CN104897732B - A kind of preparation method of formaldehyde gas sensor air-sensitive film - Google Patents
A kind of preparation method of formaldehyde gas sensor air-sensitive film Download PDFInfo
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- CN104897732B CN104897732B CN201410076956.XA CN201410076956A CN104897732B CN 104897732 B CN104897732 B CN 104897732B CN 201410076956 A CN201410076956 A CN 201410076956A CN 104897732 B CN104897732 B CN 104897732B
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Abstract
The present invention describes a kind of preparation method of formaldehyde gas sensor air-sensitive film.This method is using unformed indium sesquioxide powder as starting material, under the high temperature conditions, the first reduction decomposition in ammonia flow, is re-introduced into air and is aoxidized, via the control of degree of supersaturation, obtain octahedra string-like indium sesquioxide product and be deposited directly to the air-sensitive film formed on earthenware.The sensor PARA FORMALDEHYDE PRILLS(91,95) being made up of the air-sensitive film has stable linear response.Under the conditions of other interference gases are existing indoors, the gas sensor shows that PARA FORMALDEHYDE PRILLS(91,95) is preferably selective, can monitor as little as 5ppm formaldehyde gas concentration.
Description
Technical field
The present invention relates to a kind of preparation method of self assembly formaldehyde gas sensor air-sensitive film.Specifically use and partly lead
The method that body metal oxide prepares micrometer structure gas sensitization film, it is related to material preparation and sensory field.
Background technology
Formaldehyde is that a kind of important contaminative organic compound, its generation mostly come from indoor family in indoor environment
Tool, coating and dyestuff.For a long time exposed to higher concentration formaldehyde atmosphere in, serious harm can be caused to human body, as rhinitis,
Pneumonia, even leukaemia etc..Therefore, the monitoring to indoor formaldehyde gas seems necessity particularly.
Detection and analysis for formaldehyde gas at present be still mainly analyzed with large-scale instrument based on, such as gas chromatography, red
The analysis methods such as outer absorption, electrochemistry.The complex pretreatment of these large-scale instrument analysis methods, cumbersome, instrument maintenance into
This costliness, field monitoring can not be carried out, the quick analysis detection to formaldehyde gas brings inconvenience.Therefore, development cost
Cheap portable formaldehyde gas sensor is extremely urgent.Just because of these demands, the quick hair of gas sensor has been promoted
Exhibition, gas sensing property material have been to be concerned by more and more people.
In numerous gas sensing property materials, the metal oxide of semiconductor is because its is cheap, energy consumption is low, stability is good, compatible
The advantages that property is good, easy miniaturization and be widely used in the preparation and exploitation of gas sensor.Wherein, indium sesquioxide is as one
The typical metal oxide semiconductor of kind, a width of 3.7eV of forbidden band, in gas sensor, thin film transistor (TFT), photocell, catalyst
Aspect, excellent performance is shown, triggered the research interest of numerous scholars.In recent years, have much based on indium sesquioxide
Gas sensor is used for the report of the gases such as ethanol, formaldehyde, hydrogen sulfide, ammonia, nitrogen dioxide, hydrogen detection, embodies three oxygen
Change two phosphide materials in the extensive prospect of gas sensor application aspect.
It is general all comparatively laborious, time-consuming that gas sensitive is assembled into the process of gas sensor, such as drop-coating, spin-coating method
Deng.And the gas sensor assembled using these methods, because the connection between gas sensitive and substrate is not very firmly gas
It is quick often to be come off from substrate so that the performance of sensor is unstable, is greatly bothered to analysis and detection band.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to propose a kind of indium sesquioxide self assembly formaldehyde gas sensor gas
The preparation method of quick film.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of formaldehyde gas sensor air-sensitive film, unformed indium sesquioxide powder is used as starting material,
Reduced at high temperature with ammonia flow, generate indium steam, be subsequently introduced air so that indium steam is oxidized the octahedra string-like three of generation
Aoxidize two indiums；The octahedra string-like indium sesquioxide material of preparation is directly self-assembled on earthenware, forms formaldehyde gas sensing
Device air-sensitive film.
Methods described includes step in detail below：
1）Quartz boat in tube furnace quartz ampoule will be fixed on for preparing the earthenware of formaldehyde gas sensor air-sensitive film
Normal position 0.5-2 centimeters, 3-10 centimetres of the insulating brick of the horizontal level of earthenware apart from tube furnace quartz ampoule gas outlet；
2）The ammonolysis of indium sesquioxide：Unformed indium sesquioxide powder is placed in quartz boat as start material,
Reduction decomposition is carried out in high temperature process furnances under ammonia flow, generates indium steam, air pressure keeps normal pressure, reaction time 2-5 in tube furnace
Hour；
3）The oxidation of indium steam：Ammonia flow is closed, tube furnace quartz ampoule is opened close to one end of earthenware, makes air free
It is diffused into tube furnace quartz ampoule, makes indium steam that oxidation reaction occur with air, is kept for pyroreaction 1-2 hours；
4）Reaction terminates rear tube furnace and naturally cools to room temperature, obtains having the octahedra oxidation of string-like three two on earthenware
Phosphide material air-sensitive film.
The start material is unformed indium sesquioxide powder, and 50~500mg indium sesquioxide powder is taken before reaction,
Ultrasonic disperse forms suspension in 1~100mL ethanol solution, then this suspension is uniformly applied to the interior table of quartz boat
Face, slowly air-dried in fume hood.
The high temperature is 500~900 degrees Celsius.
The ammonia flow is 50~500mL/min pure ammonia.
The invention has the advantages that:
1. during the course of the reaction, product is firmly assembled on the surface of earthenware by way of chemical vapor deposition.
The mode of this self assembly, effectively material can be avoided to depart from from substrate, therefore resulting gas sensor stability
Preferably.
2. pass through the control to reaction volume, reaction time, reaction temperature and deposited distance etc., Reasonable Regulation And Control saturation
Vapour pressure so that we can obtain micron-sized indium sesquioxide octahedron String structure, be compared to traditional nano junction
Structure, the micron-sized indium sesquioxide octahedron String structure show the special response of PARA FORMALDEHYDE PRILLS(91,95), and to other indoor possible
Existing interference gas does not have obvious response signal.
3. the earthenware for having deposited product is carried out into simple wire overlap joint to handle, it is possible to be easily assembled into gas
Body sensor.The mode of this self assembly, eliminate as some cumbersome number of assembling steps such as drop coating, spin coating, substantially reduce whole
Time spent by individual preparation technology.
Brief description of the drawings
Fig. 1 is the reaction unit figure for preparing formaldehyde gas sensor air-sensitive film；
Wherein, 1- indium sesquioxides powder；2- quartz boats；3- earthenwares；4- tube furnaces；5- insulating bricks；
Fig. 2（a）For pattern of the air-sensitive film under 100 μm of scales under ESEM；
Fig. 2（b）For pattern of the air-sensitive film under 10 μm of scales under ESEM；
Fig. 2（c）For pattern of the air-sensitive film under 2 μm of scales under ESEM；
Fig. 3（a）For response of the sensor air-sensitive film to various concentrations formaldehyde and recovery curve；
Fig. 3（b）For concentration of formaldehyde logarithm and the linear fit curve of sensor air-sensitive film response logarithm；
Fig. 4 is response test of the sensor air-sensitive film to other indoor interference gases.
Embodiment
1）As shown in figure 1, quartz in the quartz ampoule of tube furnace 4 will be fixed on for preparing the earthenware 3 of sensor air-sensitive film
The normal position 0.5-2 centimeters of boat 2, the insulating brick 5 of the horizontal level of earthenware 3 apart from the quartz ampoule gas outlet of tube furnace 4
Distance is 3-10 centimetres；
2）The ammonolysis of indium sesquioxide：The unformed indium sesquioxide powder 1 of 50~500mg is made into start material, ultrasound
It is dispersed in 1~100mL ethanol solution and forms suspension, then this suspension is uniformly applied to the inner surface of quartz boat 2,
Slowly air-dried in fume hood；By the quartz boat 2 in high temperature（500~900 degrees Celsius）Ammonia flow in tube furnace 4（50~
500mL/min）Lower carry out reduction decomposition, air pressure is kept for normal pressure, hour in reaction time 2-5 in tube furnace 4；
3）The oxidation of indium steam：Ammonia flow is closed, the quartz ampoule of tube furnace 4 is opened close to one end of earthenware 3, allows air certainly
By being diffused into the quartz ampoule of tube furnace 4, make indium steam that oxidation reaction occur with air, keep high temperature（500~900 degrees Celsius）
React 1-2 hours；
4）Reaction terminates rear tube furnace 4 and naturally cools to room temperature, obtains that there is octahedra string-like three to aoxidize on earthenware 3
The air-sensitive film of two phosphide materials.
Embodiment 1
It is 1. quartzy by being fixed on for the earthenware (4mm × 1.2mm × 0.8mm) for preparing sensor in tube furnace quartz ampoule
Boat（18cm×2.6cm×1.5cm）Normal position 0.5cm, the horizontal level of earthenware is apart from tube furnace quartz ampoule outlet
The insulating brick 3cm distances of mouth；
2. the ammonolysis of indium sesquioxide：The unformed indium sesquioxide powder 250mg of commercialization is taken, ultrasonic disperse is 5mL's
Suspension is formed in ethanol solution, then this suspension is uniformly applied to the inner surface of quartz boat, in fume hood slowly
Air-dry.
The quartz boat is placed in tube furnace, the temperature of tube furnace rises to 700 degrees Celsius in 30min from room temperature, pipe
250mL/min pure ammonia is inside passed through, the temperature of reaction system keeps constant 2h.Whole process is in the atmosphere of ammonia,
The pressure of system is maintained at normal pressure.
3. the oxidation of indium steam：At the end of reaction, ammonia source is closed, opens quartz ampoule close to one end of earthenware, allows sky
Gas is freely spread in system, and is maintained at 700 degrees Celsius and is continued to react 2h.
4. reaction terminates rear tube furnace and naturally cools to room temperature；Take out earthenware, it is seen that one layer of surface yellow product, it is tied
Structure such as Fig. 2（a）、（b）、（c）It is shown.
5. tumbling in two wires in ceramic pipe surface, and a heater strip is passed through in earthenware；Two wires respectively with
Measuring circuit is connected, and heater strip is connected with heater circuit, is assembled into formaldehyde gas sensor.
6. the measure of formaldehyde：By adjusting heating voltage, the operating temperature of sensor is controlled at 420 degrees Celsius.Load electricity
The voltage of resistance is by the output signal as record.Under conditions of loop voltage is constant, by recording the electric signal of load resistance,
Obtain resistance variations of the sensor in air and under test gas.
The response of sensor is：
S=Ra/Rg,
Wherein, RaThe aerial resistance of representative sensor, Rg are the resistance under test gas.
In all test process, ambient humidity is controlled 50%.
Draw 0.265 μ L respectively, 0.53 μ L, 1.06 μ L, 2.67 μ L, 5.34 μ L, 10.68 μ L formalin（37-40%）
Volatilized in 18L test boxs, by the exposure of formaldehyde gas sensor air-sensitive film wherein, prepare 5,10,20,50,100,200ppm is dense
The formaldehyde standard gas of gradient is spent, its response is determined, curve is done with its response PARA FORMALDEHYDE PRILLS(91,95) concentration, obtains concentration of formaldehyde standard
Gradient curve, such as Fig. 3（a）、（b）It is shown.Same procedure is used simultaneously, prepares ammonia, toluene, the adjacent diformazan of 100ppm concentration
The calibrating gas of benzene, dichloromethane and chloroform, formaldehyde interference gas that may be present, measure formaldehyde gas pass in simulated air atmosphere
Sensor exposes response therein, to evaluate the antijamming capability of formaldehyde gas sensor, as a result as shown in figure 4, only formaldehyde shows
Show relatively large response.
By sensor in the atmosphere of unknown concentration of formaldehyde, sensor response S=1.1 are obtained, it is denseer than PARA FORMALDEHYDE PRILLS(91,95)
Gradient standard curve is spent, it is 3.58ppm to obtain corresponding concentration of formaldehyde.
Claims (4)
- A kind of 1. preparation method of formaldehyde gas sensor air-sensitive film, it is characterised in that：Using unformed indium sesquioxide powder (1) it is starting material, is reduced at high temperature with ammonia flow, generate indium steam, be subsequently introduced air so that indium steam is oxidized generation Octahedra string-like indium sesquioxide；The octahedra string-like indium sesquioxide material of preparation is directly self-assembled on earthenware (3), shape Into formaldehyde gas sensor air-sensitive film；Methods described includes step in detail below：1) quartz boat in tube furnace (4) quartz ampoule will be fixed on for the earthenware (3) for preparing formaldehyde gas sensor air-sensitive film (2) normal position 0.5-2 centimeters, the horizontal level of earthenware (3) is apart from the heat-insulated of tube furnace (4) quartz ampoule gas outlet 3-10 centimetres of brick (5)；2) ammonolysis of indium sesquioxide：Unformed indium sesquioxide powder (1) is placed in quartz boat (2) as start material, Reduction decomposition is carried out under tube furnace (4) interior ammonia flow, generates indium steam, the interior air pressure of tube furnace (4) is kept for normal pressure, reaction time 2-5 hours；3) oxidation of indium steam：Ammonia flow is closed, tube furnace (4) quartz ampoule is opened close to one end of earthenware (3), allows air certainly By being diffused into tube furnace (4) quartz ampoule, make indium steam that oxidation reaction occur with air, kept for pyroreaction 1-2 hours；4) reaction terminates rear tube furnace (4) and naturally cools to room temperature, obtains that there is octahedra string-like three to aoxidize on earthenware (3) The air-sensitive film of two phosphide materials.
- 2. according to the preparation method described in claim 1, it is characterised in that：The start material is unformed indium sesquioxide Powder, the unformed indium sesquioxide powder (1) of 50~500mg are taken before reaction, ultrasonic disperse is in 1~100mL ethanol solution Suspension is formed, then this suspension is uniformly applied to the inner surface of quartz boat (2), slowly air-dried in fume hood.
- 3. according to the preparation method described in claim 1, it is characterised in that：The high temperature is 500~900 degrees Celsius.
- 4. according to the preparation method described in claim 1, it is characterised in that：The ammonia flow is 50~500mL/min pure ammonia Gas.
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| CN108132246B (en) * | 2016-12-01 | 2021-03-09 | 中国科学院大连化学物理研究所 | Method for rapidly detecting copper ions in water by photochemical colorimetry |
| CN110455977B (en) * | 2019-06-30 | 2021-06-08 | 北京联合大学 | Low-temperature catalytic luminescence sensitive material of formaldehyde and ammonia |
| CN113899859B (en) * | 2021-09-29 | 2022-08-30 | 宁波市宁乐建筑工程检测有限公司 | Testing box for formaldehyde emission in indoor air and detection method thereof |
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| US5228975A (en) * | 1989-11-25 | 1993-07-20 | Ngk Spark Plug Co., Ltd. | Gas sensor having hermetic and electrically insulating seal in housing |
| CN102557114A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院上海光学精密机械研究所 | Preparation method of indium oxide-based gas-sensitive material with three-dimensional hollow multi-stage structure and application thereof |
| CN202421111U (en) * | 2011-11-30 | 2012-09-05 | 昆明理工大学 | Formaldehyde gas sensing and alarming device |
| CN103105421A (en) * | 2013-01-16 | 2013-05-15 | 大连理工大学 | Nanowire semiconductor gas sensitive material based on GaN-Ga2O3 core-shell structure |
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| JP3950812B2 (en) * | 2003-04-28 | 2007-08-01 | 日本特殊陶業株式会社 | Gas sensor and manufacturing method thereof |
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| US5228975A (en) * | 1989-11-25 | 1993-07-20 | Ngk Spark Plug Co., Ltd. | Gas sensor having hermetic and electrically insulating seal in housing |
| CN202421111U (en) * | 2011-11-30 | 2012-09-05 | 昆明理工大学 | Formaldehyde gas sensing and alarming device |
| CN102557114A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院上海光学精密机械研究所 | Preparation method of indium oxide-based gas-sensitive material with three-dimensional hollow multi-stage structure and application thereof |
| CN103105421A (en) * | 2013-01-16 | 2013-05-15 | 大连理工大学 | Nanowire semiconductor gas sensitive material based on GaN-Ga2O3 core-shell structure |
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