CN102520018A - Semiconductor oxide sensitivity-based integrated carbon dioxide sensor - Google Patents
Semiconductor oxide sensitivity-based integrated carbon dioxide sensor Download PDFInfo
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- CN102520018A CN102520018A CN2011104125341A CN201110412534A CN102520018A CN 102520018 A CN102520018 A CN 102520018A CN 2011104125341 A CN2011104125341 A CN 2011104125341A CN 201110412534 A CN201110412534 A CN 201110412534A CN 102520018 A CN102520018 A CN 102520018A
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- semiconductor oxide
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Abstract
The invention discloses a semiconductor oxide sensitivity-based integrated carbon dioxide sensor, which is characterized in that: a detection unit is set as the following that: one end of an n-type semiconductor oxide sensitive element and one end of a p-type semiconductor oxide sensitive element are connected to a half-bridge output end of the detection unit; the other end of the n-type semiconductor oxide sensitive element is taken as a first electrode lead terminal of the test unit; the other end of the p-type semiconductor oxide sensitive element is taken as a second electrode lead terminal of the detection unit; on the backside of the ceramic substrate, heating resistors are respectively disposed corresponding to each n-type semiconductor oxide sensitive element and each p-type semiconductor oxide sensitive element. The sensor of the invention can effectively improve the detection accuracy and reliability of the sensor.
Description
Technical field
The present invention relates to CO
2Field of gas detection, the integrated CO that particularly a kind of based semiconductor oxide is responsive
2Sensor.
Background technology
Carbon dioxide is a kind of gas of colorless and odorless, and tart flavour is arranged, and density is greater than air, and water-soluble.The detection of carbon dioxide has significance at aspects such as agricultural production, Detection of Air Quality.
Present CO
2Gas detection is mainly infrared spectrum formula gas sensor.Like application number: 201010216518.0, the applying date: " a kind of main stream-type carbon dioxide concentration measurement device " on July 2nd, 2010; Comprise infrared light supply, gas detection module, filtering circuit, amplifying circuit, computing unit, gas main channel and measure passage; The gas detection module comprises main measuring junction, reference edge, is arranged on the temperature sensor between main measuring junction and the reference edge; Infrared light supply is positioned at a side of gas main channel; Main measuring junction and reference edge each other near and be positioned at the opposite side of gas main channel, measure channel vertical in the gas main channel; Measure passage and be provided with light source filter plate, receiving end, main measuring junction and reference edge filter plate.This operation of equipment is simple, the reaction rapid sensitive, and cleaned and changed convenient and swift, real-time, degree of accuracy is high; But this infrared sensor involves great expense.
Solid electrolyte formula CO in addition
2Gas sensor also is used to detect CO as a kind of electrochemical transducer[sensor
2Gas.Like application number: 200510086426.4, the applying date: " a kind of dual-solid electrolyte CO on September 14th, 2005
2Sensor and preparation method thereof ", the solid electrolyte of the doped zirconia solid electrolyte of oxide ion conduction and cationic electroconductive is compound, and adopt and contain the cationic carbonate of this kind and do auxiliary electrode, form the sensor of chip or other shapes.This sensor prepares simple, easy to use, and two-electrolyte sensor measurement precision is lower, though through the irreversible thermodynamics correction its measuring accuracy, but still fundamentally do not solve its measuring accuracy problem.
Semiconductor resistor formula gas sensor is highly sensitive owing to it, energy consumption is low, simple in structure, size is little, easy of integration, be prone to batch process, low cost and other advantages become with fastest developing speed in the gas sensor, use the widest one type.The carbon dioxide sensor that the based semiconductor oxide is responsive can be realized CO
2Volume fraction is a kind of more promising CO in 100ppm to 10% range detection
2Checkout equipment.Like application number: " detecting the manufacturing approach of the semiconductor transducer gas sensor of carbon dioxide " of 02160100.3, the applying date: 2002-12-31, adopt 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.Application number: 200310109271.2, the applying date: 2003-12-11 " detecting the manufacturing approach of the Lanthanum monochloride monoxide film sensitive element of carbon dioxide " adopts lanthana to realize CO as sensitive material
2Detection.This type sensor has advantage simple in structure, that preparation technology is simple, with low cost.Sensitivity is low, stable, the problem of poor reliability but such carbon dioxide gas sensor also exists at present, and its detection effect of particularly single sensitive element is relatively poor.
Summary of the invention
The present invention be directed to the deficiency of prior art, provide the based semiconductor oxide responsive integrated carbon dioxide sensor, to improve detection sensitivity and measuring accuracy.
Technical solution problem of the present invention adopts following technical scheme:
The design feature that the present invention is based on the responsive integrated carbon dioxide sensor of conductor oxidate is:
Detecting unit is set is: n type semiconductor oxide sensitive element is connected detecting unit half-bridge output terminal jointly with an end of an one of which end and a p type semiconductor oxide sensitive element; With the other end of said n type semiconductor oxide sensitive element as the detecting unit first contact conductor end; With the other end of said p type semiconductor oxide sensitive element as the detecting unit second contact conductor end;
Eight groups to CO
2Have the integrated surface that is arranged on same ceramic substrate of detecting unit of different sensitivity characteristics, each is organized the half-bridge output terminal of detecting unit and independently draws separately, and the first contact conductor end interconnects jointly draws, and the second contact conductor end interconnects jointly draws;
The back side at said ceramic substrate; Be provided with n type semiconductor oxide sensitive element heating resistor corresponding to each n type semiconductor oxide sensitive element, be provided with p type semiconductor oxide sensitive element heating resistor corresponding to each p type semiconductor oxide sensitive element; And the n type semiconductor oxide sensitive element heating resistor and the p type semiconductor oxide sensitive element heating resistor that are in the same detecting unit are provided with for series connection.
The characteristics that the present invention is based on the responsive integrated carbon dioxide sensor of conductor oxidate also are:
The said n type semiconductor oxide sensitive element of respectively organizing in the detecting unit is with SnO
2For adding La in the basis
2O
3Constitute matrix material, in said matrix material, add the adjuvant of Different Weight number percent; Said La
2O
3Consumption be SnO by weight percentage
240%～50% of consumption;
The said p type semiconductor oxide sensitive element of respectively organizing in the detecting unit is with SnO
2Add CuO for the basis and constitute matrix material, in said matrix material, add the adjuvant of Different Weight number percent; The consumption of said CuO is SnO by weight percentage
240%～50% of consumption.
The present invention is based on the responsive integrated CO of conductor oxidate
2The characteristics of sensor also are:
The adjuvant that is used for preparing said n type semiconductor oxide sensitive element is CeO
2, Ag
2O, SiO
2And CaO, the addition of each adjuvant is 5%～10% of matrix material by weight percentage;
The adjuvant that is used for preparing said p type semiconductor oxide sensitive element is CeO
2, Ag
2O, Bi
2O
3, SiO
2, CaO and BaO, the addition of each adjuvant is 5%～10% of matrix material by weight percentage.
Compared with present technology, beneficial effect of the present invention is embodied in:
The present invention is based on the responsive integrated CO of conductor oxidate
2Sensor has the sensing unit of eight different sensitivity characteristics, exports eight sensitive signals simultaneously, the CO that common reflection is detected
2Gas concentration, eight output signals are handled through information fusion technology, can improve the accuracy of detection and the reliability of sensor.Each sensing unit is made up of a n N-type semiconductor N gas detecting element and a p N-type semiconductor N gas detecting element respectively, and n N-type semiconductor N gas detecting element and p N-type semiconductor N gas detecting element are to CO
2Gas has antipodal sensitivity characteristic; They are formed half-bridge; Can improve detection sensitivity, simultaneously, n N-type semiconductor N gas detecting element and p N-type semiconductor N gas detecting element have close sensitivity characteristic again to temperature, humidity; Export signal with the half-bridge mode, can reduce environment temperature, humidity greatly and change the interference that is produced.
Description of drawings
Fig. 1 distributes and connection lead-in wire synoptic diagram for 16 sensitive elements in front of ceramic substrate among the present invention;
Fig. 2 distributes for 16 heating resistors in the ceramic substrate back side among the present invention and connects the lead-in wire synoptic diagram;
Label among the figure: 1 is ceramic substrate; 2 is n type semiconductor oxide sensitive element; 3 is p type semiconductor oxide sensitive element; 4 is detecting unit half-bridge output terminal; 5 is the detecting unit first contact conductor end; 6 is the detecting unit second contact conductor end; 7 is n type semiconductor oxide sensitive element heating resistor; 8 is p type semiconductor oxide sensitive element heating resistor.
Embodiment
Referring to Fig. 1, the responsive integrated CO of based semiconductor oxide in the present embodiment
2The version of sensor is:
Detecting unit is set is: n type semiconductor oxide sensitive element 2 is connected detecting unit half-bridge output terminal 4 jointly with an end of an one of which end and a p type semiconductor oxide sensitive element 3; With the other end of n type semiconductor oxide sensitive element 2 as the detecting unit first contact conductor end 5; With the other end of p type semiconductor oxide sensitive element 3 as the detecting unit second contact conductor end 6;
Eight groups to CO
2The integrated surface that is arranged on same ceramic substrate 1 of detecting unit with different sensitivity characteristics; Each is organized the half-bridge output terminal 4 of detecting unit and independently draws separately; Each detecting unit first contact conductor end 5 interconnects jointly draws, and each detecting unit second contact conductor end 6 interconnects jointly draws;
The back side at ceramic substrate 1; Be provided with n type semiconductor oxide sensitive element heating resistor 7 corresponding to each n type semiconductor oxide sensitive element 2, be provided with p type semiconductor oxide sensitive element heating resistor 8 corresponding to each p type semiconductor oxide sensitive element 3; And the n type semiconductor oxide sensitive element heating resistor 7 that is in the same detecting unit is provided with for series connection with p type semiconductor oxide sensitive element heating resistor 8.
In the practical implementation, each n type semiconductor oxide sensitive element 2 of organizing in the detecting unit is with SnO
2For adding La in the basis
2O
3Constitute matrix material, in matrix material, add the adjuvant of Different Weight number percent; La
2O
3Consumption be SnO by weight percentage
240%～50% of consumption;
Each p type semiconductor oxide sensitive element 3 of organizing in the detecting unit is with SnO
2Add CuO for the basis and constitute matrix material, in matrix material, add the adjuvant of Different Weight number percent; The consumption of CuO is SnO by weight percentage
240%～50% of consumption.
The adjuvant that is used for preparing said n type semiconductor oxide sensitive element is CeO
2, Ag
2O, SiO
2And CaO, the addition of each adjuvant is 5%～10% of matrix material by weight percentage;
The adjuvant that is used for preparing said p type semiconductor oxide sensitive element is CeO
2, Ag
2O, Bi
2O
3, SiO
2, CaO and BaO, the addition of each adjuvant is 5%～10% of matrix material by weight percentage.
Preparation has the sensitive material of the n type semiconductor oxide sensitive element 2 of different sensitivity characteristics:
With SnCl
45H
2O is dissolved in deionized water, and dropping ammonia reaches about 4～5 pH value, and the deposition of generation is through dried after being washed repeatedly, 600 ℃ of following sintering 2 hours, obtains SnO
2Material; At LaCl
37H
2Dropping ammonia in the O WS, the deposition of generation be through dried after being washed repeatedly, 600 ℃ of following sintering 2 hours, obtains La
2O
3Material is with SnO
2Be the basis, add 40%～50% La by weight percentage
2O
3, for example, with SnO
2Be the basis, add 40%, 45% and 50% La by weight percentage respectively
2O
3Constitute three kinds of different matrix material prescriptions, have a Different L a what 600 ℃ of following sintering promptly obtained n type semiconductor oxide sensitive element 2 in 1 hour again after fully grinding
2O
3Three kinds of different matrix materials of addition;
Is the basis with the matrix material, adds that to account for its percentage by weight respectively be 5%～10% CeO
2, Ag
2O, SiO
2And CaO, for example, with the matrix material basis, add that to account for its percentage by weight be 5% CeO
2, 5% Ag
2O, 5% SiO
2Obtain a sensitive material prescription with 5% CaO, add that to account for its percentage by weight respectively be 10% CeO
2, 10% Ag
2O, 10% SiO
2Obtain another sensitive material prescription with 10% CaO, or the like, promptly obtain having the sensitive material of the n type semiconductor oxide sensitive element 2 of different sensitivity characteristics after fully grinding.
Preparation has the sensitive material of the p type semiconductor oxide sensitive element 3 of different sensitivity characteristics:
With SnCl
45H
2O is dissolved in deionized water, and dropping ammonia reaches about 4～5 pH value, and the deposition of generation is through dried after being washed repeatedly, 600 ℃ of following sintering 2 hours, obtains SnO
2Material; At CuCl
2Dropping ammonia in the WS, the deposition of generation be through dried after being washed repeatedly, 600 ℃ of following sintering 2 hours, obtains the CuO material, with SnO
2Be the basis, add 40%～50% CuO by weight percentage, for example, with SnO
2Be the basis; Add 40%, 45% by weight percentage respectively and constitute three kinds of different matrix material prescriptions, promptly obtained the different matrix material with different CuO additions of p type semiconductor oxide sensitive element 3 after fully grinding again at 600 ℃ of following sintering in 1 hour with 50% CuO;
Be that the basis adds that to account for its percentage by weight respectively be 5%～10% CeO with the matrix material
2, Ag
2O, Bi
2O
3, SiO
2, CaO and BaO, for example, be the basis with the matrix material, add that to account for its percentage by weight be 5% CeO
2, 5% Ag
2O, 5% Bi
2O
3, 5% SiO
2, 5% CaO and 5% BaO obtain a sensitive material prescription, adds that to account for its percentage by weight be 10% CeO
2, 10% Ag
2O, 10% Bi
2O
3, 10% SiO
2, 10% CaO and 10% BaO obtain another sensitive material prescription, or the like, promptly obtain having the sensitive material of the p type semiconductor oxide sensitive element 3 of different sensitivity characteristics after fully grinding.
Element one: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 40%
2O
3Constitute matrix body material, be the basis, add the CeO of matrix material consumption 5% with the matrix material consumption
2, 5% Ag
2O, 5%SiO
2And 5%CaO;
Element two: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 40%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 10% with the matrix material consumption
2, 10% Ag
2O, 10%SiO
2And 10%CaO;
Element three: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 45%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 5% with the matrix material consumption
2, 5% Ag
2O, 5%SiO
2And 5%CaO;
Element four: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 45%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 8% with the matrix material consumption
2, 8% Ag
2O, 8%SiO
2And 8%CaO;
Element five: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 45%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 10% with the matrix material consumption
2, 10% Ag
2O, 10%SiO
2And 10%CaO;
Element six: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 50%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 5% with the matrix material consumption
2, 5% Ag
2O, 5% SiO
2And 5%CaO;
Element seven: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 50%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 8% with the matrix material consumption
2, 8% Ag
2O, 8%SiO
2And 8%CaO;
Element eight: with SnO
2Material usage is the basis, adds SnO
2The La of material usage 50%
2O
3Constitute matrix material, be the basis, add the CeO of matrix material consumption 10% with the matrix material consumption
2, 10% Ag
2O, 10%SiO
2And 10%CaO.
Embodiment 2: the concrete formula examples of sensitive material for preparing eight p type semiconductor oxide sensitive elements 3 with different sensitivity characteristics is following:
Element one: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 40% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 5%
2, 5% Ag
2O, 5% Bi
2O
3, 5% SiO
2, 5% CaO and 5% BaO;
Element two: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 40% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 10%
2, 10% Ag
2O, 10% Bi
2O
3, 10% SiO
2, 10% CaO and 10% BaO;
Element three: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 45% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 5%
2, 5% Ag
2O, 5% Bi
2O
3, 5% SiO
2, 5% CaO and 5% BaO;
Element four: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 45% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 8%
2, 8% Ag
2O, 8% Bi
2O
3, 8% SiO
2, 8% CaO and 8% BaO;
Element five: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 45% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 10%
2, 10% Ag
2O, 10% Bi
2O
3, 10% SiO
2, 10% CaO and 10% BaO;
Element six: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 50% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 5%
2, 5% Ag
2O, 5% Bi
2O
3, 5% SiO
2, 5% CaO and 5% BaO;
Element seven: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 50% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 8%
2, 8% Ag
2O, 8% Bi
2O
3, 8% SiO
2, 8% CaO and 8% BaO;
Element eight: with SnO
2Material usage is the basis, adds SnO
2The CuO of material usage 50% constitutes matrix material, is the basis with the matrix material consumption, adds the CeO of matrix material consumption 10%
2, 10% Ag
2O, 10% Bi
2O
3, 10% SiO
2, 10% CaO and 10% BaO.
The back side at ceramic substrate 1; With the ruthenium-oxide slurry serves as that the basis is through thick film screen printing prepared n type semiconductor oxide sensitive element heating resistor 7 and p type semiconductor oxide sensitive element heating resistor 8; During detection; The n type semiconductor oxide sensitive element heating resistor 7 that is in the series connection setting in the same detecting unit adds certain DC voltage to provide element testing needed working temperature with p type semiconductor oxide sensitive element heating resistor 8 two ends, and its optimum working temperature scope is 250 ℃～280 ℃.
Claims (3)
1. the responsive integrated carbon dioxide sensor of a based semiconductor oxide is characterized in that:
Detecting unit is set is: a n type semiconductor oxide sensitive element (2) is connected detecting unit half-bridge output terminal (4) jointly with an end of an one of which end and a p type semiconductor oxide sensitive element (3); With the other end of said n type semiconductor oxide sensitive element (2) as the detecting unit first contact conductor end (5); With the other end of said p type semiconductor oxide sensitive element (3) as the detecting unit second contact conductor end (6);
Eight groups to CO
2The integrated surface that is arranged on same ceramic substrate (1) of detecting unit with different sensitivity characteristics; Each is organized the half-bridge output terminal (4) of detecting unit and independently draws separately; The first contact conductor end (5) interconnects jointly draws, and the second contact conductor end (6) interconnects jointly draws;
The back side in said ceramic substrate (1); Be provided with n type semiconductor oxide sensitive element heating resistor (7) corresponding to each n type semiconductor oxide sensitive element (2), be provided with p type semiconductor oxide sensitive element heating resistor (8) corresponding to each p type semiconductor oxide sensitive element (3); And the n type semiconductor oxide sensitive element heating resistor (7) and the p type semiconductor oxide sensitive element heating resistor (8) that are in the same detecting unit are provided with for series connection.
2. the integrated carbon dioxide sensor that based semiconductor oxide according to claim 1 is responsive is characterized in that:
The said n type semiconductor oxide sensitive element of respectively organizing in the detecting unit (2) is with SnO
2For adding La in the basis
2O
3Constitute matrix material, in said matrix material, add the adjuvant of Different Weight number percent; Said La
2O
3Consumption be SnO by weight percentage
240%～50% of consumption;
The said p type semiconductor oxide sensitive element of respectively organizing in the detecting unit (3) is with SnO
2Add CuO for the basis and constitute matrix material, in said matrix material, add the adjuvant of Different Weight number percent; The consumption of said CuO is SnO by weight percentage
240%～50% of consumption.
3. the integrated CO that based semiconductor oxide according to claim 2 is responsive
2Sensor is characterized in that:
The adjuvant that is used for preparing said n type semiconductor oxide sensitive element is CeO
2, Ag
2O, SiO
2And CaO, the addition of each adjuvant is 5%～10% of matrix material by weight percentage;
The adjuvant that is used for preparing said p type semiconductor oxide sensitive element is CeO
2, Ag
2O, Bi
2O
3, SiO
2, CaO and BaO, the addition of each adjuvant is 5%～10% of matrix material by weight percentage.
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|---|---|---|---|
| CN2011104125341A CN102520018A (en) | 2011-12-12 | 2011-12-12 | Semiconductor oxide sensitivity-based integrated carbon dioxide sensor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104125341A CN102520018A (en) | 2011-12-12 | 2011-12-12 | Semiconductor oxide sensitivity-based integrated carbon dioxide sensor |
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| CN102520018A true CN102520018A (en) | 2012-06-27 |
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| CN104280343A (en) * | 2013-07-09 | 2015-01-14 | 青岛中一监测有限公司 | Gas sensitive element for environment monitoring sensor and environment monitoring sensor |
| CN107003263A (en) * | 2014-12-22 | 2017-08-01 | 罗伯特·博世有限公司 | Sensor and its manufacture method for measuring the gas concentration lwevel in admixture of gas |
| CN115452757A (en) * | 2022-11-11 | 2022-12-09 | 电子科技大学 | CO based on sensor 2 Concentration monitoring system |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104280343A (en) * | 2013-07-09 | 2015-01-14 | 青岛中一监测有限公司 | Gas sensitive element for environment monitoring sensor and environment monitoring sensor |
| CN107003263A (en) * | 2014-12-22 | 2017-08-01 | 罗伯特·博世有限公司 | Sensor and its manufacture method for measuring the gas concentration lwevel in admixture of gas |
| CN115452757A (en) * | 2022-11-11 | 2022-12-09 | 电子科技大学 | CO based on sensor 2 Concentration monitoring system |
| CN115452757B (en) * | 2022-11-11 | 2023-02-14 | 电子科技大学 | CO based on sensor 2 Concentration monitoring system |
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Application publication date: 20120627 |