CN101046459B - Multilayer nanometer porous SnO2 film synthesis process - Google Patents
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- CN101046459B CN101046459B CN2007100400057A CN200710040005A CN101046459B CN 101046459 B CN101046459 B CN 101046459B CN 2007100400057 A CN2007100400057 A CN 2007100400057A CN 200710040005 A CN200710040005 A CN 200710040005A CN 101046459 B CN101046459 B CN 101046459B
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Abstract
The multilayer nanometer porous SnO2 film and its synthesis process belongs to the field of gas sensitive material and gas sensor preparing technology. Nanometer porous SnO2 film in 6-12 layers are deposited successively onto monocrystalline silicon substrate through the following six steps: preparing solution with SnCl2.2H2O as the precursor and anhydrous alcohol as solvent, adding surfactant, preparing sol, homogenizing, annealing, etc. The present invention has simple technological process, and the multilayer nanometer porous SnO2 film has high chemical stability, small power consumption, great specific surface area and high gas sensitivity, and is suitable for making gas sensor for measuring micro amount of gas.
Description
Technical field
The present invention relates to porous SnO 2 (SnO
2) multi-layer nano film and synthetic method thereof, the technical field of genus air-sensitive sensing material and air-sensitive sensor preparing.
Background technology
The industrial revolution has improved labour productivity, has enriched people's material and cultural life, has also brought serious environmental problem simultaneously.In recent years, airborne NOx, SOx and HCl cause acid rain; Airborne CO
2, CH
4, NO
2, O
3And fluorocarbon (fluorine Lyons) gas causes greenhouse effect; Airborne fluorocarbon and halocarbon cause depletion of the ozone layer; NH
3, H
2S gives out a pungent smell, and acid rain, greenhouse effect, depletion of the ozone layer etc. are threatening human existence, cause the concern of the whole society.The conveyance conduit regular meeting of liquefied petroleum gas (LPG) and rock gas leaks, fire hazardous, and blast and intoxication accident press for the gas sensor that detects inflammable gas.The automobile that the city increases has day by day made things convenient for people's trip, but the pollution of tail gas forces people to research and develop the gas sensor that detects NO.The development of petrochemical industry has improved people's basic necessities of life condition, and the SIC (semiconductor integrated circuit) progress of industry has improved human lives's quality, but these industry have also produced H
2S, CO, AsH
3(arsine), PH
3Toxic gases such as (phosphines) presses for the gas sensor that these gases are examined in research and development.In addition, alcohol, smog, the detection of the freshness of meat and halitosis etc. all requires to use a large amount of panoramic gas sensors.Research and develop above-mentioned these gas sensors, become hot subject.
Tin ash (SnO is found in the Tian Kou Shangyi of Japan in 1962
2) powder is very responsive to various inflammable gass, SnO in various inflammable gas
2The conductivity of powder has nothing in common with each other.Made practical inflammable gas gas sensor according to this characteristic, nineteen sixty-eight, Japan Figaro company released first SnO
2Semiconductor inflammable gas gas sensor commodity.Along with going deep into of research, people have found other gas sensitive again, as γ-Fe
2O
3, ZnO, LaFeO
3Deng.Same SnO
2Compare γ-Fe
2O
3Chemical stability is relatively poor, can irreversiblely become α-Fe mutually at 350 ℃～450 ℃
2O
3The shortcoming of ZnO is that power consumption is bigger; LaFeO
3Be the P-type semiconductor material of finding in the recent period, but its air-sensitive sensitivity and the gas species aspect that can detect are not so good as n section bar material.
SnO
2Basic functional principle as gas sensor is: be exposed to airborne SnO
2The meeting adsorption of oxygen, the oxygen atom of absorption carries out the transition to chemisorption by physisorption, captures the free electron of material internal, the free electron of material surface is reduced, form surperficial acceptor state and surperficial negative space charge, impel to be with and bend, form Schottky barrier and also depletion layer occurs.The height of potential barrier and the thickness of depletion layer depend on the chemisorption concentration and the suction type of oxygen.When the surface adsorbed oxygen constant concentration, because adsorb oxygen is from SnO
2The surface trapping electronics makes the increase of surface negative charge density, band curvature, electricity lead decline.When material surface touches H
2, during reducibility gas such as CO, these reducibility gas can react with the oxonium ion that is adsorbed on material surface, cause the desorption of oxonium ion and the oxygen adsorption concentration of material surface to reduce, the original electronics of being captured by the acceptor state adsorb oxygen, re-inject into material internal, thereby charge carrier increase, potential barrier reduction, depletion layer attenuate, material monolithic resistance are descended.Gas sensor is to come probe gas by the resistance of measuring material, and the concentration of tested gas is high more, and the resistance of material is more little.
Because SnO
2Have good gas sensing property, almost all gas is all had in various degree response, so SnO
2Be most widely used so far, use maximum gas sensitives.Especially film-type SnO
2Highly sensitive with it, high conformity, response speed is fast, and working temperature is low and be easy to miniaturization, advantage such as integrated, comes into one's own just day by day.The scientific research personnel in this field is devoted to research and develop SnO always
2Nanometer air-sensitive film and research improve its air-sensitive sensitivity of method.Existing SnO
2The nanometer air-sensitive film is when surveying minimum gas, and its performance still can not be satisfactory.SnO
2The specific surface area size of nanometer air-sensitive film is to SnO
2The air-sensitive sensitivity of nanometer air-sensitive film has fundamental influence, therefore how to improve SnO
2The specific surface area of nanometer air-sensitive film is a problem demanding prompt solution.
Summary of the invention
The technical matters that the present invention will solve is to propose a kind of multilayer nanometer porous SnO 2 film, it is characterized in that this film is that multilayer is deposited on the porous SnO 2 nano thin-film on the monocrystal silicon substrate successively, and the number of plies is 6～12 layers.This film has the big and highly sensitive advantage of air-sensitive of specific surface area.
Another technical matters that the present invention will solve is to release a kind of synthetic method of multilayer nanometer porous SnO 2 film.For solving above technical matters, the present invention adopts following technical scheme: with metal inorganic salt SnCl
22H
2O and absolute ethyl alcohol are respectively presoma and solvent, the process preparation is used for making solution, adding surfactant, preparation colloidal sol, even glue, the annealing of stannic oxide nanometer film and gets six steps of finished product, be deposited on multi-layer porous stannic oxide nanometer film on the monocrystal silicon substrate successively, the number of plies of described film is at least 6 layers, make finished product, multilayer nanometer porous SnO 2 film.
Now describe technical scheme of the present invention in detail.
A kind of synthetic method of multilayer nanometer porous SnO 2 film is characterized in that, the concrete operations step:
First step preparation is used for making the solution of stannic oxide nanometer film
With metal inorganic salt SnCl
22H
2O and absolute ethyl alcohol are made into the solution of 0.38～0.45mol/L concentration respectively as presoma and solvent, make the precursor aqueous solution that is used for making the stannic oxide nanometer film;
Second step added surfactant
The precursor aqueous solution that makes to the first step adds surfactant, and the weight ratio of surfactant and described solution is 0.1～3.18%;
The 3rd step preparation colloidal sol
Under 25～80 ℃, the solution that second step of magnetic agitation makes 2.5～3 hours, speed of agitator is 400～600 rev/mins, ageing 24～60 hours makes colloidal sol;
Even glue of the 4th step
Adopt traditional centrifugal even glue method, under 2500～4000 rev/mins rotating speed, even glue 25 seconds spreads over the surface of monocrystal silicon substrate with described colloidal sol, and film thickness is 150～250 nanometers;
The 5th step annealing
Under 350～1100 ℃, the 4th surface spreading that obtain of step there is the monocrystal silicon substrate short annealing 15～30 seconds of glued membrane;
The 6th go on foot finished product
The monocrystal silicon substrate that the 4th surface spreading that obtain of step is had glued membrane cycling N time between fourth, fifth step, to make the porous SnO 2 nano thin-film of desired thickness, the mean diameter in hole is 150～950 nanometers, N is an integer, 4＜N＜12.
Technical scheme of the present invention is further characterized in that in second step, described surfactant is a Macrogol 2000.
Technical scheme of the present invention is further characterized in that in second step, described surfactant is a Macrogol 4000.
Technical scheme of the present invention is further characterized in that in the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111).
Technical scheme of the present invention is further characterized in that in the 4th step, rotating speed is 2500 rev/mins.
Technical scheme of the present invention is further characterized in that, in the 6th step, and N=5.
The principle of work of technical scheme of the present invention:
By in being used for making the solution of tin dioxide thin film, adding surfactant, through stir, ageing, make colloidal sol; Even glue makes and deposits a layer thickness on the monocrystal silicon substrate is nano level glued membrane, i.e. the stannic oxide nanometer film; Through short annealing, drive away the surfactant in the glued membrane, make a large amount of trickle hole and the spaces of appearance on the stannic oxide nanometer film on the monocrystal silicon substrate, these holes and space have increased the specific surface area of the product of method of the present invention, thereby have improved the air-sensitive sensitivity of stannic oxide nanometer film.
Method technology of the present invention is simple, can make the multilayer nanometer porous SnO 2 film that chemical stability is good, power consumption is little, specific surface area is big and air-sensitive is highly sensitive, and this film is suitable for being used for making the gas sensor of measuring minimum gas.
Description of drawings
Fig. 1 is the operational flowchart of embodiments of the invention 1.
Embodiment
All embodiment operate according to the operation steps of the synthetic method of multilayer nanometer porous SnO 2 film in " summary of the invention ".
Embodiment 1:
In the first step, metal inorganic salt SnCl
22H
2The consumption of O and absolute ethyl alcohol is respectively 40ml and 3.462g, and the concentration that being used for of making made the precursor aqueous solution of stannic oxide nanometer film is 0.38mol/L; In second step, surfactant is a Macrogol 2000, and addition is 0.036g, surfactant and precursor aqueous solution weight ratio 0.1%; In the 3rd step, under 25 ℃, magnetic agitation 2.5 hours, speed of agitator is 400 rev/mins, ageing 24 hours, used magnetic stirring apparatus is that model is the digital display constant temperature blender with magnetic force of HOI-1B; In the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111), under 2500 rev/mins rotating speed, and even glue 25 seconds, film thickness is 150 nanometers, used sol evenning machine is the desk-top sol evenning machine of KW-4A type; In the 5th step, there is the monocrystal silicon substrate of glued membrane to put into quick anneal oven going on foot the surface spreading obtain with the 4th, under 350 ℃, short annealing 15 seconds, rapid thermal anneler is PTP-300RAPID THERMAL PROCESSOR (a PTP-300 type rapid thermal anneler); In the 6th step, N=5.
Embodiment 2:
In the first step, metal inorganic salt SnCl
22H
2The consumption of O and absolute ethyl alcohol is respectively 40ml and 3.644g, and the concentration that being used for of making made the precursor aqueous solution of stannic oxide nanometer film is 0.4mol/L; In second step, surfactant is a Macrogol 2000, and addition is 0.4g, surfactant and precursor aqueous solution weight ratio 1.1%; In the 3rd step, under 80 ℃, magnetic agitation 3 hours, speed of agitator is 500 rev/mins, ageing 42 hours, used magnetic stirring apparatus is that model is the digital display constant temperature blender with magnetic force of HOI-1B; In the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111), under 3000 rev/mins rotating speed, and even glue 35 seconds, film thickness is 200 nanometers, used sol evenning machine is the desk-top sol evenning machine of KW-4A type; In the 5th step, there is the surface spreading that the 4th step was obtained the monocrystal silicon substrate of glued membrane to put into quick anneal oven, under 750 ℃, short annealing 23 seconds, used rapid thermal anneler is PTP-300RAPID THERMAL PROCESSOR (a PTP-300 type rapid thermal anneler); In the 6th step, N=8.
Embodiment 3:
In the first step, metal inorganic salt SnCl
22H
2The consumption of O and absolute ethyl alcohol is respectively 40ml and 4.1g, and the concentration that being used for of making made the precursor aqueous solution of stannic oxide nanometer film is 0.45mol/L; In second step, surfactant is a Macrogol 2000, and addition is 1.2g, surfactant and precursor aqueous solution weight ratio 3.18%; In the 3rd step, under 95 ℃, magnetic agitation 3.5 hours, speed of agitator is 600 rev/mins, ageing 60 hours, used magnetic stirring apparatus is that model is the digital display constant temperature blender with magnetic force of HOI-1B; In the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111), under 3000 rev/mins rotating speed, and even glue 50 seconds, film thickness is 250 nanometers, used sol evenning machine is the desk-top sol evenning machine of KW-4A type; In the 5th step, there is the surface spreading that the 4th step was obtained the monocrystal silicon substrate of glued membrane to put into quick anneal oven, under 1100 ℃, short annealing 30 seconds, used rapid thermal anneler is PTP-300RAPID THERMAL PROCESSOR (a PTP-300 type rapid thermal anneler); In the 6th step, N=11.
Embodiment 4:
Remove in second step, surfactant is outside the Macrogol 4000, and the operation steps of all the other operation stepss and embodiment 2 is identical.
Multilayer nanometer porous SnO 2 film of the present invention is particularly suitable for being used for making the gas sensor of measuring minimum gas.
Claims (6)
1. the synthetic method of a multilayer nanometer porous SnO 2 film is characterized in that, the concrete operations step:
First step preparation is used for making the solution of stannic oxide nanometer film
With metal inorganic salt SnCl
22H
2O and absolute ethyl alcohol are made into the solution of 0.38～0.45mol/L concentration respectively as presoma and solvent, make the precursor aqueous solution that is used for making the stannic oxide nanometer film;
Second step added surfactant
The precursor aqueous solution that makes to the first step adds surfactant, and the weight ratio of surfactant and described solution is 0.1～3.18%, and surfactant is Macrogol 2000 or Macrogol 4000;
The 3rd step preparation colloidal sol
Under 25～80 ℃, the solution that second step of magnetic agitation makes 2.5～3 hours, speed of agitator is 400～600 rev/mins, ageing 24～60 hours makes colloidal sol;
Even glue of the 4th step
Adopt traditional centrifugal even glue method, under 2500～4000 rev/mins rotating speed, even glue 25 seconds spreads over the surface of monocrystal silicon substrate with described colloidal sol, and film thickness is 150～250 nanometers;
The 5th step annealing
Under 350～1100 ℃, the 4th surface spreading that obtain of step there is the monocrystal silicon substrate short annealing 15～30 seconds of glued membrane;
The 6th go on foot finished product
The monocrystal silicon substrate that the 4th surface spreading that obtain of step is had glued membrane cycling N time between fourth, fifth step, to make the porous SnO 2 nano thin-film of desired thickness, the mean diameter in hole is 150～950 nanometers, N is an integer, 4＜N＜12.
2. the synthetic method of multilayer nanometer porous SnO 2 film according to claim 1 is characterized in that, in the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111).
3. the synthetic method of multilayer nanometer porous SnO 2 film according to claim 1 is characterized in that, in the 4th step, rotating speed is 2500 rev/mins.
4. the synthetic method of multilayer nanometer porous SnO 2 film according to claim 1 is characterized in that, in the 6th step, and N=5.
5. the synthetic method of multilayer nanometer porous SnO 2 film according to claim 1, it is characterized in that, in second step, described surfactant is a Macrogol 2000, in the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111), and rotating speed is 2500 rev/mins, in the 6th step, N=5.
6. the synthetic method of multilayer nanometer porous SnO 2 film according to claim 1, it is characterized in that, in second step, described surfactant is a Macrogol 4000, in the 4th step, monocrystal silicon substrate is the silicon chip that resistivity, thickness and crystal orientation are respectively 8 Ω cm, 380 ± 10 μ m and (111), and rotating speed is 2500 rev/mins, in the 6th step, N=5.
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| CN101339959B (en) * | 2008-08-07 | 2012-03-14 | 清华大学 | Thin film transistor and preparation of semiconductor film |
| CN102602986A (en) * | 2012-04-13 | 2012-07-25 | 山东大学 | Preparation method of micronano stannic oxide porous rod with controllable shape |
| CN104132987B (en) * | 2014-05-30 | 2016-11-16 | 中国石油化工股份有限公司青岛安全工程研究院 | Preparation method for the gas sensor of hydrocarbon gas detection |
| CN104634830A (en) * | 2015-01-26 | 2015-05-20 | 南京大学 | PMMA-SnO2-based thin-film gas sensor for detecting methane |
| CN105403598B (en) * | 2015-12-11 | 2018-10-16 | 南京信息工程大学 | A kind of sensing material and preparation method thereof converted to N-type based on adjustable P |
| CN107311695A (en) * | 2017-05-24 | 2017-11-03 | 江苏时瑞电子科技有限公司 | A kind of preparation method of tin ash air-sensitive film |
| CN108046829B (en) * | 2017-12-20 | 2020-06-16 | 东北大学 | Nonmetal mineral porous substrate and preparation method and application thereof |
| CN108398546A (en) * | 2017-12-26 | 2018-08-14 | 成都鼎信致远科技有限公司 | A kind of drunk driving detector |
| CN108275715A (en) * | 2018-03-29 | 2018-07-13 | 苏州聚康新材料科技有限公司 | The preparation method of the porous composite nano materials of tin oxide |
| CN111024775B (en) * | 2018-10-09 | 2021-05-25 | 中国科学院物理研究所 | Gas-sensitive sensing device for ozone gas sensor and preparation method |
| CN109682867B (en) * | 2019-01-23 | 2022-05-24 | 陕西科技大学 | Micron-sized tin dioxide gas-sensitive material and preparation method and application thereof |
| CN111044582A (en) * | 2019-12-04 | 2020-04-21 | 中国工程物理研究院化工材料研究所 | Fluorocarbon film/metal oxide gas-sensitive film composite laminated device and preparation method thereof |
| CN111453767B (en) * | 2020-04-09 | 2021-11-16 | 吉林大学 | Porous SnO2Micron sheet, preparation method thereof and application of micron sheet to positive electrode of lead-carbon battery |
| CN112993168B (en) * | 2021-02-07 | 2022-10-28 | 广东技术师范大学 | Tin dioxide porous structure perovskite photovoltaic cell without annealing effect and preparation method thereof |
| CN113189151A (en) * | 2021-04-30 | 2021-07-30 | 重庆文理学院 | High-response high-thermal-stability tin dioxide sensor and preparation method thereof |
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| CN1444292A (en) * | 2003-01-09 | 2003-09-24 | 中国科学院等离子体物理研究所 | New-type nano porous film and its preparation method |
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| CN1444292A (en) * | 2003-01-09 | 2003-09-24 | 中国科学院等离子体物理研究所 | New-type nano porous film and its preparation method |
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