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 PDF

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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
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gas sensor
carbon dioxide
thick film
batio
manufacture method
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CN1269234C (en
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焦正
吴明红
顾建中
俎建华
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Shanghai University
University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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

Detect the manufacture method of the semiconductor transducer gas sensor of carbon dioxide
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.
CN02160100.3A 2002-12-31 2002-12-31 Manufacturing method for semiconductor gas-sensing device of testing carbon dioxide Expired - Fee Related CN1269234C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
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

Cited By (6)

* Cited by examiner, † Cited by third party
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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