CN1048770A - Hydrogen-sensitive element and autofrettage - Google Patents
Hydrogen-sensitive element and autofrettage Download PDFInfo
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- CN1048770A CN1048770A CN 90104738 CN90104738A CN1048770A CN 1048770 A CN1048770 A CN 1048770A CN 90104738 CN90104738 CN 90104738 CN 90104738 A CN90104738 A CN 90104738A CN 1048770 A CN1048770 A CN 1048770A
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- hydrogen
- sensitive element
- oxide semiconductor
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Abstract
Hydrogen-sensitive element of the present invention and manufacture method, it is characterized in that described hydrogen-sensitive element is the sensitive membrane that a kind of upgrading is handled the Metal Oxide Semiconductor Gas Sensing element, forms the upgrading type metal oxide semiconductor hydrogen-sensitive element that the silicon dioxide hydrogen with molecular sieve filtration function sees through film.Its manufacture method is the Metal Oxide Semiconductor Gas Sensing element that comprises hydrogen by the traditional handicraft preparation to be positioned in the specific organosilicon salt atmosphere exert a gradual, uplifting influence on, and the certain thickness silicon dioxide hydrogen of self-sow sees through film.Hydrogen-sensitive element of the present invention has the high selectivity of hydrogen and response excellent results.
Description
Hydrogen-sensitive element of the present invention and autofrettage relate to a kind of surfaction type metal oxide semiconductor hydrogen-sensitive element and autofrettage thereof more specifically, belong to electronics sensitive technology field.
In the past, with the sensitive material of metal oxide semiconductor material, it was formed sensitive membrane on the solid substrate that semiconductor, insulator and various gas sensor are used as the flammable gas that comprises hydrogen.This gas sensor and manufacture method have been known.
This class comprises the flammable gas gas sensor of hydrogen, as disclosed thin film SnO 2 gas-sensitive element of Chinese patent CN85100030 and manufacture method "; propose a kind of thin film type metal oxide semiconductor gas sensor, the disclosed technology of this file is representational at film-type semiconductor gas sensor and manufacturing thereof.And for example Chinese patent CN87216840 disclosed " planar-type semiconductor gas sensor " provides a kind of metal oxide planar-type semiconductor gas sensor with room temperature gas sensitive effect of suitable production in enormous quantities, and it is formed in plane gas sensor aspect also is representative.The QM-N5 type heater-type sintered-type gas sensor that Tongjiang, Harbin Transistor Factory produces, it constitutes as shown in Figure 1, the outer heat resisting porcelain pipe (2) that is with of heater coil (1), the sensitive body (3) of the metal oxide semiconductor material that porcelain tube outer wall roller coating thickness is suitable, connection electrode lead-in wire (4) is through the high temperature sintering moulding, and this structure and method also are representational in sintered-type gas sensor.
Above-mentioned various types of semiconductor gas sensor, its metal-oxide semiconductor (MOS) sensitive membrane all is exposed to the element extexine, directly contact environment gas.Because of the sensitive membrane self property determines, to all gases such as H
2, CO, CH
4, C
H
, C
4H
10, CH
OH can produce sensitlzing effect.Accompanying drawing 2 illustrates the impedance curve of gas sensor to several inflammable gases.When gas concentration is lower than 200ppm, gas sensor to the ratio of the output impedance value of hydrogen and other gas output impedance values between 1.4～0.8.When gas concentration was 700ppm, above-mentioned impedance ratio was also only between 4～0.5.Common gas sensor resistance value between hydrogen and other inflammable gas is more or less the same, and therefore its common deficiency of above-mentioned gas sensor is to lack the selectivity to gas with various, lacks the single selective to hydrogen.Even between certain several gas, there is not selectivity at all.
Hydrogen is explosive hazardous gas commonly used in the industry, and hydrogen leak is easy to breaking out of fire and explosion accident, in order to prevent that accident from taking place to carry out safety detection and controlling alarm to the leakage of hydrogen.It is totally unfavorable that existing gas sensor hydrogen in to environment has in the application of exclusive test, and heat must influence test accuracy, stability and credible.
The present invention is to exclusive optionally breakthrough improvement of hydrogen and innovation to above-mentioned Metal Oxide Semiconductor Gas Sensing element.Not changing the sensitive membrane material and using on the traditional handicraft basis,, metal oxide sensitive membrane statement upgrading forms a kind of hydrogen-sensitive element that hydrogen is had high selectivity and response characteristic according to above-mentioned gas sensor deficiency from being started with.
The present invention also provides corresponding method of manufacture.
The present invention is the improvement to original metal-oxide semiconductor (MOS) flammable gas (comprising hydrogen) gas sensor, the Metal Oxide Semiconductor Gas Sensing element is handled through surfaction and is formed a kind of hydrogen-sensitive element, it is characterized by on the metal-oxide semiconductor (MOS) sensitive membrane of described gas sensor and see through film with layer of silicon dioxide hydrogen, environmental gas has only through outer silicon dioxide film just can enter sensitive membrane.The silica coating that is formed by special process is a kind of rete with the effect of molecular sieve permeation filtration, and it is 10 that silicon dioxide hydrogen sees through film thickness
～1 μ m, it only has by effect the little hydrogen of molecular diameter, and other macromolecular structure gas is had iris action.Therefore, rete effectively intercepts except that hydrogen other gas to the interference of sensitive membrane, and only experiences a kind of gas of hydrogen.This all has the gas sensor of gas sensitive effect to possess exclusive selectivity to the hydrogen sensitivity with regard to making originally to multiple gases, promptly forms the very high hydrogen-sensitive element of a kind of selectivity.
Form the initial element that hydrogen-sensitive element of the present invention uses-be that gas sensor can be to select in slug type, (comprising internal heat type and heater-type) film-type, plane or integrated-type metal-oxide semiconductor (MOS) flammable gas gas sensor.
It can be SnO that upgrading of the present invention is handled gas sensor
2Or ZnO
2Or Fe
2O
3Semiconductor gas sensor.
The method of making hydrogen-sensitive element is that the Metal Oxide Semiconductor Gas Sensing element that common process is made is exerted a gradual, uplifting influence in specific organosilicon salt atmosphere, sensitive membrane is made surperficial upgrading handle.Self-sow layer of silicon dioxide hydrogen sees through film on the metal-oxide semiconductor (MOS) sensitive membrane, said particular atmosphere is meant 100～500 ℃ of temperature, the sealed gas chamber of upgrading concentration 30%～100%, ambient temperature is selected to satisfy upgrading liquid atomizing requirement, and upgrading liquid concentration and edifying time are proportional.Upgrading liquid concentration height, the edifying time can shorten; Concentration is little, and the edifying time can extend, and reaches specific thickness with satisfied edifying back silicon dioxide hydrogen through film and is advisable.But concentration upgrading liquid in general the selection, excessive because of concentration, upgrading is handled wayward, and concentration is too small, and the edifying time is long again.
Edifying process sectional carries out, and midfeather is carried out burin-in process in the time.
See through film surface quality and molecular sieves stabilized permeability for improving silicon dioxide hydrogen, can put into 600 ℃ high temperature heat treatment after the edifying.
Described hydrogen-sensitive element manufacture method, the organosilicon salt of preparation upgrading liquid can be from dichlorosilane-SiH
2Cl
2, trim,ethylchlorosilane-(CH
3)
3SiCl
4, or tetraethoxysilane-Si(OC
2H
3)
4The middle selection.
Accompanying drawing
Fig. 1 heater-type sintered-type gas sensor structural representation.
Fig. 2 gas sensor in comprising the flammable gas of hydrogen, the response curve of gas concentration and output impedance.
Fig. 3 slug type hydrogen-sensitive element structural representation.
Fig. 4 plane hydrogen-sensitive element structural representation.
Fig. 5 film-type hydrogen-sensitive element structural representation.
Fig. 6 hydrogen-sensitive element of the present invention is to variable concentrations gas sensitization curve.
Fig. 7 Fig. 8, for hydrogen-sensitive element resonse characteristic of the present invention.
Description of drawings:
Fig. 1 heater-type sintered-type gas sensor, it is the gas sensor substrate that heater coil (1) is set in porcelain tube (2), will be that Metal Oxide Semiconductor Gas Sensing material roller coating sintering formation sensitive membrane (3) in substrate of major ingredient adds loading electrode (4) lead-in wire with the tin ash.
Fig. 2 gas sensor is to comprising the flammable gas of hydrogen, the response curve of gas concentration and output impedance, and curve 1 is H
2Impedance curve, curve 2 is C
2H
3The impedance curve of OH, curve 3 is the impedance curve of CO, curve 4 is CH
4Impedance curve, curve 5 is C
3H
6Impedance curve, curve 6 is C
4H
10Impedance curve, wherein dotted line is the impedance curve of air.
Other accompanying drawing is in conjunction with the embodiments in explanation.
Embodiment one:
(1) preparation of initial element before sintered-type gas sensor-the be upgrading
The gas sensitive preparation:
50% SnCl
4(or SnCl
2) aqueous solution and an amount of NH
30H
2O(concentration is 25%) reaction, the product oven dry is also pulverized, and carries out 700 ℃ of roastings in a hour, presses following mixed behind the sintering
SnO
2Al
2O
3PdCl
2SiO
2
80～90% 0.5～18% 0～10% 0～2%
(more than be weight percentage)
Compound fully grinds, at the even certain thickness above-mentioned compound of roller coating in the porcelain tube that heater coil (1) is housed (2) outside, sintering in 750 ℃ of high temperature, form sensitive membrane (3), welding lead (4) becomes the preceding initial element of upgrading that sintered-type gas sensor is hydrogen-sensitive element of the present invention.
(2) modulation of upgrading liquid and method for modifying
In following ratio preparation upgrading liquid
（CH
3）
3SiCl
4∶H
2O＝（99-70）%∶（1-30）%
It is 10 liters closed container that the above-mentioned initial element for preparing is put into volume, keep 450 ℃ of temperature, spray into upgrading liquid, upgrading liquid concentration is 3500ppm in the container, element exerted a gradual, uplifting influence in atmosphere 1 hour, element surface be sensitive membrane (3) gradually growthing silica hydrogen see through film (5).Thicknesses of layers 250
, see Fig. 3;
The edifying process can be carried out step by step, and burin-in process is made in blanking time in each edifying back.
Heat treatment 1 hour in 650 ℃ of high temperature at last.
Embodiment two:
(1) the plane gas sensor is the preparation of initial element before the upgrading.
Adopt semiconductor device " planar technique ", on the surface, silicon device drift region and injection region electrode of the horizontal P-N knot of having of planar structure, be deposited with the metal-oxide semiconductor (MOS) cover layer of gas-sensitive activity-be sensitive membrane, rete adopts SnO
2, ZnO
2Or Fe
2O
3, can adopt homogenous material, also can form the plane gas sensor, as initial element before the hydrogen-sensitive element upgrading with the mixture of different materials.Wherein substrate (11), drift region (7), injection region (8), electrode and SiO
2Protective layer (6) formation has horizontal P-N junction plane type silicon device.Equal deposit one deck gas-sensitive activity metal oxide sensitive membrane (3) on drift region (7) and injection region (8) and the electrode.
(2) modulation of upgrading liquid and method for modifying are identical with embodiment one.
After upgrading is handled, go up growth one deck SiO in sensitive membrane (3)
2Hydrogen sees through film (5), and thicknesses of layers should be strict controlled in claimed range.(see figure 4)
Embodiment three:
(1) initial element is made before thin film type gas-sensitive element-the be upgrading.
Form tin ash heating film (10) in substrate (9) one side through the cryochemistry deposition, form metal oxide sensitive membrane (3) at another side, the sensitive membrane raw material are butter of tin, 300～500 ℃ of substrate temperatures, 100～200 ℃ of raw material evaporating temperatures.Weld metal goes between, and makes the initial element of film-type of hydrogen-sensitive element of the present invention.
(2) to be analogous to embodiment one described for upgrading liquid modulation and method for modifying, and after upgrading was handled, in sensitive membrane (3) growth one layer thickness being arranged was 10
The silicon dioxide hydrogen of～1 μ m sees through film (5) and forms a kind of film-type hydrogen-sensitive element.(see figure 5)
The major parameter test
One, sensitivity and selectivity test
Fig. 7 is the output impedance correlation curve of hydrogen-sensitive element of the present invention to gas with various.Test condition: V
C=10V; R
L=2K Ω; V
H=5V; Room temperature
The result shows that hydrogen-sensitive element of the present invention is widely different to hydrogen and other gas responsive impedance.When gas concentration was 200ppm, hydrogen and other gas impedance ratio were greater than 25, and when the 800ppm gas concentration, above-mentioned ratio this shows that greater than 200 the present invention has good selectivity and response characteristic to hydrogen.
Two, heating voltage changes influences the hydrogen-sensitive element selectivity.Test condition: V
C=10V; R
L=2K Ω; Density of hydrogen 100ppm, by Fig. 8 curve as can be known, the variation of heating-up temperature is very little to hydrogen-sensitive element sensitivity influence: i.e. the selectivity of hydrogen-sensitive element, not to rely on the control heating-up temperature to realize, but because the hydrogen of the molecular sieve filtration effect that surfaction forms sees through the membrane interaction result, thereby the raising selectivity design approach that breaks traditions, it is simple, convenient to use hydrogen-sensitive element circuit design of the present invention.
Three, hydrogen-sensitive element response characteristic.
Fig. 9 illustrates hydrogen-sensitive element resonse characteristic, test condition V
C=10V; R
L=2K Ω V
H=5V; Density of hydrogen=100ppm; Curve shows hydrogen-sensitive element response of the present invention and recovers rapidly.
Method provided by the present invention is not changing gas sensor sensitive membrane material and continuing to use on the traditional handicraft basis and can greatly improve the exclusive selectivity of gas sensor to hydrogen, and hydrogen is easy through the film film thickness monitoring, steady quality, function admirable.
Especially meaningfully the present invention has introduced a kind of brand-new route that improves the semiconductor gas sensor performance, for production, the research work of gas sensor provides more technological means and research approach.
Claims (7)
1, the Metal Oxide Semiconductor Gas Sensing element that comprises hydrogen is handled and a kind of hydrogen-sensitive element of formation through surfaction, it is characterized in that the metal-oxide semiconductor (MOS) sensitive membrane of described gas sensor sees through film with layer of silicon dioxide hydrogen;
2, hydrogen-sensitive element according to claim 1 is characterized in that it is 10 that silicon dioxide hydrogen sees through film thickness
～1 μ m;
3, hydrogen-sensitive element according to claim 1 is characterized in that described gas sensor, can select in slug type, film-type, plane or integrated-type Metal Oxide Semiconductor Gas Sensing element;
4, hydrogen-sensitive element according to claim 3 is characterized in that the gas sensor that upgrading is handled can be SnO
2, ZnO
2Or Fe
2O
3Semiconductor gas sensor;
5, a kind of hydrogen-sensitive element manufacture method, be the flammable gas Metal Oxide Semiconductor Gas Sensing element that comprises hydrogen that common process is made exert a gradual, uplifting influence in specific organosilicon salt atmosphere and do surperficial upgrading processing, self-sow layer of silicon dioxide hydrogen sees through film on the Metal Oxide Semiconductor Gas Sensing element, said particular atmosphere is meant temperature at 100～500 ℃, the sealed gas chamber of upgrading liquid concentration 30%～100%;
6, hydrogen-sensitive element manufacture method according to claim 5 is characterized in that described organosilicon salt can be from dichlorosilane-SiH
2CI
2, trim,ethylchlorosilane-(CH
3)
3SiCI
4Or tetraethoxysilane Si(OC
2H
5)
4The middle selection;
7,, it is characterized in that silicon dioxide hydrogen sees through film and grew into behind the predetermined thickness in 400～700 ℃ of temperature heat treatment 1～4 hour according to claim 5,6 described described hydrogen-sensitive element manufacture methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104738 CN1018780B (en) | 1990-07-17 | 1990-07-17 | Hydrogen-sensitive element and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104738 CN1018780B (en) | 1990-07-17 | 1990-07-17 | Hydrogen-sensitive element and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048770A true CN1048770A (en) | 1991-01-23 |
| CN1018780B CN1018780B (en) | 1992-10-21 |
Family
ID=4878721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90104738 Expired CN1018780B (en) | 1990-07-17 | 1990-07-17 | Hydrogen-sensitive element and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018780B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2010249247A1 (en) * | 2009-12-14 | 2011-06-30 | Kidde Technologies, Inc | Sensor apparatus and method therefor |
| CN101084433B (en) * | 2004-12-23 | 2011-07-20 | 因菲康有限公司 | Selective gas sensor |
| CN105334245A (en) * | 2015-11-10 | 2016-02-17 | 湖北大学 | Making method for molybdenum oxide nano-fiber paper hydrogen sensor |
| CN107589155A (en) * | 2017-09-12 | 2018-01-16 | 华南师范大学 | A kind of capacitance type sensor and preparation method thereof |
| CN107884449A (en) * | 2017-11-06 | 2018-04-06 | 钟永松 | One kind is directed to H2The high gas sensor of selectivity |
| CN111118330A (en) * | 2019-12-16 | 2020-05-08 | 北京凯恩特技术有限公司 | Palladium-based ternary alloy hydrogen-sensitive material, film, element, preparation method and hydrogen sensor |
-
1990
- 1990-07-17 CN CN 90104738 patent/CN1018780B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084433B (en) * | 2004-12-23 | 2011-07-20 | 因菲康有限公司 | Selective gas sensor |
| AU2010249247A1 (en) * | 2009-12-14 | 2011-06-30 | Kidde Technologies, Inc | Sensor apparatus and method therefor |
| AU2010249247B2 (en) * | 2009-12-14 | 2013-02-14 | Kidde Technologies, Inc | Sensor apparatus and method therefor |
| US8534117B2 (en) | 2009-12-14 | 2013-09-17 | Kidde Technologies, Inc. | Sensor apparatus and method therefor |
| CN105334245A (en) * | 2015-11-10 | 2016-02-17 | 湖北大学 | Making method for molybdenum oxide nano-fiber paper hydrogen sensor |
| CN107589155A (en) * | 2017-09-12 | 2018-01-16 | 华南师范大学 | A kind of capacitance type sensor and preparation method thereof |
| CN107884449A (en) * | 2017-11-06 | 2018-04-06 | 钟永松 | One kind is directed to H2The high gas sensor of selectivity |
| CN111118330A (en) * | 2019-12-16 | 2020-05-08 | 北京凯恩特技术有限公司 | Palladium-based ternary alloy hydrogen-sensitive material, film, element, preparation method and hydrogen sensor |
| CN111118330B (en) * | 2019-12-16 | 2021-05-04 | 北京凯恩特技术有限公司 | Palladium-based ternary alloy hydrogen-sensitive material, film, element, preparation method and hydrogen sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1018780B (en) | 1992-10-21 |
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