CN86106681A - The making of zinc metastannate (zinc stannate) gas sensor - Google Patents

The making of zinc metastannate (zinc stannate) gas sensor Download PDF

Info

Publication number
CN86106681A
CN86106681A CN86106681.2A CN86106681A CN86106681A CN 86106681 A CN86106681 A CN 86106681A CN 86106681 A CN86106681 A CN 86106681A CN 86106681 A CN86106681 A CN 86106681A
Authority
CN
China
Prior art keywords
gas
gas sensor
type
zinc
sno
Prior art date
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.)
Withdrawn
Application number
CN86106681.2A
Other languages
Chinese (zh)
Other versions
CN1015936B (en
Inventor
吴兴惠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yunnan University YNU
Original Assignee
Yunnan University YNU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Yunnan University YNU filed Critical Yunnan University YNU
Priority to CN86106681.2A priority Critical patent/CN1015936B/en
Publication of CN86106681A publication Critical patent/CN86106681A/en
Publication of CN1015936B publication Critical patent/CN1015936B/en
Expired legal-status Critical Current

Links

Landscapes

  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

The present invention ZnSnO 3Or Zn 2Sn 4, add certain SiO 2, Al (OH) 3As filling agent and bonding agent, can be made into semiconductor gas sensors such as directly-heated type, heater-type by technologies such as grinding, coating, sintering.Adopt screen printing technique, vacuum evaporation and sputtering technology, also can make thick film or film-type semiconductor gas sensor.Show that after tested the gas sensor with above-mentioned material and technology are made to gas sensitizations such as hydrogen, water gas, has advantages of higher stability and selectivity.Can be used for the detection and the warning of hydrogen, water gas, oil liquefied gas etc.

Description

The making of zinc metastannate (zinc stannate) gas sensor
The invention belongs to gas detection device technical field.
Human comings and goings all is to carry out in the environment of atmosphere, produces and the also too busy to get away certain atmosphere of life activity.The situation of atmosphere has tremendous influence for human existence.
Along with science and technology development, industrial kind and scale enlarge gradually, and gaseous species that produces in gas raw material of Shi Yonging and the production run and quantity are also increasing aborning.It much is inflammable and explosive having in these gases.They leak in the air not only contaminated environment seriously, but also might cause fire and explosion accident, give to produce and life security is brought danger.In addition, because the development and the growth in the living standard of producing, liquefied petroleum gas (LPG), town gas and rock gas etc. are popularized rapidly as family's fuel, because of blast and fire failure that the leakage of these inflammable gass causes also increasing.Therefore, in order to guarantee safety in production and life, prevent the generation of the various accidents that cause thus, what help producing and living normally carries out, various inflammable and explosive property gases are detected, in time take preventive measures, become one of important process in the gas detection.
The gas detection method of present existing practicality mainly contains electrochemical method; Light source method (comprising luminous); Several different methods such as electrical method.Utilizing the semiconductor gas sensing device to come the method for detected gas, is a kind of method of electrical detection gas.Aspect the inflammable and explosive property gas of detection, the semiconductor gas sensing device has easy to use, low price, highly sensitive, advantages such as good reliability.Therefore, be one of better method of detecting inflammable and explosive property gas.
Electronics industry science and technology committee sensitive element consulting group: " sensitive element special edition ", (1983); Clear, the little long well of high bridge is sincere: " セ Application サ I レ Network ト ロ ニ Network ス ", documents such as (1984, clear rolling hall) shows that semiconductor gas sensor zinc oxide films membrane module the earliest is to succeed in developing at the initial stage in the sixties.It is to utilize under heating condition, and the zinc oxide films film resistance descends with the increase of the concentration of the inflammable gas of contact, thereby realizes N 2The detection of O and CO gas.Develop SnO later on again 2Series, r-Fe 2O 3Gas sensors such as series.Semiconductor gas sensor is divided into resistor-type and non-resistor-type, and resistive type generally is to measure tested gas with its resistance value with the variation of gas concentration, and device architecture mostly is porous sintered article.Non-resistor-type is to utilize gas absorption to influence semi-conductive work function to change and come detected gas.Existing SnO commonly used 2, r-Fe 2O 3The type gas sensor, general fabrication cycle is longer, needs to add noble metals such as pt, pd and makes catalyzer, and constant temperature time needs several hours and even tens hours.
Because semiconductor gas sensor has characteristics such as highly sensitive, of many uses.Therefore obtained development rapidly in recent decades.Further carrying out the research of many kinds semiconductor air-sensitive new material and element thereof, is one of the important topic in current semiconductor gas sensor gas detection technology field.
In order to seek new semiconductor air-sensitive material and the element made from this material thereof, reduce and use price, enlarge measurement range, promote the development of China's semiconductor air-sensitive material and device research.Department of physics of Yunnan University has succeeded in developing and has used ZnSnO 3And Sn 2SnO 4Make gas sensor.Primary Study shows that it does not resemble SnO commonly used now 2, r-Fe 2O 3The type gas sensor need add noble metals such as pt, pd when making and make catalyzer, only needs to add low-cost SiO 2, Al(OH) 3As filling agent and bonding agent; Manufacture craft is simple, and constant temperature time is short, can shorten fabrication cycle, saves the energy and manpower; Can be made into directly-heated type, multiple structures such as heater-type, film, thick film; The heating-up temperature of control element can obtain the susceptibility of gas with various.After tested and analyze, all responsive to gases such as hydrogen, carbon monoxide, water gas.By selected prescription and improvement manufacturing process, also can make it have higher selectivity and stability, can be used for the detection and the warning of liquefied petroleum gas (LPG), household fuel gas, temperature etc.
The present invention is through the World Patent Index 74-8616 phase, " chemical abstracts " 74-86(104,1-8 volume), Chinese thematic information retrieval in 86 years shows, finds manufacture craft and the element identical with the present invention as yet.
Material technology of the present invention is that the employing chemical preparation process is the synthetic ZnSnO of wet method 3(Zn 2SnO 4), concrete grammar be with zinc salt and pink salt as base stock, at first make zinc ammonium complex ion Zn(NH 3) 4, the hydrate Zn (Sn(OH) of synthetic again zinc tin oxide), through the calcination dehydration, then can be made into ZnSnO 3(Zn 2SnO 4).Concrete steps are:
Get a certain amount of ZnSO 4Solution, the certain density ammoniacal liquor of agitation and dropping under the room temperature generates white precipitate, continues dropping ammonia, clarifies until solution.Its reaction is
In above-mentioned solution, add equimolar SnCl 4Solution stirs above-mentioned solution at a certain temperature, generates white precipitate Zn (Sn(OH) immediately 6) ↓.Its reaction can be shown:
Gained solution is filtered washing, the white precipitate Zn (Sn(OH) that obtains 6) put into platinum crucible, to 400 degree calcination dehydrations, then can be made into ZnSnO at 380 degree Celsius 3Its reaction is:
When being heated to 800 degree Celsius during the left and right sides, can obtain Zn 2SnO 4
Ultimate principle of the present invention is ZnSnO 3The semiconductor sensitive material is a kind of senior high-frequency insulation material, is heated to Celsius approximately 800 when spending in high temperature, ZnSnO 3Can resolve into Zn 2SnO 4And SnO 2, form three's composite material.Because SnO 2, Zn 2SnO 4It also all is the semiconductor sensitive material, oxonium ion in these material lattice, acid ion take place vacant, and it is less and when losing the gas molecule in electronics or hole easily, carrier concentration increases to run into dissociation energy, resistance reduces, thereby responsive especially to gases such as hydrogen, water gas.It is generally acknowledged that because the semiconductor surface adsorption gas molecule is filled the omission in the lattice, discharge electronics or hole, charge carrier increases in the crystal thereby make, resistivity decreased.When gas molecule was overflowed, resistivity was recovered initial value again.So just can connect the content of change in resistance and test gas by a simple test circuit.By quantitative test, just can measure the gas of variable concentrations.
Element manufacture craft of the present invention is to adopt directly-heated type, heater-type, thick-film type structure and sintering process.With the directly-heated type structure is that the manufacture craft of example is earlier at ZnSnO 3Add SiO in the material 2, Al(OH) 3Acid-washed asbestos is through grinding, sintering, add technology such as welded tube seat and make element.
Concrete technology is to press ZnSnO 390~95%, SiO 22~5%, Al(OH) 3The material that 2~5% prescription weighs up grinds alms bowl with bowl mill or agate and grinds, and is thin more good more.The electrode diameter is 0.04~0.09 millimeter, and resistance is that 4~20 ohm platinum wire is made, the coiling tubulose, and about about 10 circles, spiral pipe is about 1 millimeter.
With ground matrix material, the furnishing starchiness is coated in the good and sound electrode die, thereby wants all topped firmly helix electrode to make tube core.
Tube core with coating after air dry, is placed on the special carriage, puts sintering in the sintering furnace into.The condition of sintering is: heat to 500~800 degree Celsius, constant temperature 5~30 minutes (heating rate be 1-4 degree Celsius/minute) is cooled to room temperature rapidly behind the constant temperature.
With the energising heating tube core behind the sintering is worn out then; Tube core is welded on the base, puts into special-purpose agingtable energising and wear out.Time is more than 100 hours, so that improve the performance of device, increases stability, makes pottery and eliminates unacceptable product.
Device after aging is carried out the measurement of parameters,, seal, check after tested, qualified packing warehouse-in with 100 order double-layer stainless steels with qualified tube core.
Directly-heated type structure and heater-type structural detail sintering process flow process are as follows:
Weighing → grinding → coating → add electrode → sintering → welded tube seat → preliminary survey.
With above-mentioned directly-heated type or heater-type structure sintering process, utilize screen printing technique, heating material adopts RuO, and electrode material adopts Au, can be made into the thick-film type element.
Also can be made into the film-type element with vacuum evaporation or the low-priced technology of penetrating.
Fig. 1 is ZnSnO 3The gas sensor resistance value is with the variation of all gases concentration.As seen from the figure, when the concentration of hydrogen was increased to 1000ppm gradually, its resistance can change to several kilo-ohms by last megaohm, and its variation range is that hundred times arrives nearly thousand times.As seen its sensitivity is very high, and water gas can reach nearly a hundred times.Though also responsive to methane, its variation only is about twice.
In addition, measure and to show that also the response time of this kind element and release time are also fast.
Utilize ZnSnO 3The semiconductor gas sensor of making has following characteristic: the working temperature of element is 100~350 degree Celsius.Show that after tested inflammable gass such as hydrogen, carbon monoxide, water gas, oil liquefied gas, alkanes gas, gasoline, acetone, alcohol are had sensitivity in various degree, but especially with the most responsive to hydrogen.With regard to hydrogen, methane, water gas, oil liquefied gas, heating power is 1 watt-hour, sensitivity β 0.5=(R A)/(R 0.5) be respectively 150~350,1.5~2.5,35~45,10~12.R wherein ABe the resistance of sample in the clean air, R 0.5Resistance when containing percent 0.5 tested gases in the air.With regard to the SnO that surpasses far away with regard to the sensitivity of hydrogen 2Series of elements and Fe 2O 3Series of elements, with regard to regard to water gas also than other two class components sensitivity.
Utilize Zn 2SnO 4, adopt similar above-mentioned prescription also to can be made into the gas sensor of similar said structure and characteristic.

Claims (4)

1, a kind of semiconductor gas sensor is characterized in that adopting ZnSn 3Or Zn 2SnO 4Make element material, make with certain prescription and sintering process.
2, gas sensor according to claim 1 is characterized in that described prescription is ZnSnO 3Or Zn 2SnO 4Be 90~95%, SiO 2Be 2~5%, Al(OH) 3Be 2~5%.
3, gas sensor according to claim 1 is characterized in that described sintering process is with 1~4 ℃/minute heating rate element to be heated to 500~800 ℃, and constant temperature 5~30 minutes is cooled to room temperature afterwards rapidly.
4, gas sensor according to claim 1 is characterized in that can be made into directly-heated type, heater-type, thick-film type film-type structure.
CN86106681.2A 1986-10-09 1986-10-09 Fabrication of zinc metastannate (or zinc stannate) gas-sensitive devices Expired CN1015936B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN86106681.2A CN1015936B (en) 1986-10-09 1986-10-09 Fabrication of zinc metastannate (or zinc stannate) gas-sensitive devices

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN86106681.2A CN1015936B (en) 1986-10-09 1986-10-09 Fabrication of zinc metastannate (or zinc stannate) gas-sensitive devices

Publications (2)

Publication Number Publication Date
CN86106681A true CN86106681A (en) 1987-10-21
CN1015936B CN1015936B (en) 1992-03-18

Family

ID=4803319

Family Applications (1)

Application Number Title Priority Date Filing Date
CN86106681.2A Expired CN1015936B (en) 1986-10-09 1986-10-09 Fabrication of zinc metastannate (or zinc stannate) gas-sensitive devices

Country Status (1)

Country Link
CN (1) CN1015936B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100360423C (en) * 2006-01-09 2008-01-09 浙江理工大学 Process for synthesizing spinel zine stannate nano rod
CN101251508B (en) * 2008-04-01 2011-06-22 重庆大学 Method for manufacturing gas sensor for testing hydrogen
CN108709915A (en) * 2018-09-01 2018-10-26 罗杰雄 A kind of harmful gas in vehicle detection device
CN109187662A (en) * 2018-08-31 2019-01-11 天津大学 Work in the metal oxide base ethyl alcohol gas sensor preparation method of room temperature
CN110108758A (en) * 2019-05-13 2019-08-09 上海理工大学 Formaldehyde sensitive material and sensing element and preparation method thereof
CN116380997A (en) * 2023-05-26 2023-07-04 深圳市道合顺传感实业有限公司 Gas-sensitive material, preparation method and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100360423C (en) * 2006-01-09 2008-01-09 浙江理工大学 Process for synthesizing spinel zine stannate nano rod
CN101251508B (en) * 2008-04-01 2011-06-22 重庆大学 Method for manufacturing gas sensor for testing hydrogen
CN109187662A (en) * 2018-08-31 2019-01-11 天津大学 Work in the metal oxide base ethyl alcohol gas sensor preparation method of room temperature
CN108709915A (en) * 2018-09-01 2018-10-26 罗杰雄 A kind of harmful gas in vehicle detection device
CN108709915B (en) * 2018-09-01 2021-11-19 山东多瑞电子科技有限公司 Harmful gas detection device in car
CN110108758A (en) * 2019-05-13 2019-08-09 上海理工大学 Formaldehyde sensitive material and sensing element and preparation method thereof
CN116380997A (en) * 2023-05-26 2023-07-04 深圳市道合顺传感实业有限公司 Gas-sensitive material, preparation method and application thereof
CN116380997B (en) * 2023-05-26 2023-08-15 深圳市道合顺传感实业有限公司 Gas-sensitive material, preparation method and application thereof

Also Published As

Publication number Publication date
CN1015936B (en) 1992-03-18

Similar Documents

Publication Publication Date Title
Yuan et al. Detection and identification of volatile organic compounds based on temperature-modulated ZnO sensors
Watson The tin oxide gas sensor and its applications
Coles et al. Selectivity studies on tin oxide-based semiconductor gas sensors
US20100012919A1 (en) Gas sensor having zinc oxide nano-structures and method of fabricating the same
CN101281159B (en) Nanometer zinc oxide multifunctional gas-sensitive sensor device and making method thereof
WO2002039103A9 (en) Thin film metal hydride hydrogen sensor
WO2002082045A2 (en) Thin film sensor array for the detection of gases and a method of making
CN109946358A (en) One kind is with MTiO3Electric potential type SO is blended together for the YSZ base of sensitive electrode2Sensor, preparation method and applications
US20060102494A1 (en) Gas sensor with nanowires of zinc oxide or indium/zinc mixed oxides and method of detecting NOx gas
US4013943A (en) Solid state electrolytic cell gas sensor head
CN86106681A (en) The making of zinc metastannate (zinc stannate) gas sensor
CN108844999A (en) For detecting the utilization g-C of VOCs3N4The synthetic method of the porous zinc bloom nanometer sheet composite air-sensitive material of modification
Hunter A survey and analysis of commercially available hydrogen sensors
CN113533453A (en) Based on CdSnO3Acetone gas sensor and preparation method thereof
CN112782153A (en) Tungsten trioxide-palladium-platinum composite nano-film optical fiber hydrogen sensor
Kocache Gas sensors
Obvintseva Metal oxide semiconductor sensors for determination of reactive gas impurities in air
CN208103923U (en) A kind of hydrogen gas sensor
CN2874479Y (en) Gas pollutant quick detector
CN114088779B (en) Double-coating H resistant to organosilicon poisoning 2 Sensor and preparation method thereof
Malinovskaya et al. Carbon Monoxide Semiconductor Sensors Based on SnO 2-Bi 2 O 3
CN115290704A (en) Preparation method of NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor
Majewski Cross-sensitivity of hydrogen sensors to relative humidity
CN1157412A (en) Tin dioxide gas (hydrogen sensitive type) sensitive element and preparation method thereof
Pijolat et al. Low pressure chemical vapor deposition of tin oxide thin films from an organometallic compound. Application to gas detection

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C13 Decision
GR02 Examined patent application
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee