CN105866189A - Cobalt doped tin dioxide semiconductor ethanol sensor, and making method and application thereof - Google Patents
Cobalt doped tin dioxide semiconductor ethanol sensor, and making method and application thereof Download PDFInfo
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Abstract
The invention discloses an ethanol sensor made of a cobalt doped tin dioxide semiconductor nanofiber sensitive material obtained based on an electrostatic spinning technology, a making method thereof, and an application of the ethanol sensor in detection of ethanol steam in indoor environment, and belongs to the technical field of gas sensors. The sensor comprises: an Al2O3 insulation ceramic plate, wherein the front side of the Al2O3 insulation ceramic plate is provided with two separate L-shaped gold electrodes, and the back side of the Al2O3 insulation ceramic plate is provided with a ruthenium oxide heating layer with the surface provided with two separate rectangular gold electrodes; and cobalt ion doped tin dioxide semiconductor nanofiber sensitive material films coated on the L-shaped gold electrodes and on the front side of the Al2O3 insulation ceramic plate. Doping of cobalt ions changes the morphological characteristics of tin dioxide semiconductor nanofibers and reduces the concentration of electrons in a tin dioxide material, so the sensitivity of the sensor is improved.
Description
Technical field
The invention belongs to gas sensor technical field, be specifically related to a kind of cobalt obtained based on electrostatic spinning technique
The ethanol sensor of doping stannic oxide oxide semiconductor nanofiber sensitive material, preparation method and in room
Interior environment detects the application in terms of alcohol vapour.
Background technology
In recent years, the aggravation of air environmental pollution, the taking place frequently of industrial/household security incident, food/pharmaceutical quality
Severe and urgent need in fields such as medical treatment, social welfare, fossil energy, military project and aviation/space flight, sense
Device, as the means of the information of acquisition, will be in the forward position of Information Technology Development, and can be paid close attention to widely and business
Change application.Although having been obtained for the biggest progress in the research of oxide semiconductor gas sensor, but
In order to meet its use requirement at each detection field, still need to improve the sensitivity of sensor, selectivity further
With reduction operating temperature.
It is true that deepen constantly round the research improving oxide-semiconductor sensor sensitivity always,
Especially developing into of nanoscale science and technology is improved sensor performance and is provided good opportunity.Research shows, gas
The identification function of quick material, translation function and sensitive body utilization rate decide the sensitivity of oxide-semiconductor sensor
Degree.It is found that the semiconductor oxide composite adulterated by heterogeneous adulterant can significantly improve biography
The sensitivity of sensor.This is primarily due to doping dissimilar metal ion can improve the carrier mobility of sensing material
Rate, thus improve its " translation function ", secondly, some dissimilar metal adulterant can make as catalyst
Occur to be catalyzed at the corresponding redox reaction in conductor oxidate surface, the selection of sensor can be improved
Property, improve " the identification function " of sensing material.Based on this point, carry out the oxide half of dissimilar metal doping
The design of conductor and preparation, the application for enlargement gas sensor has highly important scientific meaning.
Summary of the invention
It is an object of the invention to provide a kind of cobalt doped tin ash oxide half prepared based on electrostatic spinning technique
The ethanol sensor of conductor sensitive material, preparation method and answering in terms of detection alcohol vapour in indoor environment thereof
With.The present invention, by being doped semi-conducting material, increases the sensitivity of sensor, improves the sound of sensor
Answer speed, improve the repeatability of sensor, promote practical in field of gas detection of this kind of sensor.
Sensor obtained by the present invention is in addition to having higher sensitivity, and has preferably repeatability and length
Phase stability.The Monitoring lower-cut of this sensor is 2ppm, can be used for the detection of alcohol vapour content in indoor environment.
As it is shown in figure 1, cobalt doped tin ash oxide semiconductor ethanol sensor of the present invention, by front
With 2 discrete L-shaped gold electrodes 5, the back side with ruthenium-oxide zone of heating 3 and on ruthenium-oxide zone of heating 3 surface
Al with 2 discrete rectangle gold electrodes 62O3Insulated ceramic plates 1, it is coated in L-shaped gold electrode 5 and Al2O3
The quasiconductor sensitive material film 2 in insulated ceramic plates 1 front forms;Each L-shaped gold electrode 5 and rectangle gold electricity
Pole 6 is the most each welded with 1 platinum line 4, by measuring between the two platinum lines welded with 2 L-shaped gold electrodes 5
Resistance can obtain the resistance between two L-shaped gold electrodes, and can by the platinum line 4 welded with rectangle gold electrode 6
So that ruthenium-oxide zone of heating 3 is applied voltage, to Al2O3Insulated ceramic plates 1 heats;According to sensitivity S
Definition S=Ra/Rg, by measuring RaAnd Rg, it is computed the sensitivity of available sensor;It is characterized in that:
Quasiconductor sensitive material is the tin ash oxide semiconductor nanofiber of cobalt doped, cobalt ion and tin ion
Mol ratio is 0.01~0.05:1;This sensitive material is to use electrostatic spinning technique to prepare, and is pressed in through calcining after heat
L-shaped gold electrode 5 and Al2O3The front of insulated ceramic plates 1;The incorporation of cobalt ion, on the one hand changes titanium dioxide
The shape characteristic of tin oxide semiconductor nanofiber;On the other hand the electronics in tin dioxide material is decreased dense
Degree, thus improve the sensitivity of sensor.Additionally, tablet type sensor and the processing technology of oxide semiconductor
Simply, the most industrial batch production.The diameter of the tin dioxide nano fiber of tin ash and cobalt doped
80-100nm, a length of 5-40 micron.
A kind of cobalt doped tin ash oxide semiconductor obtained based on electrostatic spinning technique of the present invention is received
The preparation method of the ethanol sensor of rice fiber sensitive material, its step is as follows:
1) first by 0.02~0.10mmol CoCl6、2mmol SnCl2, 1g polyvinylpyrrolidone dissolve
In the mixed solution of 5mL dehydrated alcohol and 5mL dimethylformamide, stir 4~8 hours and form colloidal sol;
2) above-mentioned colloidal sol being loaded in electrostatic spinning apparatus, the distance of collecting board and spinning nozzle is 13~15cm,
Applying voltage between spinning nozzle and collecting board is 10~15kV, collecting board ground connection, and spinning 2~after 5 hours is being collected
Nanometer Electrospun product is obtained on plate;
3) above-mentioned nanometer Electrospun product is calcined 2~5 hours at 450~500 DEG C obtain cobalt doped tin ash
Conductor oxidate nanofiber sensitive material, is placed on commercially available front discrete with 2 by this sensitive material
L-shaped gold electrode 5, the back side is with ruthenium-oxide zone of heating 3 and discrete with 2 on ruthenium-oxide zone of heating 3 surface
The insulation Al of rectangle gold electrode 62O3The front of ceramic wafer 1, and make sensitive material that L-shaped gold electrode is completely covered
5, then hot pressing 15~30 minutes at 200~260 DEG C, form the sensitive material film 2 of 10~30 μm;Pottery
A length of the 1.3 of porcelain plate~1.7mm, a width of 0.8~1.3mm, thickness is 0.08~0.12mm;
4) by step 3) the insulation Al that obtains2O3Ceramic wafer 1 sinters 2~4 hours at 500~550 DEG C, finally will
Above-mentioned device welds and encapsulates, thus obtains ethanol sensor of the present invention.
Advantages of the present invention:
(1) sensor utilizes common N-type semiconductor material silica stannum, they have good electrical conductivity and
Chemical stability;
(2) utilize the tin ash being doped with cobalt ion that the sensitivity of sensor can be made to significantly improve, promote it
Practical, at home and abroad have no report;
(3) cobalt doped tin dioxide nano fiber is to utilize electrostatic spinning technique to make, and manufacture method is simple, makes
The cheap commercial production being beneficial to mass of valency.
Accompanying drawing explanation
Fig. 1: the structural representation of cobalt doped tin ash oxide semiconductor ethanol sensor;
Fig. 1 (a) is sensor front schematic view;Fig. 1 (b) sensor schematic rear view;
In Fig. 2: comparative example, embodiment 1, embodiment 2 and embodiment 3 sensor in different operating temperature to 100
The Sensitivity comparison curve of ppm ethanol;
The standard working curve of the concentration of alcohol-sensitivity of Fig. 3: comparative example and embodiment 2.
As it is shown in figure 1, each component names is: Al2O3Insulated ceramic plates 1;Quasiconductor sensitive material 2;Ruthenium-oxide
Zone of heating 3;Platinum line 4;L-shaped gold electrode 5;Rectangle gold electrode 6.
Fig. 2 is that the sensitivity to 100ppm ethanol of device made by comparative example and embodiment 1,2,3 is with work
The change curve of temperature.It can be seen that the optimum working temperature of comparative example is 275 DEG C, now sensitivity
It is 9.49;The optimum working temperature of embodiment 1 is 300 DEG C, and now sensitivity is 22.26;Embodiment 2 is
Good operating temperature is 300 DEG C, and now sensitivity is respectively 40.1;The optimum working temperature of embodiment 3 is 325 DEG C,
Now sensitivity is respectively 5.55.Under optimum working temperature, the sensitivity of embodiment 2 is the highest, is about contrast
4 times of example sensitivity.As can be seen here, the reaction effect of sensitive material and ethanol can be improved by mixing cobalt ion
Rate, and then obtained one there is highly sensitive cobalt doped tin ash oxide semiconductor ethanol sensor.
Fig. 3 is comparative example and embodiment 2 standard working curve the concentration of alcohol-sensitivity of 300 DEG C.Sensitive
Degree method of testing: first sensor is put into gas cabinet, record now platinum by the ammeter being connected with sensor
The resistance at line two ends, obtains the sensor i.e. R of aerial resistance valuea;Then use microsyringe to gas
Case injects the ethanol of 2~1000ppm, obtains sensor resistance value in different concentration ethanol i.e. by measurement
Rg, according to the defined formula S=R of sensitivity Sa/Rg, by being calculated the sensitivity of variable concentrations lower sensor,
Finally give the standard working curve of concentration of alcohol-sensitivity.It can be seen that the detection of this sensor
Lower limit is 2ppm, and the now sensitivity of comparative example and embodiment 2 is respectively 1.2 and 1.92;Concentration of alcohol is
During 1000ppm, sensitivity now is respectively 60.74 and 228.
R can be recorded by above-mentioned way during actual measurementa、Rg, obtain after Sensitirity va1ue with concentration of alcohol-sensitivity
Standard working curve contrast, thus obtain the ethanol content in environment.It addition, work as gas as shown in the figure
During concentration less (< 200ppm), transducer sensitivity linear preferably, these features make this kind of ethanol sensor
Can be good at being applied to the detection of alcohol gas in indoor environment.
Detailed description of the invention
Comparative example:
Flat ethanol sensor, its concrete making is made as sensitive material using tin dioxide nano fiber
Journey:
First by 2mmol SnCl2, 1g polyvinylpyrrolidone be dissolved in 5mL dehydrated alcohol and 5mL dimethyl
In the mixed solution of Methanamide, stir 4 hours and form colloidal sol;
2. above-mentioned colloidal sol being loaded in electrostatic spinning apparatus, the distance of collecting board and spinning nozzle is 13cm, spinning nozzle
Applying voltage is 10kv, collecting board ground connection, after spinning 3 hours, obtains nanometer Electrospun product on collecting board;
3. above-mentioned nanometer Electrospun product is calcined 3 hours at 500 DEG C and obtain tin dioxide nano fiber sensitivity
Material, is placed on commercially available outer surface from the insulation Al with 2 L-shaped gold electrodes 5 by this sensitive material2O3Pottery
The front of porcelain plate 1, uses hot press 200 DEG C of hot pressing 15 minutes, forms the sensitive material film 2 of 20 μm,
A length of 1.5mm of ceramic wafer, a width of 1.0mm, a height of 0.1mm, and make sensitive material that L-shaped gold electricity is completely covered
Pole 5;
4. insulation Al2O3Ceramic wafer 1 sinters 3 hours at 500 DEG C;Finally by above-mentioned device according to conventional flat-panel
Formula gas sensor welds and encapsulates, thus obtains tin ash oxide semiconductor ethanol of the present invention
Sensor.
Embodiment 1:
Cobalt doped tin ash oxide semiconductor using the mol ratio of cobalt ion/tin ion as 0.01:1 is as quick
Sense material makes ethanol sensor, and its manufacturing process is
First by 0.02mmol CoCl6、2mmol SnCl2, that 1g polyvinylpyrrolidone is dissolved in 5mL is anhydrous
In the mixed solution of ethanol and 5mL dimethylformamide, stir 4 hours and form colloidal sol;
2. above-mentioned colloidal sol being loaded in electrostatic spinning apparatus, the distance of collecting board and spinning nozzle is 13cm, spinning nozzle
Applying voltage is 10kv, collecting board ground connection, after spinning 3 hours, obtains nanometer Electrospun product on collecting board;
3. above-mentioned nanometer Electrospun product is calcined 3 hours at 500 DEG C and obtain cobalt doped stannic oxide nanometer fibre
Dimension sensitive material, is placed on commercially available outer surface from the insulation with 2 L-shaped gold electrodes 5 by this sensitive material
Al2O3The front of ceramic wafer 1, uses hot press 200 DEG C of hot pressing 15 minutes, forms the sensitive material of 20 μm
Thin film 2, a length of 1.0mm of ceramic wafer, external diameter is 1.5mm, and makes sensitive material that L-shaped gold electrode is completely covered
5;
4. insulation Al2O3Ceramic wafer 1 sinters 3 hours at 500 DEG C;Finally by above-mentioned device according to conventional flat-panel
Formula gas sensor welds and encapsulates, thus obtains cobalt doped tin ash oxide of the present invention and partly lead
Body ethanol sensor.
Embodiment 2:
Cobalt doped tin ash oxide semiconductor using the mol ratio of cobalt ion/tin ion as 0.03:1 is as quick
Sense material makes ethanol sensor, and its manufacturing process is
First by 0.06mmol CoCl2、2mmol SnCl2, that 1g polyvinylpyrrolidone is dissolved in 5mL is anhydrous
In the mixed solution of ethanol and 5mL dimethylformamide, stir 4 hours and form colloidal sol;
2. above-mentioned colloidal sol being loaded in electrostatic spinning apparatus, the distance of collecting board and spinning nozzle is 13cm, spinning nozzle
Applying voltage is 10kv, collecting board ground connection, after spinning 3 hours, obtains nanometer Electrospun product on collecting board;
3. above-mentioned nanometer Electrospun product is calcined 3 hours at 500 DEG C and obtain cobalt doped stannic oxide nanometer fibre
Dimension sensitive material, is placed on commercially available outer surface from the insulation with 2 L-shaped gold electrodes 5 by this sensitive material
Al2O3The front of ceramic wafer 1, uses hot press 200 DEG C of hot pressing 15 minutes, forms the sensitive material of 20 μm
Thin film 2, a length of 1.0mm of ceramic wafer, external diameter is 1.5mm, and makes sensitive material that L-shaped gold electrode is completely covered
5;
4. insulation Al2O3Ceramic wafer 1 sinters 3 hours at 500 DEG C;Finally by above-mentioned device according to conventional flat-panel
Formula gas sensor welds and encapsulates, thus obtains cobalt doped tin ash oxide of the present invention and partly lead
Body ethanol sensor.
Embodiment 3:
With the cobalt doped tin ash oxide semiconductor that mol ratio is 0.05:1 of cobalt ion/tin ion as quick
Sense material makes ethanol sensor, and its manufacturing process is
First by 0.1mmol CoCl2、2mmol SnCl2, that 1g polyvinylpyrrolidone is dissolved in 5mL is anhydrous
In the mixed solution of ethanol and 5mL dimethylformamide, stir 4 hours and form colloidal sol;
2. above-mentioned colloidal sol being loaded in electrostatic spinning apparatus, the distance of collecting board and spinning nozzle is 13cm, spinning nozzle
Applying voltage is 13kv, collecting board ground connection, after spinning 3 hours, obtains nanometer Electrospun product on collecting board;
3. above-mentioned nanometer Electrospun product is calcined 3 hours at 500 DEG C and obtain cobalt doped stannic oxide nanometer fibre
Dimension sensitive material, is placed on commercially available outer surface from the insulation with 2 L-shaped gold electrodes 5 by this sensitive material
Al2O3The front of ceramic wafer 1, uses hot press 200 DEG C of hot pressing 15 minutes, forms the sensitive material of 20 μm
Thin film 2, a length of 1.0mm of ceramic wafer, external diameter is 1.5mm, and makes sensitive material that L-shaped gold electrode is completely covered
5;
4. insulation Al2O3Ceramic wafer 1 sinters 3 hours at 500 DEG C;Finally by above-mentioned device according to conventional flat-panel
Gas sensor welds and encapsulates, thus obtains cobalt doped tin ash oxide semiconductor of the present invention
Ethanol sensor.
Claims (5)
1. the cobalt doped tin ash oxide semiconductor ethanol sensor obtained based on electrostatic spinning technique,
By front with 2 discrete L-shaped gold electrodes (5), the back side with ruthenium-oxide zone of heating (3) and in oxidation
Ruthenium zone of heating (3) surface is with the Al of 2 discrete rectangle gold electrodes (6)2O3Insulated ceramic plates (1),
It is coated in L-shaped gold electrode (5) and Al2O3The quasiconductor sensitive material film (2) in insulated ceramic plates (1) front
Composition;It is characterized in that: quasiconductor sensitive material is the tin ash oxide semiconductor nanofiber of cobalt doped,
The mol ratio of cobalt ion and tin ion is 0.01~0.05:1;This sensitive material is to use electrostatic spinning technique system
Standby, it is pressed in L-shaped gold electrode (5) and Al through calcining after heat2O3The front of insulated ceramic plates (1).
A kind of cobalt doped tin ash oxidation obtained based on electrostatic spinning technique
Thing quasiconductor ethanol sensor, it is characterised in that: described Al2O3A length of the 1.3 of insulated ceramic plates~1.7mm,
A width of 0.8~1.3mm, thickness is 0.08~0.12mm.
A kind of cobalt doped tin ash oxidation obtained based on electrostatic spinning technique
Thing quasiconductor ethanol sensor, it is characterised in that: the tin dioxide nano fiber of tin ash and cobalt doped
Diameter 80~100nm, a length of 5~40 microns.
4. a kind of cobalt doped titanium dioxide obtained based on electrostatic spinning technique described in claim 1,2 or 3
The preparation method of tin oxide semiconductor ethanol sensor, its step is as follows:
1) first by 0.02~0.1mmol CoCl2、2mmol SnCl2, 1g polyvinylpyrrolidone dissolve
In the mixed solution of 5mL dehydrated alcohol and 5mL dimethylformamide, stir 4~8 hours
Form colloidal sol;
2) above-mentioned colloidal sol being loaded in electrostatic spinning apparatus, the distance of collecting board and spinning nozzle is 13~15cm,
Applying voltage between spinning nozzle and collecting board is 10~15kV, collecting board ground connection, spinning 2~5 hours
After, collecting board obtains nanometer Electrospun product;
3) above-mentioned nanometer Electrospun product is calcined 2~5 hours at 450~500 DEG C obtain cobalt doped dioxy
Change stannum conductor oxidate nanofiber sensitive material, this sensitive material is placed on insulation Al2O3
The front of ceramic wafer (1), and make sensitive material that L-shaped gold electrode (5) is completely covered, then exist
Hot pressing 15~30 minutes at 200~260 DEG C, form the sensitive material film (2) of 10~30 μm;
4) by step 3) the insulation Al that obtains2O3Ceramic wafer (1) sinters 2~4 hours at 500~550 DEG C,
Finally above-mentioned device is welded and encapsulates, thus obtain ethanol sensor.
5. a kind of cobalt doped dioxy obtained based on electrostatic spinning technique described in claims 1 to 3 any one
Change the application to alcohol vapour context of detection in indoor environment of the tin oxide semiconductor ethanol sensor.
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