CN104897732A - Formaldehyde gas sensor gas-sensitive membrane preparation method - Google Patents
Formaldehyde gas sensor gas-sensitive membrane preparation method Download PDFInfo
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- CN104897732A CN104897732A CN201410076956.XA CN201410076956A CN104897732A CN 104897732 A CN104897732 A CN 104897732A CN 201410076956 A CN201410076956 A CN 201410076956A CN 104897732 A CN104897732 A CN 104897732A
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Abstract
The present invention describes a formaldehyde gas sensor gas-sensitive membrane preparation method. According to the method, amorphous indium oxide powder is adopted as a starting material and is subjected to reduction decomposition in an ammonia gas stream at a high temperature, air is introduced to oxidize, and the octahedral string-like indium oxide product obtained through supersaturation degree control is directly deposited on a ceramic tube so as to form the gas-sensitive membrane. According to the present invention, the sensor formed from the gas-sensitive membrane provides stable linear response for formaldehyde, and presents good formaldehyde selectivity in the presence of other indoor interfering gases, wherein the formaldehyde with the concentration as low as 5 ppm can be monitored.
Description
Technical field
The present invention relates to a kind of preparation method of self assembly formaldehyde gas sensor air-sensitive film.Adopt metal oxide semiconductor to prepare the method for micrometer structure gas sensitization film specifically, relate to material preparation and sensory field.
Background technology
Formaldehyde is a kind of important contaminative organic compound in indoor environment, and its generation mainly comes from indoor furniture, coating and dyestuff.Be exposed in the formaldehyde atmosphere of higher concentration for a long time, serious harm can be caused to human body, as rhinitis, pneumonia, even leukaemia etc.Therefore, the monitoring of indoor formaldehyde gas is seemed necessity particularly.
Detection analysis at present for formaldehyde gas is mainly still based on large-scale instrument analysis, as analytical approachs such as vapor-phase chromatography, infrared absorption, galvanochemistry.Complex pretreatment, complex operation, the instrument maintenance cost intensive of these large-scale instrument analytical approachs, can not field monitoring be carried out, detect to the express-analysis of formaldehyde gas and bring inconvenience.Therefore, the portable formaldehyde gas sensor that cost of development is cheap is extremely urgent.Just because of these demands, promoted the fast development of gas sensor, gas sensing property material more and more receives the concern of people.
In numerous gas sensing property material, the metal oxide of semiconductor is widely used in preparation and the exploitation of gas sensor due to advantages such as it is cheap, energy consumption is low, good stability, compatibility are good, easy microminiaturizations.Wherein, indium sesquioxide is as the typical metal oxide semiconductor of one, and forbidden band is wide is 3.7eV, in gas sensor, thin film transistor (TFT), photoelectric cell, catalyzer, shows excellent performance, has caused the research interest of numerous scholar.In recent years, there is a lot of gas sensor based on indium sesquioxide for the report of the gas detect such as ethanol, formaldehyde, sulfuretted hydrogen, ammonia, nitrogen dioxide, hydrogen, embody indium sesquioxide material in gas sensor application aspect prospect widely.
Process gas sensitive being assembled into gas sensor is general all more loaded down with trivial details, consuming time, as drop-coating, spin-coating method etc.And the gas sensor using these methods to assemble, because the connection between gas sensitive and substrate is not very firm, air-sensitive often can come off from substrate, makes the unstable properties of sensor, brings great trouble to analysis and resolution.
Summary of the invention
For the problems referred to above, the object of the invention is to the preparation method proposing a kind of indium sesquioxide self assembly formaldehyde gas sensor air-sensitive film.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for formaldehyde gas sensor air-sensitive film, adopts unformed indium sesquioxide powder to be starting material, at high temperature with ammonia flow reduction, generates indium steam, introduces air subsequently, make the octahedra string-like indium sesquioxide of the oxidized generation of indium steam; The octahedra string-like indium sesquioxide material of preparation is directly self-assembled on ceramic pipe, forms formaldehyde gas sensor air-sensitive film.
Described method comprises following concrete steps:
1) ceramic pipe for the preparation of formaldehyde gas sensor air-sensitive film is fixed on the normal position 0.5-2 centimeters of quartz boat in tubular furnace quartz ampoule, the insulating brick 3-10 centimetre of the horizontal level distance tubular furnace quartz ampoule gas outlet of ceramic pipe;
2) the ammonia solution of indium sesquioxide: unformed indium sesquioxide powder is placed in quartz boat as start material, carries out reduction decomposition under ammonia flow in high temperature process furnances, generates indium steam, and tubular furnace internal gas pressure keeps normal pressure, reaction time 2-5 hour;
3) oxidation of indium steam: close ammonia flow, open tubular furnace quartz ampoule one end near ceramic pipe, allow air be freely spread in tubular furnace quartz ampoule, make indium steam and air generation oxidation reaction, keeps pyroreaction 1-2 hour;
4) reaction terminates rear tubular furnace and naturally cools to room temperature, ceramic pipe obtains have octahedra string-like indium sesquioxide material air-sensitive film.
Described start material is unformed indium sesquioxide powder, 50 ~ 500mg indium sesquioxide powder is got before reaction, ultrasonic disperse forms suspension in the ethanolic solution of 1 ~ 100mL, then by the inside surface of this suspension uniform application at quartz boat, slowly air-dry in fuming cupboard.
Described high temperature is 500 ~ 900 degrees Celsius.
Described ammonia flow is the pure ammonia of 50 ~ 500mL/min.
Tool of the present invention has the following advantages:
1., in course of reaction, product is firmly assembled on the surface of ceramic pipe by the mode of chemical vapor deposition.The mode of this self assembly, can effectively avoid material to depart from from substrate, and therefore obtained gas sensor stability is better.
2. by the control to reaction volume, reaction time, temperature of reaction and deposited distance etc., Reasonable Regulation And Control saturated vapour pressure, make us can obtain the octahedra String structure of micron-sized indium sesquioxide, be compared to traditional nanostructured, the octahedra String structure of this micron-sized indium sesquioxide shows the special response of PARA FORMALDEHYDE PRILLS(91,95), and does not have obvious response signal to the interference gas that other indoor may exist.
3. the ceramic pipe having deposited product is carried out the process of simple wire overlap joint, just can be assembled into gas sensor easily.The mode of this self assembly, eliminates picture and drips some loaded down with trivial details number of assembling steps such as painting, spin coating, substantially reduce the time spent by whole preparation technology.
Accompanying drawing explanation
Fig. 1 is the reaction unit figure preparing formaldehyde gas sensor air-sensitive film;
Wherein, 1-indium sesquioxide powder; 2-quartz boat; 3-ceramic pipe; 4-tubular furnace; 5-insulating brick;
Fig. 2 (a) is the pattern of air-sensitive film under 100 μm of scales under scanning electron microscope;
Fig. 2 (b) is the pattern of air-sensitive film under 10 μm of scales under scanning electron microscope;
Fig. 2 (c) is the pattern of air-sensitive film under 2 μm of scales under scanning electron microscope;
Fig. 3 (a) is for sensor air-sensitive film is to the response of variable concentrations formaldehyde and recovery curve;
The linear fit curve that Fig. 3 (b) is concentration of formaldehyde logarithm and sensor air-sensitive film response logarithm;
Fig. 4 is the response test of sensor air-sensitive film to other interference gases indoor.
Embodiment
1) as shown in Figure 1, ceramic pipe 3 for the preparation of sensor air-sensitive film is fixed on the normal position 0.5-2 centimeters of quartz boat 2 in tubular furnace 4 quartz ampoule, the insulating brick 5 of the horizontal level distance tubular furnace 4 quartz ampoule gas outlet of ceramic pipe 3 is apart from being 3-10 centimetre;
2) the ammonia solution of indium sesquioxide: unformed for 50 ~ 500mg indium sesquioxide powder 1 is made start material, ultrasonic disperse forms suspension in the ethanolic solution of 1 ~ 100mL, then by the inside surface of this suspension uniform application at quartz boat 2, slowly air-dry in fuming cupboard; This quartz boat 2 is carried out reduction decomposition under ammonia flow (50 ~ 500mL/min) in high temperature (500 ~ 900 degrees Celsius) tubular furnace 4, and tubular furnace 4 internal gas pressure keeps normal pressure, reaction time 2-5 hour;
3) oxidation of indium steam: close ammonia flow, open tubular furnace 4 quartz ampoule near one end of ceramic pipe 3, allow air be freely spread in tubular furnace 4 quartz ampoule, make indium steam and air generation oxidation reaction, keep high temperature (500 ~ 900 degrees Celsius) reaction 1-2 hour;
4) reaction terminates rear tubular furnace 4 and naturally cools to room temperature, and ceramic pipe 3 obtains the air-sensitive film with octahedra string-like indium sesquioxide material.
Embodiment 1
1. the ceramic pipe (4mm × 1.2mm × 0.8mm) for the preparation of sensor is fixed on the normal position 0.5cm of quartz boat in tubular furnace quartz ampoule (18cm × 2.6cm × 1.5cm), the insulating brick 3cm distance of the horizontal level distance tubular furnace quartz ampoule gas outlet of ceramic pipe;
2. the ammonia solution of indium sesquioxide: get commercialization unformed indium sesquioxide powder 250mg, ultrasonic disperse forms suspension in the ethanolic solution of 5mL, then this suspension is spread upon uniformly the inside surface of quartz boat, slowly air-dry in fuming cupboard.
Be placed in tubular furnace by this quartz boat, the temperature of tubular furnace rises to 700 degrees Celsius from room temperature in 30min, passes into the pure ammonia of 250mL/min in pipe, the temperature remained constant 2h of reaction system.Whole process is all in the atmosphere of ammonia, and the pressure of system remains on normal pressure.
3. the oxidation of indium steam: at the end of reaction, closes ammonia source, opens quartz ampoule one end near ceramic pipe, allow air be freely spread in system, and remains on 700 degrees Celsius of continuation reaction 2h.
4. reaction terminates rear tubular furnace and naturally cools to room temperature; Take out ceramic pipe, visible surface one deck yellow product, its structure is as shown in Fig. 2 (a) and (b), (c).
5. tumble in two wires on ceramic pipe surface, and through a heater strip in ceramic pipe; Two wires are connected with metering circuit respectively, and heater strip is connected with heater circuit, is assembled into formaldehyde gas sensor.
6. the mensuration of formaldehyde: by regulating heating voltage, controls the working temperature of sensor at 420 degrees Celsius.The voltage of pull-up resistor is by the output signal as record.Under the condition that loop voltage is constant, by recording the electric signal of pull-up resistor, obtain the resistance variations of sensor in air and gas to be measured.
The response of sensor is:
S=R
a/R
g，
Wherein, R
athe aerial resistance of representative sensor, Rg is the resistance in gas to be measured.
In all test processs, ambient humidity controls 50%.
Draw 0.265 μ L respectively, 0.53 μ L, 1.06 μ L, the formalin (37-40%) of 2.67 μ L, 5.34 μ L, 10.68 μ L is volatilized in 18L test box, formaldehyde gas sensor air-sensitive film is exposed wherein, preparation 5,10,20,50,100, the formaldehyde standard gas of 200ppm concentration gradient, measures its response, does curve with its response PARA FORMALDEHYDE PRILLS(91,95) concentration, obtain concentration of formaldehyde normal gradients curve, as shown in Fig. 3 (a) and (b).Adopt same procedure simultaneously, prepare the calibrating gas of the ammonia of 100ppm concentration, toluene, o-xylene, methylene chloride and chloroform, the formaldehyde interference gas that may exist in simulated air atmosphere, measure formaldehyde gas sensor exposure response wherein, to evaluate the antijamming capability of formaldehyde gas sensor, as shown in Figure 4, only formaldehyde shows relatively large response to result.
Be exposed in the atmosphere of unknown concentration of formaldehyde by sensor, obtain sensor response S=1.1, comparison concentration of formaldehyde gradient typical curve, obtaining corresponding concentration of formaldehyde is 3.58ppm.
Claims (5)
1. the preparation method of a formaldehyde gas sensor air-sensitive film, it is characterized in that: adopt unformed indium sesquioxide powder (1) to be starting material, at high temperature with ammonia flow reduction, generate indium steam, introduce air subsequently, make the octahedra string-like indium sesquioxide of the oxidized generation of indium steam; The octahedra string-like indium sesquioxide material of preparation is directly self-assembled on ceramic pipe (3), forms formaldehyde gas sensor air-sensitive film.
2. preparation method according to claim 1, is characterized in that:
Described method comprises following concrete steps:
1) ceramic pipe (3) for the preparation of formaldehyde gas sensor air-sensitive film is fixed on the normal position 0.5-2 centimeters of quartz boat (2) in tubular furnace (4) quartz ampoule, insulating brick (5) 3-10 centimetre of horizontal level distance tubular furnace (4) the quartz ampoule gas outlet of ceramic pipe (3);
2) the ammonia solution of indium sesquioxide: unformed indium sesquioxide powder (1) is placed in quartz boat (2) as start material, reduction decomposition is carried out under ammonia flow in high temperature process furnances (4), generate indium steam, tubular furnace (4) internal gas pressure keeps normal pressure, reaction time 2-5 hour;
3) oxidation of indium steam: close ammonia flow, open tubular furnace (4) quartz ampoule near one end of ceramic pipe (3), allow air be freely spread in tubular furnace (4) quartz ampoule, make indium steam and air generation oxidation reaction, keeps pyroreaction 1-2 hour;
4) reaction terminates rear tubular furnace (4) and naturally cools to room temperature, and ceramic pipe (3) obtains the air-sensitive film with octahedra string-like indium sesquioxide material.
3. according to the preparation method described in claim 1 or 2, it is characterized in that: described start material is unformed indium sesquioxide powder, 50 ~ 500mg indium sesquioxide powder (1) is got before reaction, ultrasonic disperse forms suspension in the ethanolic solution of 1 ~ 100mL, then by the inside surface of this suspension uniform application in quartz boat (2), slowly air-dry in fuming cupboard.
4. according to the preparation method described in claim 1 or 2, it is characterized in that: described high temperature is 500 ~ 900 degrees Celsius.
5. according to the preparation method described in claim 1 or 2, it is characterized in that: described ammonia flow is the pure ammonia of 50 ~ 500mL/min.
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| CN108132246A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of method that copper ion in water is quickly detected using photochemistry colorimetric method |
| CN110455977A (en) * | 2019-06-30 | 2019-11-15 | 北京联合大学 | A kind of low-temperature catalyzed luminous sensitive material of formaldehyde and ammonia |
| CN113899859A (en) * | 2021-09-29 | 2022-01-07 | 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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| CN113899859A (en) * | 2021-09-29 | 2022-01-07 | 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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