high magnification electron scanning micrograph of NiO nano thin-film prepared by the present invention；
Fig. 4 is the transmission electron microscope figure of the NiO crystal grain prepared by the present invention for constituting NiO nano thin-film；
Fig. 5 is gas sensor prepared by the present invention to 20ppm NO2Sensitivity and operating temperature between relational graph；
Fig. 6 be gas sensor prepared by the present invention when operating temperature is 150 DEG C to various concentration NO2Dynamic response
Curve graph；
Fig. 7 is gas sensor prepared by the present invention sensitivity and NO when operating temperature is 150 DEG C2Between gas concentration
Relational graph；
Fig. 8 be gas sensor prepared by the present invention when operating temperature is 150 DEG C to the sensitive of different detected gas
Degree figure；
Fig. 9 be gas sensor prepared by the present invention when operating temperature is 150 DEG C to 20ppm NO2Sensitivity at any time
Between variation diagram；
Figure 10 is the NO based on plane gold electrode surfaces growth in situ NiO nano thin-film in embodiment 3 and embodiment 42It passes
Sensor component schematic diagram；Wherein: 6: plane Al2O3Ceramic substrate；7:NiO air-sensitive coating；8: adding thermal resistance；9: gold electrode；10:
Platinum lead.
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.
Air-sensitive test macro described in following embodiments is bright Sheng science and technology WS-30A type air-sensitive test macro；The agingtable
For bright Sheng science and technology TS-60 type agingtable.
Following NO as described in the examples2Sensor is obtained by following preparation methods:
(1) quantitative nickel acetate tetrahydrate is weighed with electronic balance to be put into triangular flask, added with pipette into triangular flask
Enter quantitative ethylene glycol monomethyl ether, 3h then, which is mixed, with magnetic stirring apparatus at room temperature makes nickel acetate tetrahydrate be completely dissolved in second
Among glycol methyl ether.Solution will be formed by and stir 2h in 60 DEG C of constant temperature water baths, and be added dropwise dropwise into solution a certain amount of
Ammonium hydroxide as stabilizer/complexing agent.Wherein, nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio be 5~7:5~7:
100.Triangular flask sealing is taken out later, is aged obtains NiO colloidal sol for 24 hours at room temperature.The qualitative filter of NiO colloidal sol middling speed that will be obtained
Paper filtering, sealing are stand-by.
(2) it will be cleaned up with deionized water and ethanol solution to the electrode member of film, be then fixed in respectively
The substrate bearing of pulling coating machine, while the beaker for filling stand-by NiO colloidal sol being put into the material cup rest area of pulling coating machine.
(3) relevant parameter of setting pulling coating machine: stroke 6cm, 300~500 μm/s of decrease speed, quiescent time 30~
Then 60s, 300~400 μm/s of the rate of climb start to carry out lifting film.After lifting film, electrode is placed in electric heating drum
In wind drying box, dry 30min, takes out be cooled to room temperature later under the conditions of 80 DEG C.If you need to increase the film number of plies, then repeat
State step (3).
(4) electrode for being coated with NiO film is put into tube furnace, with the heating rate heated Tube-furnace of 3 DEG C/min to 500
DEG C and keep 1h.After tube furnace is cooled to room temperature, layer of Ni O nano thin-film can be obtained on the electrode.
(5) electrode member is soldered in the detection pedestal of air-sensitive test macro, is placed on agingtable in 300 DEG C of conditions
Lower aging is for 24 hours to get final gas sensor.
Embodiment 1
NO based on tubular ceramic electrode surface growth in situ NiO nano thin-film2Sensor element, structural schematic diagram is such as
Shown in Fig. 1, by Al2O3Ceramic tube, gold electrode, platinum lead, resistive heater and air-sensitive material layer composition.Gold electrode is overlayed on
Al2O3Ceramic pipe surface constitutes ceramic electrode, and platinum lead is welded on gold electrode surfaces, and resistive heater is transverse in Al2O3Ceramics
Guan Zhong, gas sensitive are grown in entire Al2O3Ceramic tube and gold electrode surfaces.The gas sensitive ingredient is NiO nanometer thin
Film is evenly distributed and is grown in ceramic electrode surface, the face-centered cubic phase NiO that NiO nano thin-film is 20~30nm by diameter
Crystal grain is constituted, and film surface appearance is uniform, loose porous.
A kind of NO based on tubular ceramic electrode surface growth in situ NiO nano thin-film2Sensor and preparation method thereof is pressed
It is carried out according to following steps:
(1) quantitative nickel acetate tetrahydrate is weighed with electronic balance to be put into triangular flask, added with pipette into triangular flask
Enter quantitative ethylene glycol monomethyl ether, 3h then, which is mixed, with magnetic stirring apparatus at room temperature makes nickel acetate tetrahydrate be completely dissolved in second
Among glycol methyl ether.Solution will be formed by and stir 2h in 60 DEG C of constant temperature water baths, and be added dropwise dropwise into solution a certain amount of
Ammonium hydroxide as stabilizer/complexing agent.Wherein, nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio be 1:1:20 (ammonia
For the amount of water in terms of solute, other embodiments are same).Triangular flask sealing is taken out later, is aged obtains NiO colloidal sol for 24 hours at room temperature.It will
Obtained NiO colloidal sol middling speed qualitative filter paper filtering, sealing are stand-by.
(2) by the ceramic electrode of film, (gold electrode overlays on Al2O3The electrode member that ceramic pipe surface is constituted) it spends respectively
Ionized water and ethanol solution clean up, and are then fixed in the substrate bearing of pulling coating machine, while will fill stand-by
The beaker of NiO colloidal sol is put into the material cup rest area of pulling coating machine.
(3) relevant parameter of pulling coating machine is arranged: stroke 6cm, decrease speed 500 μm/s, quiescent time 30s rise
Then 400 μm/s of speed starts to carry out lifting film.After lifting film, ceramic electrode is placed in electric drying oven with forced convection
In, dry 30min, takes out be cooled to room temperature later under the conditions of 80 DEG C.It repeats step (3) and carries out film next time.
(4) ceramic electrode for being coated with 2 layers of NiO film is put into tube furnace, with the heating rate heated Tube of 3 DEG C/min
Furnace is to 500 DEG C and keeps 1h.After tube furnace is cooled to room temperature, layer of Ni O nano thin-film can be obtained on ceramic electrode.
(5) ceramic electrode element is soldered in the detection pedestal of air-sensitive test macro, is placed on agingtable 300
Aging is for 24 hours to get final gas sensor under the conditions of DEG C.
The X ray diffracting spectrum of NiO nano thin-film is as shown in Figure 2.It can be seen from the figure that the NiO of electrode surface growth
For face-centered cubic phase crystal structure, diffraction maximum peak shape is sharp, and halfwidth is smaller, and the diffraction maximum without any other impurity, shows
NiO crystallinity is preferably and purity is higher.The scanning electron microscope (SEM) photograph of NiO nano thin-film is as shown in Figure 3.It can be seen from the figure that NiO receives
Rice film is made of small NiO crystal grain, and surface topography is uniform and loose porous.Fig. 4 is the NiO crystalline substance for constituting NiO nano thin-film
The transmission electron microscope figure of grain.As can be seen from the figure the diameter for constituting the NiO crystal grain of NiO nano thin-film is 20~30nm.
NO based on ceramic electrode surface in situ growth NiO nano thin-film2Sensor is to 20ppm NO2Sensitivity and work
The relationship for making temperature is as shown in Figure 5.It can be seen from the figure that the sensor is obtained when operating temperature is 150 DEG C to NO2Most
Atmospheric sensitivity.Fig. 6 is for the sensor at 150 DEG C of operating temperature to various concentration NO2Dynamic response curve.From figure
As can be seen that the sensor response/recovery time it is shorter and have good invertibity and stability, while increased resistance value with
NO2The reduction of concentration and reduce, show its sensitivity and NO2Concentration correlation, the sensor as shown in Figure 7 exist
Sensitivity and NO when operating temperature is 150 DEG C2Relationship between concentration more can clearly be found out.
NO based on tubular ceramic electrode surface growth in situ NiO nano thin-film2Sensitivity of the sensor to gas with various
As shown in Figure 8.As can be seen from Figure 8, the sensor is to 10ppm NO2Sensitivity much higher than to 1000ppm, other are common
The sensitivity of toxic and harmful gas shows preferable gas-selectively.This shows the sensor in complicated gaseous environment
In can be to NO2Effectively identified, shows preferable actual application prospect.Fig. 9 is the sensor to 20ppm NO2's
Sensitivity versus time curve.It can be seen from the figure that the sensor its change of sensitivity range in 30 days is smaller,
Good stability is shown, can preferably overcome the shortcomings of that existing sensor long-time stability are poor.
Embodiment 2
NO based on tubular ceramic electrode surface growth in situ NiO nano thin-film2Sensor element, structural schematic diagram is such as
Shown in Fig. 1, by Al2O3Ceramic tube, gold electrode, platinum lead, resistive heater and air-sensitive material layer composition.Gold electrode is overlayed on
Al2O3Ceramic pipe surface constitutes ceramic electrode, and platinum lead is welded on gold electrode surfaces, and resistive heater is transverse in Al2O3Ceramics
Guan Zhong, gas sensitive are grown in entire Al2O3Ceramic tube and gold electrode surfaces.The gas sensitive ingredient is NiO nanometer thin
Film is evenly distributed and is grown in ceramic electrode surface, the face-centered cubic phase NiO that NiO nano thin-film is 20~30nm by diameter
Crystal grain is constituted, and film surface appearance is uniform, loose porous.
A kind of NO based on tubular ceramic electrode surface growth in situ NiO nano thin-film2Sensor and preparation method thereof is pressed
It is carried out according to following steps:
(1) quantitative nickel acetate tetrahydrate is weighed with electronic balance to be put into triangular flask, added with pipette into triangular flask
Enter quantitative ethylene glycol monomethyl ether, 3h then, which is mixed, with magnetic stirring apparatus at room temperature makes nickel acetate tetrahydrate be completely dissolved in second
Among glycol methyl ether.Solution will be formed by and stir 2h in 60 DEG C of constant temperature water baths, and be added dropwise dropwise into solution a certain amount of
Ammonium hydroxide as stabilizer/complexing agent.Wherein, nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio be 7:7:100.It
Triangular flask sealing is taken out afterwards, is aged obtains NiO colloidal sol for 24 hours at room temperature.The NiO colloidal sol middling speed qualitative filter paper mistake that will be obtained
Filter, sealing are stand-by.
(2) by the ceramic electrode of film, (gold electrode overlays on Al2O3The electrode member that ceramic pipe surface is constituted) it spends respectively
Ionized water and ethanol solution clean up, and are then fixed in the substrate bearing of pulling coating machine, while will fill stand-by
The beaker of NiO colloidal sol is put into the material cup rest area of pulling coating machine.
(3) relevant parameter of pulling coating machine is arranged: stroke 6cm, decrease speed 300 μm/s, quiescent time 60s rise
Then 300 μm/s of speed starts to carry out lifting film.After lifting film, ceramic electrode is placed in electric drying oven with forced convection
In, dry 30min, takes out be cooled to room temperature later under the conditions of 80 DEG C.
(4) ceramic electrode for being coated with 1 layer of NiO film is put into tube furnace, with the heating rate heated Tube of 3 DEG C/min
Furnace is to 500 DEG C and keeps 1h.After tube furnace is cooled to room temperature, layer of Ni O nano thin-film can be obtained on ceramic electrode.
(5) ceramic electrode element is soldered in the detection pedestal of air-sensitive test macro, is placed on agingtable 300
Aging is for 24 hours to get final gas sensor under the conditions of DEG C.
Through detecting, the NO manufactured in the present embodiment based on NiO nano thin-film2Sensor is in 100~200 DEG C of items of operating temperature
To NO under part2With good gas-sensitive property
Embodiment 3
NO based on plane gold electrode surfaces growth in situ NiO nano thin-film2Sensor element, structural schematic diagram is as schemed
Shown in 10, by plane Al2O3Ceramic substrate, gold electrode, platinum lead, adding thermal resistance and air-sensitive material layer composition.Gold electrode is covered
In plane Al2O3Ceramic base plate surface constitutes plane gold electrode, and platinum lead is welded on gold electrode surfaces, and adding thermal resistance overlays on flat
Face Al2O3The ceramic substrate back side, gas sensitive are grown in entire plane Al2O3Ceramic substrate and gold electrode surfaces.The air-sensitive
Material composition is NiO nano thin-film, and uniform distribution is grown in electrode element surface, NiO nano thin-film by diameter be 20~
The face-centered cubic phase NiO crystal grain of 30nm is constituted, and film surface appearance is uniform, loose porous.
A kind of NO based on plane gold electrode surfaces growth in situ NiO nano thin-film2Sensor and preparation method thereof, according to
Following steps carry out:
(1) quantitative nickel acetate tetrahydrate is weighed with electronic balance to be put into triangular flask, added with pipette into triangular flask
Enter quantitative ethylene glycol monomethyl ether, 3h then, which is mixed, with magnetic stirring apparatus at room temperature makes nickel acetate tetrahydrate be completely dissolved in second
Among glycol methyl ether.Solution will be formed by and stir 2h in 60 DEG C of constant temperature water baths, and be added dropwise dropwise into solution a certain amount of
Ammonium hydroxide as stabilizer/complexing agent.Wherein, nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio be 1:1:20.It
Triangular flask sealing is taken out afterwards, is aged obtains NiO colloidal sol for 24 hours at room temperature.The NiO colloidal sol middling speed qualitative filter paper mistake that will be obtained
Filter, sealing are stand-by.
(2) by the plane gold electrode of film, (gold electrode overlays on plane Al2O3The electrode member that ceramic base plate surface is constituted)
It is cleaned up respectively with deionized water and ethanol solution, is then fixed in the substrate bearing of pulling coating machine, simultaneously will
The beaker for filling stand-by NiO colloidal sol is put into the material cup rest area of pulling coating machine.
(3) relevant parameter of pulling coating machine is arranged: stroke 6cm, decrease speed 500 μm/s, quiescent time 30s rise
Then 400 μm/s of speed starts to carry out lifting film.After lifting film, electrode is placed in electric drying oven with forced convection, In
Dry 30min, takes out be cooled to room temperature later under the conditions of 80 DEG C.It repeats step (3) and carries out film next time.
(4) the plane gold electrode for being coated with 2 layers of NiO film is put into tube furnace, with the heating rate heating tube of 3 DEG C/min
Formula furnace is to 500 DEG C and keeps 1h.After tube furnace is cooled to room temperature, layer of Ni O nanometer thin can be obtained on plane gold electrode
Film.
(5) plane gold electrode element is soldered in the detection pedestal of air-sensitive test macro, is placed on agingtable
Aging is for 24 hours to get final gas sensor under the conditions of 300 DEG C.
Through detecting, the NO manufactured in the present embodiment based on NiO nano thin-film2Sensor is in 100~200 DEG C of items of operating temperature
To NO under part2With good gas-sensitive property.
Embodiment 4
NO based on plane gold electrode surfaces growth in situ NiO nano thin-film2Sensor element, structural schematic diagram is as schemed
Shown in 10, by plane Al2O3Ceramic substrate, gold electrode, platinum lead, adding thermal resistance and air-sensitive material layer composition.Gold electrode is covered
In plane Al2O3Ceramic base plate surface constitutes plane gold electrode, and platinum lead is welded on gold electrode surfaces, and adding thermal resistance overlays on flat
Face Al2O3The ceramic substrate back side, gas sensitive are grown in entire plane Al2O3Ceramic substrate and gold electrode surfaces.The air-sensitive
Material composition is NiO nano thin-film, and uniform distribution is grown in electrode element surface, NiO nano thin-film by diameter be 20~
The face-centered cubic phase NiO crystal grain of 30nm is constituted, and film surface appearance is uniform, loose porous.
A kind of NO based on plane gold electrode surfaces growth in situ NiO nano thin-film2Sensor and preparation method thereof, according to
Following steps carry out:
(1) quantitative nickel acetate tetrahydrate is weighed with electronic balance to be put into triangular flask, added with pipette into triangular flask
Enter quantitative ethylene glycol monomethyl ether, 3h then, which is mixed, with magnetic stirring apparatus at room temperature makes nickel acetate tetrahydrate be completely dissolved in second
Among glycol methyl ether.Solution will be formed by and stir 2h in 60 DEG C of constant temperature water baths, and be added dropwise dropwise into solution a certain amount of
Ammonium hydroxide as stabilizer/complexing agent.Wherein, nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio be 7:7:100.It
Triangular flask sealing is taken out afterwards, is aged obtains NiO colloidal sol for 24 hours at room temperature.The NiO colloidal sol middling speed qualitative filter paper mistake that will be obtained
Filter, sealing are stand-by.
(2) by the plane gold electrode of film, (gold electrode overlays on plane Al2O3The electrode member that ceramic base plate surface is constituted)
It is cleaned up respectively with deionized water and ethanol solution, is then fixed in the substrate bearing of pulling coating machine, simultaneously will
The beaker for filling stand-by NiO colloidal sol is put into the material cup rest area of pulling coating machine.
(3) relevant parameter of pulling coating machine is arranged: stroke 6cm, decrease speed 300 μm/s, quiescent time 60s rise
Then 300 μm/s of speed starts to carry out lifting film.After lifting film, electrode is placed in electric drying oven with forced convection, In
Dry 30min, takes out be cooled to room temperature later under the conditions of 80 DEG C.
(4) the plane gold electrode for being coated with 1 layer of NiO film is put into tube furnace, with the heating rate heating tube of 3 DEG C/min
Formula furnace is to 500 DEG C and keeps 1h.After tube furnace is cooled to room temperature, layer of Ni O nanometer thin can be obtained on plane gold electrode
Film.
(5) plane gold electrode element is soldered in the detection pedestal of air-sensitive test macro, is placed on agingtable
Aging is for 24 hours to get final gas sensor under the conditions of 300 DEG C.
Through detecting, the NO manufactured in the present embodiment based on NiO nano thin-film2Sensor is in 100~200 DEG C of items of operating temperature
To NO under part2With good gas-sensitive property.
Claims (4)
1. a kind of NO based on electrode surface growth in situ NiO nano thin-film2Sensor, it is characterised in that: the sensor is by electricity
Pole element and uniform growth in situ are formed in the NiO film of electrode element surface, wherein the NiO film is by NiO crystal grain
It constituting, the NiO crystal grain is face-centered cubic phase crystal structure, and diameter is 20~30nm,
The sensor is described growth in situ NiO nanometers as obtained by electrode element surface growth in situ NiO nano thin-film
The method of film are as follows: NiO colloidal sol is coated in electrode element surface using lifting coating method, it is dry；Surface is coated with NiO colloidal sol
Electrode member be heat-treated, condition are as follows: be heated to 500 DEG C with the heating rate of 3 DEG C/min and keep 1h；250~300 DEG C
Lower aging for 24 hours, both obtained, wherein
The NiO colloidal sol is made as follows:
At room temperature, ethylene glycol monomethyl ether is added into nickel acetate tetrahydrate, stirs, nickel acetate tetrahydrate is made to be completely dissolved in ethylene glycol first
Among ether；Solution will be formed by continue to stir 2h in 60 DEG C, and the ammonium hydroxide of 25~28wt.% is added dropwise dropwise into solution；It is close
Envelope, be aged at room temperature for 24 hours, filtering, obtain NiO colloidal sol, wherein nickel acetate tetrahydrate, ammonium hydroxide, ethylene glycol monomethyl ether molar ratio
For 5~7:5~7:100.
2. sensor according to claim 1, it is characterised in that: the material of the electrode member is Al2O3Ceramic material or
Gold.
3. sensor according to claim 1, it is characterised in that: the shape of the electrode member is tubulose or plane.
4. sensor according to claim 1, it is characterised in that: the lifting film carries out in pulling coating machine, applies
It is dried after film, parameter is arranged in the pulling coating machine are as follows: stroke 6cm, 300~500 μm/s of decrease speed, quiescent time 30
~60s, 300~400 μm/s of the rate of climb；If you need to increase the film number of plies, then repeat the above steps.
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| CN113376191B (en) * | 2021-06-08 | 2022-09-16 | 中国科学院上海应用物理研究所 | In-situ-based device and method for high-throughput crystal culture and rapid sample loading |
| CN113433171B (en) * | 2021-06-24 | 2022-11-22 | 兰州大学 | Gas sensitive material, gas sensor and preparation method and application of gas sensitive material |
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