CN106970117A - A kind of NO based on electrode surface growth in situ nano-ZnO2Sensor - Google Patents
A kind of NO based on electrode surface growth in situ nano-ZnO2Sensor Download PDFInfo
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Abstract
The present invention relates to a kind of NO based on electrode surface growth in situ nano-ZnO2Sensor, belongs to the gas sensor technical field of one dimension semiconductor metal oxide materials.A kind of NO based on electrode surface growth in situ nano-ZnO2Sensor, it is characterised in that：The sensor be as obtained by the growth in situ ZnO nanowire array on electrode member, wherein, a diameter of 80~100nm of ZnO nano-wire, length is 600nm~1 μm, and the crystal structure of ZnO nano-wire is hexagonal phase wurtzite crystal structure.Gas sensor of the present invention is obtained to NO in 250 DEG C of operating temperature2The peak response of gas, response and recovery time are short, and invertibity and selectivity are good, are the NO with good development prospect2Sensor.
Description
Technical field
The invention belongs to the gas sensor technical field of one dimension semiconductor metal oxide materials, and in particular to Yi Zhongji
In the NO of electrode surface growth in situ ZnO nanowire array2Sensor and preparation method thereof.
Background technology
Nitrogen dioxide (NO2) it is a kind of toxic and harmful gas, mostly come from fuel combustion, industrial processes, city
Vehicle exhaust etc..NO2Gas can cause the formation of acid rain and photochemical fog, and human health can be endangered when excessive, causes earth's surface
Vegetation deterioration.Therefore to NO2Gas monitor effectively and in real time, can not only be effectively prevented from the hair of potential security incident
It is raw, while being also follow-up NO2Gas treatment provides reliable early stage guarantee.
In recent years, the gas sensor based on different gas sensitives and conduction platform is developed rapidly.Common gas
Quick material includes：Metal oxide semiconductor, conducting polymer, macromolecule and its compound, metal oxide/macromolecule are combined
Material and other new materials etc..These gas sensitives may apply to different transmission units, such as chemical-electrical resistive, table
Face sound wave type (SAW), QCM formula (QCM), optic delivery formula, field effect transistor tubular type etc..Passed in these gases
In sensor, the chemical-electrical resistive gas sensor based on metal oxide semiconductor material is due to low production cost, Gao Ling
Sensitivity, fast-response/resume speed, it is easy to use the features such as, be widely used.Presently commercially available NO2Sensor is used
Be SnO mostly2, ZnO or WO3Nano thin-film, nano particle and the micron spherical structure of base are used as gas sensitive.Relative to one
Dimension nano material, the gas sensitive structure based on above-mentioned microstructure has that specific surface area is small, the low deficiency of surface-active, so that
Cause sensitivity relatively low and response/recovery time is longer.Therefore, more concerns are placed on nanotube, nano wire, received by researcher
The synthesis and its application of the monodimension nanometer materials such as rice rod and the one-dimensional material array being made from it are upper, and with nano-wire array
Gas sensitive, due to structure is single, specific surface area and the features such as high surface-active, make it most promising gas
One of quick material.
ZnO is a kind of important semiconductor material with wide forbidden band, and its energy gap is 3.37eV at room temperature.Based on ZnO nano
The gas sensor of linear array is to NO2Gas has excellent air-sensitive performance.Preparing the method for ZnO nanowire array at present has：
Catalytic reaction growth method, template, chemical vapour deposition technique, metal organic vapor based on gas-liquid-solid (VLS) mechanism
Growth method, wet chemistry method and chemical solution method etc..These methods are typically that ZnO nanowire array is first synthesized on substrate, with
The ZnO nanowire array product on substrate is transferred on electrode surface when prepared by gas sensor afterwards, finally carried out again corresponding
Gas-sensitive property detection.However, the primary morphology that the preparation flow technique does not only result in ZnO nanowire array product occurs to break
It is bad, nor the original air-sensitive performance of ZnO nanowire array product can be reflected exactly.
The content of the invention
For the deficiency for preparing the complicated technique of ZnO nanowire array at present and its existing in terms of gas-sensitive property, this hair
It is bright that a kind of NO based on electrode surface growth in situ ZnO nanowire array is provided2Sensor and preparation method thereof, it is therefore an objective to pass through
Thermal decomposition method is prepared with advantages of good crystallization, length in electrode surface formation ZnO Seed Layers, then using hydro-thermal method in electrode surface in advance
Footpath directly assembles them into sensitivity height, invertibity than high ZnO nanowire array after last thermally treated and burin-in process
The NO for the advantages of good, response/recovery is rapid, selectivity is excellent2Sensor, to overcome existing NO2The preparation technology that sensor is present
The deficiency such as complicated, response/recovery is slower.The present invention prepares gained NO2Sensor, simplifies, production cost drops with preparation flow
It is low, the advantages of produced suitable for big batch metaplasia.
A kind of NO based on electrode surface growth in situ nano-ZnO2Sensor, the sensor is by electrode member
Obtained by upper growth in situ ZnO nanowire array, wherein,
A diameter of 80~the 100nm of ZnO nano-wire, length is 600nm~1 μm, and the crystal structure of ZnO nano-wire is six
Square phase wurtzite crystal structure.
In above-mentioned technical proposal, the ZnO nanowire array is NO2Gas gas sensitive.
In above-mentioned technical proposal, gained ZnO nano-wire pattern rule, surface are smooth.
NO of the present invention2Electrode member material described in sensor can be ceramics or gold；Shape can for interdigital, pectination,
Plane, tubulose etc., such as earthenware electrode member, plane gold electrode element or interdigital gold electrode element.
In above-mentioned technical proposal, the ZnO nanowire array, which is evenly distributed, is grown in electrode element surface.
Further, NO of the present invention2Sensor prepares gained as follows：
(1) electrode member is immersed in ethanol solution of the concentration for 0.001~0.01M Zinc diacetate dihydrate, dipping 5~
After 20s, 10~30min is dried at a temperature of 40~80 DEG C；This dipping-drying process is repeated 2~5 times；
(2) electrode member is positioned in electric tube furnace, 300~400 DEG C is warming up to simultaneously with the 10 DEG C/min rate of heat addition
10~40min is heat-treated in atmosphere, naturally cools to room temperature；
(3) it is 1 by volume by the zinc nitrate hexahydrate aqueous solution and the hexamethylenetetramine aqueous solution of same concentrations:1 mixes
Close, stir at room temperature, obtain mixed solution, wherein, the zinc nitrate hexahydrate aqueous solution and the hexamethylenetetramine aqueous solution it is dense
Spend for 0.01~0.1M；
(4) mixed solution is transferred in ptfe autoclave inner bag, then by the electricity of gained after step (2) processing
Pole element is immersed in the mixed solution, and reactor is placed in drying box after enclosed package, and 12h is reacted at a temperature of 80 DEG C；
Question response terminates and naturally cooled to after room temperature, takes out electrode member, washing, then electrode member is transferred in drying box, in
30min is dried at a temperature of 60 DEG C；
(5) dried electrode member is placed in electric tube furnace, 350 are warming up to the 10 DEG C/min rate of heat addition~
450 DEG C and in atmosphere be heat-treated 2~8h；After electrode member naturally cools to room temperature, air-sensitive test system is welded to
Pedestal on be placed on agingtable 6~24h of aging at a temperature of 350~450 DEG C, both.
It is a further object of the present invention to provide above-mentioned NO2The preparation method of sensor, methods described is walked including following techniques
Suddenly：
(1) electrode member is immersed in ethanol solution of the concentration for 0.001~0.01M Zinc diacetate dihydrate, dipping 5~
After 20s, 10~30min is dried at a temperature of 40~80 DEG C；This dipping-drying process is repeated 2~5 times；
(2) electrode member is positioned in electric tube furnace, 300~400 DEG C is warming up to simultaneously with the 10 DEG C/min rate of heat addition
10~40min is heat-treated in atmosphere, naturally cools to room temperature；
(3) it is 1 by volume by the zinc nitrate hexahydrate aqueous solution and the hexamethylenetetramine aqueous solution of same concentrations:1 mixes
Close, stir at room temperature, obtain mixed solution, wherein, the zinc nitrate hexahydrate aqueous solution and the hexamethylenetetramine aqueous solution it is dense
Spend for 0.01~0.1M；
(4) mixed solution is transferred in ptfe autoclave inner bag, then by the electricity of gained after step (2) processing
Pole element is immersed in the mixed solution, and reactor is placed in drying box after enclosed package, and 12h is reacted at a temperature of 80 DEG C；
Question response terminates and naturally cooled to after room temperature, takes out electrode member, washing, then electrode member is transferred in drying box, in
30min is dried at a temperature of 60 DEG C；
(5) dried electrode member is placed in electric tube furnace, 350 are warming up to the 10 DEG C/min rate of heat addition~
450 DEG C and in atmosphere be heat-treated 2~8h；After electrode member naturally cools to room temperature, air-sensitive test system is welded to
Pedestal on be placed on agingtable 6~24h of aging at a temperature of 350~450 DEG C, both.
In above-mentioned technical proposal, in step (1), the drying can be carried out in drying box；The electrode member is in immersion
Zinc diacetate dihydrate (Zn (CH3COO)2·2H2O preferably advanced water-filling is washed, ethanol is washed and dried before in ethanol solution).
It is commercially available in the air-sensitive test system and agingtable in step (5) in above-mentioned technical proposal.
In above-mentioned technical proposal, the electricity that electrode element surface has layer of ZnO crystal seed layer is obtained after step (1) and (2) processing
Pole element.
In above-mentioned technical proposal, in step (3), preferably by the zinc nitrate hexahydrate aqueous solution and six methines of same concentrations
Four amine aqueous solutions are 1 by volume:1 mixing, magnetic agitation 3min, obtains mixed solution at room temperature, wherein, zinc nitrate hexahydrate water
The concentration of solution is 0.01~0.1M, and the concentration of the hexamethylenetetramine aqueous solution is 0.01~0.1M.
In above-mentioned technical proposal, in step (3) and (4), six hydrations that preferably each configuration 25mL concentration is 0.01~0.1M
Zinc nitrate aqueous solution and the hexamethylenetetramine aqueous solution, and both are well mixed to obtain mixed solution；Mixed solution is placed in
In 200mL ptfe autoclave inner bags, the electrode member of gained after step (2) processing is then immersed into the mixed solution
In, reactor is placed in drying box after enclosed package, 12h is reacted at a temperature of 80 DEG C；Question response terminates and natural cooling
To room temperature, electrode member, washing are taken out, then electrode member is transferred in drying box, 30min is dried at a temperature of 60 DEG C；
Gas sensor element of the present invention based on electrode surface growth in situ ZnO nanowire array gas sensitive
Heat treatment and burin-in process, in order to keep the structure of gas sensitive and the stabilization of gas sensor performance.
Compared with existing technology of preparing, the features of the present invention and beneficial effect are：
The invention provides a kind of NO based on electrode surface growth in situ ZnO nanowire array2Sensor and its preparation
Method.From preparation method, the present invention prepares Seed Layer by thermal decomposition method in electrode surface first, then using hydro-thermal
Method is prepared with advantages of good crystallization, the ZnO nanowire array that draw ratio is high, surface-active is strong in electrode surface, last thermally treated
And gas sensor is prepared into after burin-in process.The inventive method is prepared simply, and easy to operate, whole flow process is easily achieved, and is had
The problem of traditional gas sensor preparation technology is complicated is solved to effect, and is conducive to large-scale industrial production.Pass through the party
Gas sensor prepared by method is obtained to NO in 250 DEG C of operating temperature2The peak response of gas, response and recovery time
Short, invertibity and selectivity are good, are the NO with good development prospect2Sensor.
Brief description of the drawings
Fig. 1 is the NO based on earthenware electrode element surface growth in situ ZnO nanowire array in embodiment 1~32Pass
Sensor component structural representation；Wherein：1：Earthenware；2：Gold electrode；3：Platinum lead；4：Gas sensitive layer；
Fig. 2 be embodiment 1 in ZnO nanowire array X ray diffracting spectrum；
Fig. 3 is the electron scanning micrograph of (a) electrode member and (b) ZnO nanowire array in embodiment 1；
Fig. 4 be embodiment 1 in single ZnO nano-wire transmission electron microscope photo；
Fig. 5 be gas sensor in embodiment 1 in 250 DEG C of operating temperature to various concentrations NO2The dynamic of gas is rung
Answer curve map；
Fig. 6 is gas sensor in embodiment 1 sensitivity and NO in 250 DEG C of operating temperature2Between gas concentration
Graph of a relation；
Fig. 7 be gas sensor in embodiment 1 in 250 DEG C of operating temperature to the sensitive of various concentrations detected gas
Degree；
Fig. 8 is the NO based on plane gold electrode surfaces growth in situ ZnO nanowire array in embodiment 42Sensor member
Part structural representation；Wherein：5：Platinum lead；6：Ceramic substrate；7：Gas sensitive layer；8：Gold electrode；9：Adding thermal resistance；
Fig. 9 is the NO based on interdigital gold electrode surfaces growth in situ ZnO nanowire array in embodiment 52Sensor member
Part structural representation；Wherein：10：Ceramic substrate；11：Adding thermal resistance；12：Gas sensitive layer；13：Interdigital gold electrode；14：Platinum
Lead.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments, is conventional method unless otherwise specified；The reagent, material and set
It is standby, unless otherwise specified, commercially obtain.
Air-sensitive test system described in following embodiments is bright Sheng science and technology WS-30A type air-sensitive test systems；The agingtable
For bright Sheng science and technology TS-60 type agingtables.
Embodiment 1
NO based on earthenware electrode element surface growth in situ ZnO nanowire array2Sensor element, its structural representation
Figure earthenware, gold electrode, platinum lead and air-sensitive material layer as shown in figure 1, be made up of.Gold electrode overlays on ceramic pipe surface, platinum
Gold wire is welded on gold electrode surfaces, and gas sensitive is grown in whole earthenware and gold electrode surfaces.Described gas sensitive into
It is divided into ZnO nanowire array, it, which is evenly distributed, is grown in electrode element surface, ZnO nano-wire pattern rule, surface are smooth,
And with single hexagonal phase wurtzite crystal structure, a diameter of 80~100nm, length is 600nm~1 μm, draw ratio is high.
A kind of NO based on ceramic electrode surface in situ growing ZnO nano-wire array gas sensitive2Sensor and its preparation
Method, is followed the steps below：
(1) first by electrode member respectively with deionized water and washes of absolute alcohol 3 times, and hot blast drying is used；
(2) 0.005M Zinc diacetate dihydrate (Zn (CH are prepared3COO)2·2H2O ethanol solution 20mL)；
(3) Zn (CH for immersing the electrode member in step (1) in step (2)3COO)2·2H2O ethanol solution, leaching
After stain 10s, take out electrode member and transfer them in drying box, 15min is dried at a temperature of 60 DEG C, by this dipping-drying
Process is repeated 3 times；
(4) electrode member in step (3) is placed in electric tube furnace, be warming up to 10 DEG C/min heating rate
And 20min is heat-treated in atmosphere, be then turned off electric tube furnace power supply, allow it to naturally cool to room temperature, obtain surface and contain by 350 DEG C
The electrode member of ZnO Seed Layers；
(5) 0.05M zinc nitrate hexahydrate (Zn (NO are prepared3)2·6H2O) and 0.05M hexamethylenetetramine (HMTA)
Each 25mL of the aqueous solution；Then, two kinds of solution are mixed, at room temperature magnetic agitation 3min；
(6) mixed solution by configuration in (5) is transferred in 200mL ptfe autoclave inner bag, then by (4)
In the electrode member of the Seed Layer containing ZnO immerse in the mixed solution, reactor is placed in drying box after enclosed package, in
12h is reacted at a temperature of 80 DEG C；Question response terminates and naturally cooled to after room temperature, takes out electrode member, 3 are cleaned with deionized water
It is secondary, then electrode member is transferred in drying box, 30min is dried at a temperature of 60 DEG C；
(7) dried electrode member is placed in electric tube furnace, 400 DEG C is warming up to 10 DEG C/min heating rate
And 4h is heat-treated in atmosphere；After electrode member naturally cools to room temperature, heater strip is passed through to the earthenware of electrode member, weldering
Heater strip and platinum lead are connect to the element base of air-sensitive test system, the aging at a temperature of 400 DEG C is placed on agingtable
12h, it is final to obtain the NO based on earthenware electrode element surface growth in situ ZnO nanowire array2Sensor.
X ray diffracting spectrum based on earthenware electrode element surface growth in situ ZnO nano-wire is as shown in Figure 2.As a result
Show, the product generated in electrode surface is single hexagonal phase wurtzite crystal structure, and spreading out without any other impurity
Peak is penetrated, shows that crystalline condition is excellent.The scanning electron microscopy of electrode member and the ZnO nanowire array grown in its surface in situ
Mirror photo is respectively as shown in Fig. 3 (a) and Fig. 3 (b).It should be apparent that the electrode member by earthenware, gold from Fig. 3 (a)
Electrode, platinum lead and air-sensitive material layer composition.It was found from from Fig. 3 (b), the uniform rule of ZnO nano-wire is in array-like distribution
On the surface of electrode member, nanowire diameter is 80~100nm, and length is 600nm~1 μm, and draw ratio is high.Single ZnO nano
The transmission electron microscope photo of line is as shown in figure 4, the as can be seen from the figure smooth rule in ZnO nano-wire surface, diameter and length
Degree respectively may be about 80nm and 1 μm, be consistent with the result of scanning electron microscope diagram piece.
Gas sensor based on ZnO nanowire array is in 250 DEG C of operating temperature to various concentrations NO2The dynamic of gas
Response curve is as shown in Figure 5.From figure 5 it can be seen that the gas sensor in 250 DEG C of operating temperature to NO2Gas has
Faster response/recovery time, continuously it is being passed through 1~30ppm various concentrations NO2In the reaction time of gas, the gas sensing
Device is respectively provided with good response invertibity, and resistance variations are with NO2Incremental trend is presented in the increase of gas concentration, shows
Sensitivity is with NO2The increase of gas concentration and increase, its corresponding sensitivity and NO2Relation such as Fig. 6 between gas concentration
It is shown.
Gas sensor based on ZnO nanowire array is in 250 DEG C of operating temperature to various concentrations detected gas
Sensitivity is as shown in fig. 7, detected gas therein is 1000ppm sulfur dioxide (SO2), hydrogen (H2), ammonia (NH3) and
500ppm formaldehyde (HCHO), methanol (CH3OH), dimethylbenzene (C8H10), and 5ppm NO2Gas.It can be seen that
Gas sensor based on ZnO nanowire array is to NO2The sensitivity highest of gas, selectivity preferably, shows in complicated gas
To NO under environment2Gas has good identification result and practical application advantage.
Embodiment 2
NO based on earthenware electrode element surface growth in situ ZnO nanowire array2Sensor element, its structural representation
Figure earthenware, gold electrode, platinum lead and air-sensitive material layer as shown in figure 1, be made up of.Gold electrode overlays on ceramic pipe surface, platinum
Gold wire is welded on gold electrode surfaces, and gas sensitive is grown in whole earthenware and gold electrode surfaces.Described gas sensitive into
It is divided into ZnO nanowire array, it is evenly distributed the surface for being grown in electrode member, ZnO nano-wire pattern rule, surface light
It is sliding, and with single hexagonal phase wurtzite crystal structure, a diameter of 80~100nm, length is 600nm~1 μm, draw ratio
It is high.
A kind of NO based on earthenware electrode element surface growth in situ ZnO nanowire array gas sensitive2Sensor and
Its preparation method, is followed the steps below：
(1) first by electrode member respectively with deionized water and washes of absolute alcohol 3 times, and hot blast drying is used；
(2) 0.001M Zinc diacetate dihydrate (Zn (CH are prepared3COO)2·2H2O ethanol solution 20mL)；
(3) Zn (CH for immersing the electrode member in step (1) in step (2)3COO)2·2H2O ethanol solution, leaching
After stain 20s, take out electrode member and transfer them in drying box, 30min is dried at a temperature of 40 DEG C, by this dipping-drying
Process is repeated 5 times；
(4) electrode member in step (3) is placed in electric tube furnace, be warming up to the 10 DEG C/min rate of heat addition
And 40min is heat-treated in atmosphere, be then turned off electric tube furnace power supply, allow it to naturally cool to room temperature, obtain surface and contain by 300 DEG C
The electrode member of ZnO Seed Layers；
(5) 0.01M zinc nitrate hexahydrate (Zn (NO are prepared3)2·6H2O) and 0.01M hexamethylenetetramine (HMTA)
Each 25mL of the aqueous solution；Then, two kinds of solution are mixed, at room temperature magnetic agitation 3min；
(6) mixed solution by configuration in (5) is transferred in 200mL ptfe autoclave inner bag, then by (4)
In the electrode member of the Seed Layer containing ZnO immerse in the mixed solution, reactor is placed in drying box after enclosed package, in
12h is reacted at a temperature of 80 DEG C；Question response terminates and naturally cooled to after room temperature, takes out electrode member, 3 are cleaned with deionized water
It is secondary, then electrode member is transferred in drying box, 30min is dried at a temperature of 60 DEG C；
(7) dried electrode member is placed in electric tube furnace, 350 DEG C is warming up to 10 DEG C/min firing rate
And 8h is heat-treated in atmosphere；After electrode member naturally cools to room temperature, heater strip is passed through to the earthenware of electrode member, weldering
Heater strip and platinum lead are connect to the element base of air-sensitive test system, the aging at a temperature of 350 DEG C is placed on agingtable
6h, it is final to obtain the NO based on earthenware electrode element surface growth in situ ZnO nanowire array2Sensor.
After testing, the NO manufactured in the present embodiment based on ZnO nanowire array2Sensor is in 100~350 DEG C of operating temperature
Under the conditions of to NO2Gas has good air-sensitive performance.
Embodiment 3
NO based on earthenware electrode element surface growth in situ ZnO nanowire array2Sensor element, its structural representation
Figure earthenware, gold electrode, platinum lead and air-sensitive material layer as shown in figure 1, be made up of.Gold electrode overlays on ceramic pipe surface, platinum
Gold wire is welded on gold electrode surfaces, and gas sensitive is grown in whole earthenware and gold electrode surfaces.Described gas sensitive into
It is divided into ZnO nanowire array, it is evenly distributed the surface for being grown in electrode member, ZnO nano-wire pattern rule, surface light
It is sliding, and with single hexagonal phase wurtzite crystal structure, a diameter of 80~100nm, length is 600nm~1 μm, draw ratio
It is high.
A kind of NO based on earthenware electrode element surface growth in situ ZnO nanowire array gas sensitive2Sensor and
Its preparation method, is followed the steps below：
(1) first by electrode member respectively with deionized water and washes of absolute alcohol 3 times, and hot blast drying is used；
(2) 0.01M Zinc diacetate dihydrate (Zn (CH are prepared3COO)2·2H2O ethanol solution 20mL)；
(3) Zn (CH for immersing the electrode member in step (1) in step (2)3COO)2·2H2O ethanol solution, leaching
After stain 5s, take out electrode member and transfer them in drying box, 10min is dried at a temperature of 80 DEG C, by this dipping-drying
Process is repeated 2 times；
(4) electrode member in step (3) is placed in electric tube furnace, be warming up to the 10 DEG C/min rate of heat addition
And 10min is heat-treated in atmosphere, be then turned off electric tube furnace power supply, allow it to naturally cool to room temperature, obtain surface and contain by 400 DEG C
The electrode member of ZnO Seed Layers；
(5) 0.1M zinc nitrate hexahydrate (Zn (NO are prepared3)2·6H2) and 0.1M hexamethylenetetramines (HMTA) are water-soluble O
Each 25mL of liquid；Then, two kinds of solution are mixed, at room temperature magnetic agitation 3min；
(6) mixed solution by configuration in (5) is transferred in 200mL ptfe autoclave inner bag, then by (4)
In the electrode member of the Seed Layer containing ZnO immerse in the mixed solution, reactor is placed in drying box after enclosed package, in
12h is reacted at a temperature of 80 DEG C；Question response terminates and naturally cooled to after room temperature, takes out electrode member, 3 are cleaned with deionized water
It is secondary, then electrode member is transferred in drying box, 30min is dried at a temperature of 60 DEG C；
(7) dried electrode member is placed in electric tube furnace, 450 DEG C is warming up to the 10 DEG C/min rate of heat addition
And 2h is heat-treated in atmosphere；After electrode member naturally cools to room temperature, heater strip is passed through to the earthenware of electrode member, weldering
Heater strip and platinum lead are connect on the element base of air-sensitive test system, the aging at a temperature of 450 DEG C is placed on agingtable
24h, it is final to obtain the NO based on earthenware electrode element surface growth in situ ZnO nanowire array2Sensor.
After testing, the NO manufactured in the present embodiment based on ZnO nanowire array2Sensor is right under the conditions of 100~350 DEG C
NO2Gas has good air-sensitive performance.
Embodiment 4
NO based on plane gold electrode surfaces growth in situ ZnO nanowire array2Sensor element, its electrode member front
Shown in structural representation such as Fig. 8 (a), it is made up of ceramic substrate, gold electrode, platinum lead and air-sensitive material layer, gold electrode is overlayed on
Ceramic base plate surface, platinum lead is welded on above gold electrode, and gas sensitive is grown in whole ceramic substrate and gold electrode surfaces.
(shown in such as Fig. 8 (b)) is made up of adding thermal resistance and platinum lead at the electrode member back side.Described gas sensitive composition is received for ZnO
Nanowire arrays, it is evenly distributed the front for being grown in electrode member, and ZnO nano-wire pattern rule, surface are smooth, and with single
One hexagonal phase wurtzite crystal structure, a diameter of 80~100nm, length is 600nm~1 μm, and draw ratio is high.
A kind of NO based on plane gold electrode surfaces growth in situ ZnO nanowire array gas sensitive2Sensor and its system
Preparation Method, is followed the steps below：
(1) first by electrode member respectively with deionized water and washes of absolute alcohol 3 times, and hot blast drying is used；
(2) 0.005M Zinc diacetate dihydrate (Zn (CH are prepared3COO)2·2H2O ethanol solution 20mL)；
(3) Zn (CH for immersing the electrode member in step (1) in step (2)3COO)2·2H2O ethanol solution, leaching
After stain 10s, take out electrode member and transfer them in drying box, 15min is dried at a temperature of 60 DEG C, by this dipping-drying
Process is repeated 3 times；
(4) electrode member in step (3) is placed in electric tube furnace, be warming up to the 10 DEG C/min rate of heat addition
And 20min is heat-treated in atmosphere, be then turned off electric tube furnace power supply, allow it to naturally cool to room temperature, obtain surface and contain by 350 DEG C
The electrode member of ZnO Seed Layers；
(5) 0.05M zinc nitrate hexahydrate (Zn (NO are prepared3)2·6H2O) and 0.05M hexamethylenetetramine (HMTA)
Each 25mL of the aqueous solution；Then, two kinds of solution are mixed, at room temperature magnetic agitation 3min；
(6) mixed solution of configuration in (5) is moved into 200mL ptfe autoclave inner bag, then by (4)
The electrode member of the Seed Layer containing ZnO immerse in the mixed solution, reactor is placed in drying box after enclosed package, in 80
12h is reacted at a temperature of DEG C；Question response terminates and naturally cooled to after room temperature, takes out electrode member, is cleaned with deionized water 3 times,
Electrode member is transferred in drying box again, 30min is dried at a temperature of 60 DEG C；
(7) dried electrode member is placed in electric tube furnace, 400 DEG C is warming up to the 10 DEG C/min rate of heat addition
And 4h is heat-treated in atmosphere；After electrode member naturally cools to room temperature, electrode member is welded to air-sensitive test system
On element base, the aging 12h at a temperature of 400 DEG C is placed on agingtable, it is final to obtain in situ based on plane gold electrode surfaces
The NO of growing ZnO nano-wire array2Sensor.
After testing, the NO manufactured in the present embodiment based on ZnO nanowire array2Sensor is right under the conditions of 100~350 DEG C
NO2Gas has good air-sensitive performance.
Embodiment 5
NO based on interdigital gold electrode surfaces growth in situ ZnO nanowire array2Sensor element, its structural representation is such as
Shown in Fig. 9, electrode member front is made up of ceramic substrate, interdigital gold electrode, platinum lead and air-sensitive material layer, wherein interdigital gold
Electrode overlays on ceramic substrate front, and platinum lead is welded on above interdigital gold electrode, adding thermal resistance overlays on the ceramic substrate back side, gas
Quick Material growth is in ceramic substrate and interdigital gold electrode surfaces.Described gas sensitive composition is ZnO nanowire array, and its is uniform
Ground is distributed the front for being grown in electrode member, and ZnO nano-wire pattern rule, surface are smooth, and with the fine zinc of single hexagonal phase
Ore deposit crystal structure, a diameter of 80~100nm, length is 600nm~1 μm, and draw ratio is high.
A kind of NO based on interdigital gold electrode surfaces growth in situ ZnO nanowire array gas sensitive2Sensor and its system
Preparation Method, is followed the steps below：
(1) first by electrode member respectively with deionized water and alcohol washes 3 times, and hot blast drying is used；
(2) 0.005M Zinc diacetate dihydrate (Zn (CH are prepared3COO)2·2H2O ethanol solution 20mL)；
(3) Zn (CH for immersing the electrode member in step (1) in step (2)3COO)2·2H2O ethanol solution, leaching
After stain 10s, take out electrode member and transfer them in drying box, 15min is dried at a temperature of 60 DEG C, by this dipping-drying
Process is repeated 3 times；
(4) electrode member in step (3) is placed in electric tube furnace, be warming up to the 10 DEG C/min rate of heat addition
And 20min is heat-treated in atmosphere, be then turned off electric tube furnace power supply, allow it to naturally cool to room temperature, obtain surface and contain by 350 DEG C
The electrode member of ZnO Seed Layers；
(5) 0.05M zinc nitrate hexahydrate (Zn (NO are prepared3)2·6H2O) and 0.05M hexamethylenetetramine (HMTA)
Each 25mL of the aqueous solution；Then, two kinds of solution are mixed, at room temperature magnetic agitation 3min；
(6) mixed solution of configuration in (5) is moved into 200mL ptfe autoclave inner bag, then by (4)
The electrode member of the Seed Layer containing ZnO immerse in the mixed solution, reactor is placed in drying box after enclosed package, in 80
12h is reacted at a temperature of DEG C；Question response terminates and naturally cooled to after room temperature, takes out electrode member, is cleaned with deionized water 3 times,
Electrode member is transferred in drying box again, 30min is dried at a temperature of 60 DEG C；
(7) dried electrode member is placed in electric tube furnace, 400 DEG C is warming up to the 10 DEG C/min rate of heat addition
And 4h is heat-treated in atmosphere；After electrode member naturally cools to room temperature, electrode member is welded to air-sensitive test system
On element base, the aging 12h at a temperature of 400 DEG C is placed on agingtable, it is final to obtain in situ based on interdigital gold electrode surfaces
The NO of growing ZnO nano-wire array2Sensor.
After testing, the NO manufactured in the present embodiment based on ZnO nanowire array2Sensor is right under the conditions of 100~350 DEG C
NO2Gas has good air-sensitive performance.
Claims (6)
1. a kind of NO based on electrode surface growth in situ nano-ZnO2Sensor, it is characterised in that：The sensor be by
On electrode member obtained by growth in situ ZnO nanowire array, wherein,
A diameter of 80~the 100nm of ZnO nano-wire, length is 600nm~1 μm, and the crystal structure of ZnO nano-wire is hexagonal phase
Wurtzite crystal structure.
2. sensor according to claim 1, it is characterised in that：The ZnO nanowire array is gas sensitive, and its is uniform
Ground distribution is grown in electrode element surface.
3. sensor according to claim 1, it is characterised in that：The material of the electrode member is ceramics or gold.
4. sensor according to claim 1, it is characterised in that：The electrode member is tubulose, plane, pectination or interdigital
Electrode member.
5. sensor according to claim 1, it is characterised in that：The electrode member is tubular ceramic electrode member, put down
Face gold electrode element or interdigital gold electrode element.
6. the preparation method of sensor described in claim 1, it is characterised in that：Including following processing steps：
(1) electrode member is immersed in ethanol solution of the concentration for 0.001~0.01M Zinc diacetate dihydrate, impregnates 5~20s
Afterwards, 10~30min is dried at a temperature of 40~80 DEG C；This dipping-drying process is repeated 2~5 times；
(2) electrode member is positioned in electric tube furnace, 300~400 DEG C is warming up to and in sky with the 10 DEG C/min rate of heat addition
10~40min is heat-treated in gas, room temperature is naturally cooled to；
(3) it is 1 by volume by the zinc nitrate hexahydrate aqueous solution and the hexamethylenetetramine aqueous solution of same concentrations:1 mixing, room
Stirred under temperature, obtain mixed solution, wherein, the concentration of the zinc nitrate hexahydrate aqueous solution and the hexamethylenetetramine aqueous solution is
0.01~0.1M；
(4) mixed solution is transferred in ptfe autoclave inner bag, then by the electrode member of gained after step (2) processing
Part is immersed in the mixed solution, and reactor is placed in drying box after enclosed package, and 12h is reacted at a temperature of 80 DEG C；Treat anti-
It should terminate and naturally cool to after room temperature, take out electrode member, washing, then electrode member is transferred in drying box, in 60 DEG C
At a temperature of dry 30min；
(5) dried electrode member is placed in electric tube furnace, 350~450 is warming up to the 10 DEG C/min rate of heat addition
DEG C and in atmosphere be heat-treated 2~8h；After electrode member naturally cools to room temperature, the base of air-sensitive test system is welded to
6~24h of aging at a temperature of 350~450 DEG C is placed on agingtable on seat, both.
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