CN1424778A - Manufacturing method for semiconductor gas-sensing device of testing carbon dioxide - Google Patents
Manufacturing method for semiconductor gas-sensing device of testing carbon dioxide Download PDFInfo
- Publication number
- CN1424778A CN1424778A CN02160100.3A CN02160100A CN1424778A CN 1424778 A CN1424778 A CN 1424778A CN 02160100 A CN02160100 A CN 02160100A CN 1424778 A CN1424778 A CN 1424778A
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- China
- Prior art keywords
- gas sensor
- carbon dioxide
- thick film
- batio
- manufacture method
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 23
- 239000001569 carbon dioxide Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 19
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000002019 doping agent Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 101710134784 Agnoprotein Proteins 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- 229910001922 gold oxide Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 229910002113 barium titanate Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- 238000007650 screen-printing Methods 0.000 abstract 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
A CuO-BaTiO3 series gas-sensitive element of semiconductor sensor for detecting CO2 gas is prepared by thick-film technology, which includes such steps as mixing BaCO3 with TiO2 in mole ratio of 1:1, calcining at 1300 deg.C for 6 hr, grinding, mixing with CuO in mole ratio of 1:1, grinding, adding one or more of AgNO3, PdCl4, SrO, La2O3, ZnO and Bi2O3, grinding, adding deionized water, grinding, silk screen printing on alumina substrate having Au electrodes and ruthenium oxide resistance layer for heating, and heat treating at 550 deg.C for 5 hr.
Description
Technical field
The present invention relates to a kind of manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide, belong to sensor technology and semiconductor transducer and make the field.
Background technology
Semiconductor gas sensor is meant semi-conducting material is added the gas sensor that top electrode and heating resistor are prepared from.Because the variation of environmental gas composition causes the electrical property of semiconductor gas sensor and changes the kind and the concentration of the gas that exists in the testing environment by the resistance of measuring semiconductor gas sensor.
As everyone knows, carbon dioxide is the gas that causes greenhouse effect and global warming.Common in the past detection method is to use pyroscan.The pyroscan volume is big, and the price height is not suitable for on-the-spot quick or online detection.The semi-conducting material that general semiconductor gas sensor uses is materials such as tin ash, zinc oxide, iron oxide, but they are not very sensitive to traces of carbon dioxide, are not suitable for detecting carbon dioxide.
Summary of the invention
The purpose of this invention is to provide the semiconductor transducer gas sensor and the manufacture method thereof that detect carbon dioxide.Another object of the present invention provides a kind of doped with Cu O-BaTiO
3The thick-film technique of system is with preparation technology's carbon dioxide semiconductor transducer gas sensor easy, with low cost.
A kind of manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide of the present invention is characterized in that, adopts thick-film technique to make doped with Cu O-BaTiO
3The thick film gas-sensitive element of system, dopant comprises the AgNO that contains the Ag ion
3, PdCl
4, SrO, La
2O
3, ZnO, Bi
2O
3In one or more.This CuO-BaTiO
3The base-material manufacture method of system thick film is: adopt and analyze pure BaCO
3And TiO
2With 1: 1 mixed in molar ratio, and grind evenly, mixture was calcined 6 hours down at 1300 ℃, and the taking-up back is pulverized and grind even, and gained powder and CuO are pressed 1: 1 mixed in molar ratio, ground evenly once more, promptly got the thick film base-material.In this base-material, add a certain amount of dopant, grind evenly, a certain amount of deionized water of adding in the base-material powder after doping then, and be ground to pulpous state, then slurry is printed in the silk screen mode on the end face of alumina substrate of preprocessed gold and ruthenium oxide resistance zone of heating, and, generate thick film 550 ℃ of following heat treatments 5 hours, make the gas sensor of transducer thus.
Described alumina substrate, its two ends are provided with gold electrode, be provided with the ruthenium oxide resistance zone of heating at the back side of alumina substrate, its preparation method is respectively to draw a horizontal line with gold paste at the double-edged two ends of end liner earlier being of a size of on the alumina substrate of 3 * 5mm, have four, 950 ℃ of sintering temperatures 10 minutes, form four gold electrodes; Ruthenium-oxide slurry in substrate back printing 600 ℃ of sintering temperatures 30 minutes, forms the ruthenium oxide resistance zone of heating.
The kind of dopant and doping are key technologies of the present invention.In Fig. 1, shown of the influence of Ag ion incorporation to the semiconductor transducer sensitivity.In Fig. 2, then shown doping Ag ion CuO-BaTiO
3The sensitivity of system semiconductor transducer and the relation curve of gas concentration lwevel.
Advantage of the present invention and effect are: adopt the thick-film technique preparation based on doped with Cu O-BaTiO
3The gas sensor of system makes this transducer gas sensor can improve sensitive property to carbon dioxide greatly, makes this transducer gas sensor good sensitivity characteristic all be arranged to carbon dioxide in 100ppm to 10% concentration range.So it can be applied to fields such as agricultural, environmental pollution and gas analysis.The inventive method can provide a kind of manufacturing process easy, the semiconductor transducer gas sensor of cheap detection carbon dioxide.
Description of drawings
Fig. 1 be in the semiconductor transducer Ag ion incorporation to the influence of its sensitivity.
Fig. 2 is the CuO-BaTiO of doping Ag ion
3The sensitivity of system semiconductor transducer and the relation curve of gas concentration lwevel.
Fig. 3 is the structural representation of carbon dioxide gas sensor gas sensor.
Embodiment
Now in conjunction with the accompanying drawings and embodiments the present invention further is described in the back:
Embodiment one: with CuO-BaTiO
3Be base-material, the preparation method of base-material is: with analytically pure BaCO
3And TiO
2With 1: 1 mixed in molar ratio, and grind evenly, mixture was calcined 6 hours down at 1300 ℃, and the taking-up back is pulverized and grind even, and gained powder and CuO are pressed 1: 1 mixed in molar ratio, ground evenly once more, promptly got the thick film base-material.Use AgNO
3Add in the above-mentioned base-material as dopant by 0.8mol% by 1mol%, SrO, grind evenly, the deionized water that adds 3mol then, and be ground to pulpous state, then slurry is printed in the silk screen mode on the end face of alumina substrate of preprocessed gold and ruthenium oxide resistance zone of heating, and, generate thick film 550 ℃ of following heat treatments 5 hours, make the gas sensor of transducer thus.
Described alumina substrate, its two ends are provided with gold electrode, be provided with the ruthenium oxide resistance zone of heating at the back side of alumina substrate, its preparation method is respectively to draw a horizontal line with gold paste at the double-edged two ends of substrate earlier being of a size of on the alumina substrate of 3 * 5mm, have four, 950 ℃ of sintering temperatures 10 minutes, form four gold electrodes; Ruthenium-oxide slurry in substrate back printing 600 ℃ of sintering temperatures 30 minutes, forms the ruthenium oxide resistance zone of heating.
The structure of the semiconductor transducer gas sensor of the detection carbon dioxide that finally makes as shown in Figure 3.Among Fig. 3,1 is gold electrode, and 2 is the thick film sensitive layer, and 3 is the ruthenium oxide resistance zone of heating, and 4 is alumina substrate.
Embodiment two: with CuO-BaTiO
3Be base-material, the preparation method of its base-material and embodiment one are identical.Use AgNO
3Press 0.5mol%, PdCl
4Press 1mol%, La
2O
3Add in the above-mentioned base-material as dopant by 1mol%, grind evenly, the deionized water that adds 3mol then, and be ground to pulpous state, then slurry is printed in the silk screen mode on the end face of alumina substrate of preprocessed gold and ruthenium oxide resistance zone of heating, and, generate thick film 550 ℃ of following heat treatments 5 hours, make the gas sensor of transducer thus.
Described alumina substrate, its two ends are provided with gold electrode, are provided with the ruthenium oxide resistance zone of heating at the back side of alumina substrate, its preparation method fully with previous embodiment one in identical.The structure of the semiconductor transducer gas sensor of the detection carbon dioxide that finally makes as shown in Figure 3.
Embodiment three: with CuO-BaTiO
3Be base-material, the preparation method of its base-material and embodiment one are identical.Use AgNO
3Press 0.5mol%, ZnO and press 1mol%, Bi
2O
3Add in the above-mentioned base-material as dopant by 1mol%, grind evenly, the deionized water that adds 3mol then, and be ground to pulpous state, then slurry is printed in the silk screen mode on the end face of alumina substrate of preprocessed gold and ruthenium oxide resistance zone of heating, and, generate thick film 550 ℃ of following heat treatments 5 hours, make the gas sensor of transducer thus.
Described alumina substrate, its two ends are provided with gold electrode, are provided with the ruthenium oxide resistance zone of heating at the back side of alumina substrate, its preparation method fully with previous embodiment one in identical.The structure of the semiconductor transducer gas sensor of the detection carbon dioxide that finally makes as shown in Figure 3.
This semiconductor transducer gas sensor is when reality is used, when promptly detecting in containing the traces of carbon dioxide environment, because the CuO-BaTiO on the gas sensor
3Variation has taken place in the electrical property of thick film sensitive layer, therefore just can learn the concentration of carbon dioxide in the environment by the measuring resistance size.Also essential in when work by the gold electrode input direct voltage, the ruthenium oxide resistance zone of heating is under 200 ℃ the working temperature, make the transducer can operate as normal.
Claims (5)
1. a manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide is characterized in that, adopts thick-film technique to make doped with Cu O-BaTiO
3The thick film gas-sensitive element of system, dopant comprises AgNO
3, PdCl
4, SrO, La
2O
3, ZnO, Bi
2O
3In one or more; This CuO-BaTiO
3The base-material manufacture method of system thick film is: adopt and analyze pure BaCO
3And TiO
2With 1: 1 mixed in molar ratio, and grind evenly, mixture was calcined 6 hours down at 1300 ℃, and the taking-up back is pulverized and grind even, and gained powder and CuO are pressed 1: 1 mixed in molar ratio, ground evenly once more, promptly got the thick film base-material; In this base-material, add a certain amount of dopant, grind evenly, a certain amount of deionized water of adding in the base-material powder after doping then, and be ground to pulpous state; Then slurry is printed in the silk screen mode on the end face of alumina substrate of preprocessed gold and ruthenium oxide resistance zone of heating, and, generates thick film, make the gas sensor of transducer thus 550 ℃ of following heat treatments 5 hours.
2. a kind of manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide according to claim 1, it is characterized in that, the two ends of described alumina substrate are provided with gold electrode, be provided with the ruthenium oxide resistance zone of heating at the back side of alumina substrate, its preparation method is respectively to draw a horizontal line with gold paste at the double-edged two ends of substrate earlier being of a size of on the alumina substrate of 3 * 5mm, have four,, form four gold electrodes 950 ℃ of sintering temperatures 10 minutes; Ruthenium-oxide slurry in substrate back printing 600 ℃ of sintering temperatures 30 minutes, forms the ruthenium oxide resistance zone of heating.
3. a kind of manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide according to claim 1 is characterized in that described doped with Cu O-BaTiO
3The dopant of system thick film is the AgNO that contains the Ag ion
3Mixture with SrO.
4. a kind of manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide according to claim 1 is characterized in that described doped with Cu O-BaTiO
3The dopant of system thick film is the AgNO that contains the Ag ion
3And PdCl
4, La
2O
3Mixture.
5. a kind of manufacture method that detects the semiconductor transducer gas sensor of carbon dioxide according to claim 1 is characterized in that described doped with Cu O-BaTiO
3The dopant of system thick film is the AgNO that contains the Ag ion
3With ZnO, Bi
2O
3Mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02160100.3A CN1269234C (en) | 2002-12-31 | 2002-12-31 | Manufacturing method for semiconductor gas-sensing device of testing carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02160100.3A CN1269234C (en) | 2002-12-31 | 2002-12-31 | Manufacturing method for semiconductor gas-sensing device of testing carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424778A true CN1424778A (en) | 2003-06-18 |
| CN1269234C CN1269234C (en) | 2006-08-09 |
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ID=4753399
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02160100.3A Expired - Fee Related CN1269234C (en) | 2002-12-31 | 2002-12-31 | Manufacturing method for semiconductor gas-sensing device of testing carbon dioxide |
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|---|---|
| CN (1) | CN1269234C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320667C (en) * | 2003-07-10 | 2007-06-06 | 上海大学 | Manufacturing method of hydrogen sulfide semiconductor sensor gas sensitive element |
| CN101158661B (en) * | 2007-11-16 | 2011-05-11 | 华中科技大学 | Semi-conductor oxidate gas sensor preparation method |
| CN102080268A (en) * | 2010-12-07 | 2011-06-01 | 吉林大学 | Orderly arranged In2O3 nanofibers and application of same in preparation of ultra-fast response alcohol sensor |
| CN104502417A (en) * | 2015-01-10 | 2015-04-08 | 吉林大学 | La2O3-WO3 oxide semiconductor acetone gas sensor and preparation method thereof |
| CN108845004A (en) * | 2018-06-15 | 2018-11-20 | 浙江大学 | A kind of photoelectric current carbon dioxide sensor |
-
2002
- 2002-12-31 CN CN02160100.3A patent/CN1269234C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320667C (en) * | 2003-07-10 | 2007-06-06 | 上海大学 | Manufacturing method of hydrogen sulfide semiconductor sensor gas sensitive element |
| CN101158661B (en) * | 2007-11-16 | 2011-05-11 | 华中科技大学 | Semi-conductor oxidate gas sensor preparation method |
| CN102080268A (en) * | 2010-12-07 | 2011-06-01 | 吉林大学 | Orderly arranged In2O3 nanofibers and application of same in preparation of ultra-fast response alcohol sensor |
| CN104502417A (en) * | 2015-01-10 | 2015-04-08 | 吉林大学 | La2O3-WO3 oxide semiconductor acetone gas sensor and preparation method thereof |
| CN108845004A (en) * | 2018-06-15 | 2018-11-20 | 浙江大学 | A kind of photoelectric current carbon dioxide sensor |
| CN108845004B (en) * | 2018-06-15 | 2020-10-13 | 浙江大学 | Photocurrent carbon dioxide sensor |
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| Publication number | Publication date |
|---|---|
| CN1269234C (en) | 2006-08-09 |
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Granted publication date: 20060809 Termination date: 20100201 |