CN103293197B - The preparation method of the titania-doped base film acetone gas sensor of tin ash - Google Patents

The preparation method of the titania-doped base film acetone gas sensor of tin ash Download PDF

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CN103293197B
CN103293197B CN201210308813.8A CN201210308813A CN103293197B CN 103293197 B CN103293197 B CN 103293197B CN 201210308813 A CN201210308813 A CN 201210308813A CN 103293197 B CN103293197 B CN 103293197B
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CN103293197A (en
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何平
潘国峰
高金雍
白卫芹
杨帆
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Hebei University of Technology
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Abstract

The invention discloses the preparation method of the titania base film acetone gas sensor of a kind of tin ash doping.The present invention carries out according to lower step: first configuration concentration is the SnCl of 14.9% 45H 2o solution, instillation hydrochloric acid drips ammoniacal liquor simultaneously, until stop dripping ammoniacal liquor when the pH value of solution changes to about 6; Stir 30 minutes again, then place at room temperature, dry after aging 2 days; Then be the butyl titanate solution of 23.1% with absolute ethyl alcohol configuration concentration; Remove ionized water and acetic acid carries out volume ratio 1:1 mixing, take the SnO of preparation 2powder is added to this mixed solution, adds SnO 2with TiO 2mol ratio be 1:25-50, leave standstill three hours; 100 DEG C of dry 2h, grind in agate mortar, are doping SnO 2nano-TiO 2powder; Get above-mentioned powder to mix in 1:1 ratio with methylcellulose, be applied on ceramic pipe, carry out the annealing of 500 DEG C of temperature.Highly sensitive to acetone of this sensing element, response recovery time is short, and working temperature is low.

Description

The preparation method of the titania-doped base film acetone gas sensor of tin ash
Technical field
The invention belongs to gas-sensitive sensing element field, particularly a kind of titania (TiO 2) film has the preparation method of the gas-sensitive sensing element of high selectivity to acetone.
Background technology
Gas sensor is the core component of gas sensor, in air-sensitive film sensor, and TiO 2as a kind of n-type semiconductor, there are unique optics, electricity and chemical property.TiO 2be a kind of important Semiconductor gas sensors material, there is excellent chemical stability, TiO 2film shows sensitivity characteristic to multiple gases, such as: H 2, O 2, alcohol vapour etc., show the broad spectrum activity to multiple gases, its selectivity is poor, and sensitivity is lower; In addition, TiO 2the working temperature of air-sensitive film sensor is usually more than 400 DEG C, and power consumption is larger.
Summary of the invention
Technical matters to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of preparation method acetone steam to the titania base film acetone gas sensor adulterated compared with the tin ash of high selectivity
The preparation method of the titania base film acetone gas sensor of tin ash doping of the present invention, carries out according to lower step:
1. the preparation of tin ash gel
Be the SnCl of 14.9% with deionized water configuration concentration 45H 2o solution, instills two hydrochloric acid and stirs, drip ammoniacal liquor simultaneously, until stop dripping ammoniacal liquor when the pH value of solution changes to about 6; Stir 30 minutes again, then place at room temperature, aging 2 days; After obtaining the colloidal sol of layering, remove clear liquid and repeatedly wash, put into drying baker and dry, obtain gel; Finally, put into muffle furnace 500 DEG C annealing, obtain SnO 2gel powder;
2 doped Ti O 2the preparation of powder
A. be the butyl titanate solution of 23.1% with absolute ethyl alcohol configuration concentration, mixed solution stirred half an hour, butyl titanate is dissolved in absolute ethyl alcohol completely; Remove ionized water and acetic acid carries out volume ratio 1:1 mixing, take the SnO of preparation 2powder is added to this mixed solution, adds SnO 2with TiO 2mol ratio be 1:25-50, and dropwise join in the butyl titanate ethanolic solution in stirring, after stirring a period of time, solution enters collosol state, then leaves standstill three hours, obtains the gel with fixed sturcture;
B. by above-mentioned wet gel 100 DEG C of dry 2h in constant temperature electric heating case, remove ethanol wherein and moisture, obtaining xerogel is fluffy yellow crystals particle; Yellow crystals particle is ground in agate mortar, obtains white powder, be doping SnO 2nano-TiO 2powder;
3 annealing in process
Get appropriate doping SnO 2tiO 2nanometer powder mixes in 1:1 ratio with methylcellulose, then instills two deionized waters, is applied on ceramic pipe, carries out the annealing of 3 hours of 500 DEG C of constant temperature, obtain the ceramic pipe of cover film.
Gas sensor prepared by the present invention is only responsive to acetone, substantially insensitive to other common gases (as ethanol, toluene, formaldehyde, methyl alcohol, ammonia etc.), therefore this sensor can detect acetone vapor in mixed gas existence whether and concentration.This sensor has very high sensitivity to acetone, and response recovery time is very short, and has the low advantage of working temperature.
The present invention compared with prior art has the following advantages:
(1) at Al 2o 3ceramic pipe outside surface prepares TiO 2film, what the present invention adopted is sol-gel process, and quality of forming film is better.
(2), when adopting Preparation of Thin Films by Sol-Gel Method, select technological parameter of the present invention, gas sensor can be made best to acetone selectivity, the interference of other gas can be resisted.
(3) highly sensitive to acetone of this sensing element, response recovery time is short, and working temperature is low.
The present invention adopts sol-gel process at alundum (Al2O3) (Al 2o 3) on ceramic pipe and silicon chip preparation mix tin ash (SnO 2) TiO 2film, after different temperatures annealing, by the gas-sensitive property of the testing of equipment films such as air-sensitive test box.Main application of the present invention: detect acetone steam.In numerous gas, selectively can detect existence and the concentration thereof of acetone steam.
Accompanying drawing explanation
Figure 1 shows that test circuit;
Figure 2 shows that gas sensor test typical consequence figure.
Embodiment:
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Sol-gel process is at Al 2o 3on ceramic pipe and silicon chip, SnO is mixed in preparation 2tiO 2film, doping is 4%.
The preparation of 1 doped raw material tin ash gel
With the SnCl of 4.37g 45H 2o is dissolved in 25mL deionized water, instills two hydrochloric acid and stirs, drip ammoniacal liquor simultaneously, until stop dripping ammoniacal liquor when the pH value of solution changes to about 6.Stir 30 minutes again, then place at room temperature, aging 2 days.After obtaining the colloidal sol of layering, remove clear liquid and repeatedly wash, put into drying baker and dry, obtain gel; Finally, put into muffle furnace 200 DEG C annealing, obtain SnO 2gel powder.
2 doped Ti O 2the preparation of powder
A. adulterate SnO 2with TiO 2mol ratio be 1:25, as calculated SnO 2quality be 102.6mg.Get the absolute ethyl alcohol of 20mL, pour in beaker, slowly add the butyl titanate of 6mL wherein and stir, mixed solution is stirred half an hour, butyl titanate is dissolved in absolute ethyl alcohol completely; The acetic acid of the deionized water and 2mL of getting 2mL mixes, and takes the SnO of preparation 2powder 102.6mg is added to this mixed solution, and dropwise joins in the butyl titanate ethanolic solution in stirring, and after stirring a period of time, solution enters collosol state, then leaves standstill three hours, obtains the gel with fixed sturcture.
B. by above-mentioned wet gel 100 DEG C of dry 2h in constant temperature electric heating case, remove ethanol wherein and moisture, obtaining xerogel is fluffy yellow crystals particle; Yellow crystals particle is ground in agate mortar, obtains white powder, be doping SnO 2the nano-TiO of 4% 2powder.
3 annealing in process
Get appropriate doping SnO 2tiO 2nanometer powder mixes in 1:1 ratio with methylcellulose, then instills two deionized waters, is applied on ceramic pipe, carries out the annealing of 500 DEG C of temperature, obtain the ceramic pipe of cover film.
4 air-sensitive tests
Ceramic pipe with film is welded on pedestal, carries out testing the air-sensitive of acetone with the HW-10A air-sensitive tester that Henan Hanwei Electronics Co., Ltd produces.As shown in Figure 1, wherein Rz is sensitive element resistance to test circuit, and R is pull-up resistor, and R selects according to Rz size.Vc is test loop service voltage; Vout is the test voltage exported.Vh is the service voltage of heating circuit, selects according to the heating-up temperature needed.
After test, the operating temperature range of gas sensor of the present invention is 60 DEG C-120 DEG C.Its air-sensitive test result is as follows: this sensing element is only responsive to acetone, and its response-recovery time is 2-3 second.Insensitive to other interference gases.
Table 1 is depicted as gas sensor test typical consequence and sums up, and shows that gas sensor involved in the present invention is to the sensitivity of acetone and other gas (as ethanol, toluene, formaldehyde, methyl alcohol, ammonia etc.) and response recovery time.Gas sensor test typical consequence as shown in Figure 1.
Embodiment 2
Sol-gel process is at Al 2o 3on ceramic pipe and silicon chip, SnO is mixed in preparation 2tiO 2film, doping is 2%.
The preparation of 1 doped raw material tin ash gel
With the SnCl of 4.37g 45H 2o is dissolved in 25mL deionized water, instills two hydrochloric acid and stirs, drip ammoniacal liquor simultaneously, until stop dripping ammoniacal liquor when the pH value of solution changes to about 6.Stir 30 minutes again, then place at room temperature, aging 2 days.After obtaining the colloidal sol of layering, remove clear liquid and repeatedly wash, put into drying baker and dry, obtain gel; Finally, put into muffle furnace 200 DEG C annealing, obtain SnO 2gel powder.
2 doped Ti O 2the preparation of powder
A. adulterate SnO 2with TiO 2mol ratio be 1:50, as calculated SnO 2quality be 51.3mg.Get the absolute ethyl alcohol of 20mL, pour in beaker, slowly add the butyl titanate of 6mL wherein and stir, mixed solution is stirred half an hour, butyl titanate is dissolved in absolute ethyl alcohol completely; The acetic acid of the deionized water and 2mL of getting 2mL mixes, and takes the SnO of preparation 2powder 51.3mg is added to this mixed solution, and dropwise joins in the butyl titanate ethanolic solution in stirring, and after stirring a period of time, solution enters collosol state, then leaves standstill three hours, obtains the gel with fixed sturcture.
B. by above-mentioned wet gel 100 DEG C of dry 2h in constant temperature electric heating case, remove ethanol wherein and moisture, obtaining xerogel is fluffy yellow crystals particle; Yellow crystals particle is ground in agate mortar, obtains white powder, be doping SnO 2the nano-TiO of 4% 2powder.
3 annealing in process
Get appropriate doping SnO 2tiO 2nanometer powder mixes in 1:1 ratio with methylcellulose, then instills two deionized waters, is applied on ceramic pipe, carries out the annealing of 600 DEG C of temperature, obtain the ceramic pipe of cover film.
4 air-sensitive tests
Ceramic pipe with film is welded on pedestal, carries out testing the air-sensitive of acetone with the HW-10A air-sensitive tester that Henan Hanwei Electronics Co., Ltd produces.
After test, the operating temperature range of gas sensor of the present invention is 60 DEG C-120 DEG C.Its air-sensitive test result is as follows: this sensing element is not only responsive to acetone, also has certain gas-sensitive property to ethanol and methyl alcohol.Present wide spectrum characteristic.
The present invention adopts sol-gal process to prepare TiO 2film, at Al 2o 3ceramic pipe outside surface prepares TiO 2film, places tungsten filament in ceramic pipe, for heating Al 2o 3ceramic pipe.Ceramic pipe two ends are wound around platinum wire electrode.By tungsten filament and TiO 2platinum electrode on film is connected with test circuit with heater circuit respectively.The concentration of the acetone steam utilizing the electrical resistance of ZnO film to introduce and time variations and change, just can measure the concentration of acetone steam.Element shows only to the gas-sensitive property of the high selectivity of acetone vapor sensitivity.
Gas-sensitive property is relevant with the absorption on gas surface, because this adsorption makes the surface energy of semiconductor change, causes material electric conductivity to change, thus achieves gas sensing performance.When gas sensitive adsorption organic gas, Preferential adsorption be Lacking oxygen position in plane of crystal, according to the change of temperature, absorption substep carries out, first there is gas molecule and occupy Lacking oxygen and the physisorption that produces, along with temperature raises, the gas molecule of part physical absorption can be converted into chemisorption and ionize, and organic gas is ejected electron in ionization process, therefore along with the increase of temperature, the increase of gas concentration, in gas sensitive, charge carrier increases, thus component resistance diminishes.Therefore, gas molecule Chemisorption is the controlling factor of material air-sensitive performance change.
The test of gas sensor adopts distribution method, and instrument used is the HW-30 Testing system of gas-sensor built of Henan Han Wei company limited.Can detect that this sensor is to the sensitivity of gas, response time, release time.This sensor is characterized only best to the gas-sensitive property of acetone according to these three parameters.

Claims (1)

1. a preparation method for the titania-doped base film acetone gas sensor of tin ash, is characterized in that, carry out according to lower step:
(1) preparation of tin ash gel
Be the SnCl of 14.9% with deionized water configuration concentration 45H 2o solution, instills two hydrochloric acid and stirs, drip ammoniacal liquor simultaneously, until stop dripping ammoniacal liquor when the pH value of solution changes to about 6; Stir 30 minutes again, then place at room temperature, aging 2 days; After obtaining the colloidal sol of layering, remove clear liquid and carry out at least three washings, put into drying baker and dry, obtain gel; Finally, put into muffle furnace 500 DEG C annealing, obtain SnO 2gel powder;
(2) doped Ti O 2the preparation of powder
A. be the butyl titanate solution of 23.1% with absolute ethyl alcohol configuration concentration, mixed solution stirred half an hour, butyl titanate is dissolved in absolute ethyl alcohol completely; Remove ionized water and acetic acid carries out volume ratio 1:1 mixing, take the SnO of preparation 2powder is added to this mixed solution, adds SnO 2with TiO 2mol ratio be 1:25-50, and dropwise join in the butyl titanate ethanolic solution in stirring, after stirring a period of time, solution enters collosol state, then leaves standstill three hours, obtains the gel with fixed sturcture;
B. by wet gel 100 DEG C of dry 2h in constant temperature electric heating case, remove ethanol wherein and moisture, obtaining xerogel is fluffy yellow crystals particle; Yellow crystals particle is ground in agate mortar, obtains white powder, be doping SnO 2tiO 2nanometer powder;
(3) annealing in process
Get appropriate doping SnO 2tiO 2nanometer powder mixes in 1:1 ratio with methylcellulose, then instills two deionized waters, is applied on ceramic pipe, carries out the annealing of 500 DEG C of temperature, obtain the ceramic pipe of cover film.
CN201210308813.8A 2012-08-28 2012-08-28 The preparation method of the titania-doped base film acetone gas sensor of tin ash Expired - Fee Related CN103293197B (en)

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CN104820068B (en) * 2015-04-22 2016-06-29 上海纳米技术及应用国家工程研究中心有限公司 Stannum oxide alumina base low concentration acetone gas sensor and preparation method thereof
CN107492234A (en) * 2016-06-13 2017-12-19 中国科学院过程工程研究所 A kind of field effect transistor switch type gas sensor alarm control circuit
CN107311695A (en) * 2017-05-24 2017-11-03 江苏时瑞电子科技有限公司 A kind of preparation method of tin ash air-sensitive film
JP7112854B2 (en) * 2018-02-19 2022-08-04 住友化学株式会社 tin oxide powder
CN108732213A (en) * 2018-06-10 2018-11-02 叶建民 A kind of preparation method of room temperature high-performance ethanol-sensing material
CN110133087A (en) * 2019-06-13 2019-08-16 哈尔滨理工大学 A kind of preparation of tin dioxide gas-sensitive material and method of modifying
CN117169293B (en) * 2023-11-01 2024-02-27 之江实验室 MOS-based gas-sensitive material, and preparation method and application thereof

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