CN105301064A - In2O3-based hotline type semiconductor gas sensor with environment temperature and humidity self-compensation capabilities - Google Patents
In2O3-based hotline type semiconductor gas sensor with environment temperature and humidity self-compensation capabilities Download PDFInfo
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Abstract
The invention belongs to the technical field of gas sensors and particularly discloses an In2O3-based hotline type semiconductor gas sensor with environment temperature and humidity self-compensation capabilities. The gas sensor comprises a sensitive element and a compensation element, and is characterized in that a sensitive material of the sensitive element is In2O3 added with noble metal; a compensation material of the compensation element is In2O3 added with noble metal and doped with X, wherein X is at least one of Zn, Cu, Si, Al, Ca and Mg; and the noble metal of the sensitive material and the compensation material is at least one of Pd and Pt. According to the In2O3-based hotline type semiconductor gas sensor, the In2O3 added with the noble metal is used as the sensitive material and the specific resistance of the material is increased by doping in the In2O3 and the material is used as the compensation material, so that the composition, structure, and color and the like of the compensation material and the sensitive material are the same; and the sensitive material and the compensation material have same moisture absorption and heat transferring performances and self compensation of the changes of environment temperature and humidity is realized.
Description
Technical field
The invention belongs to gas sensor technical field, be specifically related to a kind of In with environment epidemic disaster self compensation ability
2o
3base hot wire type semiconductor gas sensor.
Background technology
According to Cleaning Principle classification, gas sensor can be divided into metal oxide semiconductor gas sensor, electrochemical gas sensor, catalytic combustion type gas sensor, thermal conductance gas sensor and optical gas sensor.Electrochemical gas sensor stability and good linearity, but electrochemical sensor complex process, price are higher.Optical gas sensor signal stabilization, antijamming capability is strong, but optical gas checkout equipment volume is large, expensive.Thermal conductance gas sensitivity is lower, influenced by environmental temperature, and practical application is less.Catalytic combustion type gas sensor is at Al
2o
3the noble metals such as middle doping Pt, Pd, there is oxidation reaction and release heat in inflammable gas under certain working temperature under Pt, Pd catalysis, utilizes liberated heat that Pt wire coil temperature is raised, thus make Pt silk resistance raise the object reaching and detect inflammable gas.Catalytic combustion type gas sensor just utilizes the resistance variations of Pt wire coil before and after reaction to detect inflammable gas, so the sensitivity of catalytic combustion type gas sensor is lower, to 5000ppmCH
4, 2000ppmLPG, 1000ppmH
2its sensitivity is usually less than 20mV, and its sensitivity is lower as seen, limits by principle simultaneously, and sensor selectivity is poor.Metal oxide semiconductor gas sensor because it is highly sensitive, long service life, selectivity are better and structure is simple, technical maturity, cheap etc., so be a kind of gas sensor be most widely used in gas sensor.
But, metal oxide semiconductor gas sensor is subject to the impact of environment for use condition, environment temperature and humidity change cause sensor output signal to drift about, have a strong impact on accuracy and precision that sensor detects gas concentration, this is also cause metal oxide semiconductor gas sensor to be applied to civil area more, and the major reason of other class gas sensors of the many employings of industrial circle.This shortcoming is the medium-term and long-term Problems existing of metal oxide semiconductor gas sensor, although there is bibliographical information to reduce the method for such sensor by the change of environment epidemic disaster, but limit by metal oxide materials self character and sensor construction, lack effective ways always.Industrial external temp and the humidity sensor of adopting detects epidemic disaster signal more, is then corrected the method that sensor output signal compensates by testing circuit.Although industrial this method has certain effect, but not only increases detecting instrument cost, and the relation needing sensor signal and humiture to change, there is certain difficulty in practical application.
In
2o
3be a kind of n-type semiconductor metal oxide, be a kind of conventional Semiconductor gas sensors material, have higher sensitivity, as C to a lot of gas
2h
10oH, H
2, LPG, CO, O
3and NO
2deng.In simultaneously
2o
3compared to SnO
2resistivity is lower, have better electric conductivity, is therefore also more preferably hot wire type metal-oxide gas transducer gas sensitive.
Summary of the invention
The object of this invention is to provide a kind of In with environment epidemic disaster self compensation ability
2o
3base hot wire type semiconductor gas sensor.
For achieving the above object, the technical scheme taked of the present invention is as follows:
There is the In of environment epidemic disaster self compensation ability
2o
3base hot wire type semiconductor gas sensor, this gas sensor comprises sensitive element (also can be referred to as detecting element) and compensating element, and its special feature is: the sensitive material of sensitive element is the In adding noble metal
2o
3, the compensative material of compensating element, is the In adding noble metal and doping X
2o
3, wherein said X is at least one in Zn, Cu, Si, Al, Ca, Mg, and the noble metal in sensitive material and compensative material is at least one in Pd, Pt.
To account for the molar percent of sensitive material, the addition of noble metal is 0.1-1.5mol%, and surplus is In
2o
3; To account for the molar percent of compensative material, the doping of X is the preferred 4-10mol% of 0.01-20mol%(), the addition of noble metal is 0.1-1.5mol%, and surplus is In
2o
3.
Sensitive element prepares by the following method: (1), take chemical precipitation method to prepare sensitive material; (2), sensitive material adds water furnishing slurry, spreads upon equably on Pt coil, then calcines at least 1h through 400-800 DEG C, obtained sensitive element.
The chemical precipitation method preparation process of sensitive material is: be dissolved in the water by water-soluble indium salt, adds watery hydrochloric acid (preventing water-soluble indium salt hydrolysis), drips NH under stirring to solution
3h
2o is until pH=7, and separation, washing, drying, calcine at least 2h, obtain In for 400-800 DEG C
2o
3powder, then add noble metal mixed grinding, obtain sensitive material; Wherein, described water-soluble indium salt is In (NO
3)
3, InCl
3in at least one; Water-soluble indium salt in reaction raw materials and the In in sensitive material
2o
3all with In metering, in reaction raw materials, the mol ratio of water-soluble indium salt, noble metal equals In in sensitive material
2o
3, noble metal mol ratio.
Compensating element, prepares by the following method: (1), take chemical coprecipitation to prepare compensative material; (2), compensative material adds water furnishing slurry, spreads upon equably on Pt coil, then calcines at least 1h through 400-800 DEG C, obtained compensating element.
The chemical coprecipitation preparation process of compensative material is: being added by the salt (nitrate or chloride) of X to dissolving completely in water-soluble indium salt solusion, dripping NH under stirring to solution
3h
2o is until pH=7, and separation, washing, drying, calcine at least 2h for 400-800 DEG C, the In of the X that must adulterate
2o
3powder, then add noble metal mixed grinding, obtain compensative material; Wherein, described water-soluble indium salt is In (NO
3)
3, InCl
3in at least one; Water-soluble indium salt in reaction raw materials and the In in compensative material
2o
3all with In metering, the salt of the X in reaction raw materials measures with X, and in reaction raw materials, water-soluble indium salt, the salt of X, the mol ratio of noble metal equal In in compensative material
2o
3, X, noble metal mol ratio.
The present invention, relative to prior art, has the following advantages:
To add the In of noble metal
2o
3as sensitive material, to ensure the sensitivity that sensor is high.By at In
2o
3middle doping of Zn, Cu, Si, Al, Ca, Mg etc. increase the resistivity of material as compensative material, make compensative material consistent in composition, structure and color etc. with sensitive material, reach sensitive material and compensative material has identical moisture absorption and heat transfer property, realize auto-compensation environment epidemic disaster changed by compensating element, reduce the signal drift that epidemic disaster causes.The transducer sensitivity of development is greater than 150mV, and in 20-80%RH humidity range, the relative error that humidity causes is less than ± and 10%, in-10-80 DEG C of temperature range, temperature causes the relative error of sensor signal within ± 6%.
Accompanying drawing explanation
Fig. 1: sensor test circuit diagram.
The voltage of Fig. 2: three kinds of different sensors exports histogram.
Fig. 3: the graph of a relation between sensors A sensitivity and gas concentration.
Fig. 4: the graph of a relation between sensor B sensitivity and gas concentration.
Fig. 5: the graph of a relation between the voltage output of sensors A and B and ambient humidity.
Fig. 6: the graph of a relation between the voltage output of sensors A and B and environment temperature.
Fig. 7: the response of sensor B and restorability figure.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
Embodiment 1-5
There is the In of environment epidemic disaster self compensation ability
2o
3base hot wire type semiconductor gas sensor, this gas sensor comprises sensitive element and compensating element, and the sensitive material of sensitive element and the compensative material of compensating element, reaction raw materials used and consumption thereof are in table 1.
The concrete preparation process of sensor is as follows:
The first step, prepared by sensitive material: take In (NO by consumption shown in table 1
3)
3or InCl
3, be dissolved in appropriate amount of deionized water, add 1mL0.1M dilute hydrochloric acid solution, stirring lower ammonia spirit to the pH value dripping mass concentration 5% is 7, obtains white precipitate, centrifuging, washing more than 5 times, until with the AgNO of 0.1mol/L
3inspection does not measure Cl
-; Products therefrom is dry 24h at 100 DEG C, and the faint yellow powder grinding obtained is placed on 600 DEG C of calcining 2h in muffle furnace and obtains In
2o
3powder; Add precious metals pd and Pt catalyst mix grinding 2h by consumption shown in table 1, obtain sensitive material;
Second step, prepared by compensative material: take metal chloride by consumption shown in table 1 or metal nitrate adds In (NO
3)
3or InCl
3in solution, stir down to dissolving, the ammonia spirit dripping mass concentration 5% is 7 to pH value, precipitates through centrifuging, washing, with the AgNO of 0.1mol/L
3detect Cl
-, until Cl
-be completely removed; Products therefrom is dry 24h at 100 DEG C, and grinding is placed on the In that in muffle furnace, 600 DEG C of calcining 2h must adulterate
2o
3powder, adds precious metals pd and Pt catalyst mix grinding 2h, is compensated material;
3rd step, take appropriate sensitive material add in agate mortar deionized water grinding be modulated into the suitable slurry of viscosity, the slurry prepared is coated in ready made Pt wire coil, make it to become round bead shape, hang 2h in atmosphere, then be placed in porcelain boat, and in muffle furnace 600 DEG C calcining 1h, as sensitive element.Be coated in Pt wire coil by above-mentioned same procedure by compensative material slurry, as compensating element, compensating element, structure is identical with sensitive element;
4th step, measures the resistance of detecting element and compensating element, chooses the identical sensitive element of resistance and compensating element, pairing respectively, and by prior art, through welding, encapsulation, be assembled sensor.
Reference examples 1-2
Only be that compensating element, is different from the difference of embodiment 1 sensor: embodiment 1 is with In
2o
3(represent matrix is In to-5%Zn-0.3%Pd-0.2%Pt
2o
3zn doping is added with Pd and Pt simultaneously, and the number percent before Zn represents doping, and the number percent before Pd and Pt represents addition, doping or addition are with molar percentage shared in compensative material metering) for compensative material makes compensating element, reference examples 1 is with Al
2o
3for compensative material makes compensating element, reference examples 2 is with In
2o
3(represent matrix is In to-0.3%Pd-0.2%Pt
2o
3, non-impurity-doped but be added with Pd and Pt, the number percent before Pd and Pt represents addition, and addition is with molar percentage shared in compensative material metering) be that compensative material makes compensating element.
The sensitive element of three kinds of sensors prepared by embodiment 1 and reference examples 1-2 all adopts In
2o
3(represent matrix is In to-0.3%Pd-0.2%Pt
2o
3, non-impurity-doped but be added with Pd and Pt, the number percent before Pd and Pt represents addition, and addition is using molar percentage shared in sensitive material metering) as sensitive material, compensating element, adopts different compensative materials.Sensor mark prepared by reference examples 1 is sensors A, and sensor mark prepared by embodiment 1 is sensor B, and sensor mark prepared by reference examples 2 is sensor C.
sensor performance is tested
Adopt WS-02 gas sensor ability meter (Zhengzhou Wei Sheng Electronic Technology Co., Ltd) survey sensor air-sensitive performance, adopt static volumetric method preparation sample gas, a certain amount of object gas (or liquid) and the pure air of certain volume are mixed into the sample gas of different volumes mark.Basic test circuit as shown in Figure 1 take stone (Wheatstone) bridge circuit, by regulating Fig. 1 jackshaft road supply voltage E regulating element working temperature.In Fig. 1, E is impressed voltage, and the working temperature of sensor is that S is sensitive element, and C is compensating element, and resistance is respectively R by regulating impressed voltage E to control
sand R
c, R
1and R
2the fixed resistance of to be resistance be 2k Ω, R
wfor the adjustable potentiometer of total resistance 500 Ω, V is the output voltage values of Wheatstone electric bridge, and such sensor is to the response output valve (sensitivity) of object gas:
V
s=V
g-V
a；
In formula, V
gfor the output valve of sensor V in sample gas, V
afor the output valve of sensor V in cleaned air.In atmosphere by regulating adjustable potentiometer W Shi Qiao road to be in equilibrium state, at this moment circuit voltage exports is zero, so the voltage sensitivity of element is: V
s=V
g.
From Wheatstone electric bridge, voltage output value can be expressed as:
。
The epidemic disaster performance test of sensor is that sensor is placed in climatic chamber, the temperature and humidity of regulating thermostatic constant humidity cabinet, the output voltage of testing sensor after humiture is constant, and keeps more than 1 hour under this condition, records final voltage and exports.
Test result is as follows:
1) compensative material affects transducer sensitivity
Fig. 2 be the voltage of three kinds of different sensors export histogram (20 DEG C, under 50%RH condition).Semiconductor gas sensor causes material resistance to change the detection realized gas by the absorption of gas on gas sensitive surface and reaction, although the structure of hot wire type semiconductor gas sensor is different from traditional heater-type sensor construction, their basic gas sensing mechanism is identical.In
2o
3typical n-type semiconductor metal oxide, In
2o
3conductance be adsorbed on In
2o
3concentration (the O of the negative oxygen ion on surface
2-, O
-deng) control.Reducibility gas is (as H
2,
i-C
4h
10deng) and In
2o
3the negative oxygen ion generation chemical reaction of adsorption, causes negative oxygen ion concentration to reduce, discharges electronics, thus sensitive element conductivity of material is increased, cause the out of trim of bridge circuit shown in Fig. 1, circuit produces voltage and exports, thus reaches the object detecting object gas.Hot wire type gas sensor small volume simultaneously, have employed built-in type of heating, the thermal efficiency is high, reaches the object reducing element power consumption like this.
As seen from Figure 2, as compensative material (In
2o
3-0.3%Pd-0.2%Pt) adopt and sensitive material (In
2o
3-0.3%Pd-0.2%Pt) identical proportioning (sensor C), because object gas not only reduces sensitive element resistance, and reduce compensating element, resistance, both resistance reduce to cancel each other, do not affect expense stone bridge voltage to export, sensor C sensitivity is very little.As employing Al
2o
3or In
2o
3when-5%Zn-0.3%Pd-0.2%Pt is as compensative material, sensors A and B are to 2000ppm
i-C
4h
10, 1000ppmH
2and 5000ppmCH
4sensitivity be all greater than 120mV, sensitivity is far longer than the sensitivity of sensor C.Reason is Al
2o
3or In
2o
3-5%Zn-0.3%Pd-0.2%Pt resistance itself is larger, in object gas, sensitive element resistance reduces, circuit distributes voltage and reduces simultaneously, compensating element, distributes voltage corresponding increase, compensating element, temperature is caused to raise, and Pt resistance value raises resistance increase with temperature, result is that compensating element, resistance increases, and sensor sheet reveals high sensitivity.
As seen from Figure 2, adopt Al simultaneously
2o
3or In
2o
3-5%Zn-0.3%Pd-0.2%Pt all has higher sensitivity as sensors A during compensative material and B.But the sensitivity of sensor B comparatively Al
2o
3for the sensors A sensitivity of compensative material exceeds about 50mV.This is because In
2o
3after 0.3%Pd and 0.2%Pt modifies, the ability of the catalytic oxidation-reduction reaction that precious metals pd and Pt have had, flammable object gas burns on compensating element, surface, further increase compensating element, temperature, thus improve the resistance value of compensating element, compensative material resistance increases further, so In
2o
3-5%Zn-0.3%Pd-0.2%Pt is as comparatively Al during compensative material
2o
3about 50mV is exceeded as sensitivity during compensative material.
2) relation between transducer sensitivity and concentration
Fig. 3 is with Al
2o
3for during compensative material between sensors A sensitivity and gas concentration graph of a relation (20 DEG C, under 50%RH condition).As can be seen from Figure 3, the relation between the sensitivity of hot wire type sensor and gas concentration and between traditional heater-type transducer sensitivity and concentration relation very approximate.In low strength range, improve a lot along with gas concentration increases the sensitivity of element, in high concentration range, sensitivity reaches capacity state substantially, and gas concentration increases, and element sensitivity increases less.That is low strength range (being usually less than 1000ppm) sensitivity and the concentration linearity are better, and this is also the reason that semiconductor gas sensor is commonly used to detect light concentration gas.
Due to H
2, CH
4with LPG(liquefied petroleum gas (LPG),
i-C
4h
10and C
3h
8potpourri,
i-C
4h
10at about 70vol.%) lower explosive limit different, usual H
2, CH
41000,5000 and 2000ppm is respectively with the alarm set point concentration of LPG.In Fig. 3, sensor is to 1000ppmH
2, 5000ppmCH
4128mV, 150mV and 154mV is respectively with the voltage sensitivity of 2000ppmLPG, and to 100ppmC
2h
10the sensitivity of OH only has 25mV, responsive hardly to CO.Visible light transducer A is all greater than 100mV to the sensitivity of inflammable gas when alarm set point concentration, comparatively has high sensitivity and good selectivity to inflammable gas.
Fig. 4 is with In
2o
3graph of a relation when-5%Zn-0.3%Pd-0.2%Pt is compensative material between sensor B sensitivity and gas concentration (20 DEG C, under 50%RH condition).As can be seen from Figure 4, sensor is to 2000ppmLPG, 1000ppmH
2and 5000ppmCH
4voltage sensitivity be respectively 204mV, 175mV and 196mV, and also can arrive 55mV to the sensitivity of 100ppm ethanol.Sensor B has the ability examination and controlling low concentration LPG, H
2and CH
4, also can be used for C
2h
5the detection of OH gas.
Catalytic gas sensor is also commonly used to detect inflammable gas, and catalytic gas sensor is less than 20mV usually to sensitivity during combustible gas alarm point concentration, the sensitivity of the hot wire type combustible gas sensor of the present invention's development is as can be seen here far longer than catalytic gas sensor.The reason producing this difference is that catalytic gas sensor only utilizes temperature to detect inflammable gas to the impact of Pt silk resistance, and hot wire type gas sensors of the present invention not only utilizes the temperature variation of Pt silk, and utilize the characteristic of semiconductor material, thus the sensitivity of element is had improve significantly.
3) humidity on sensor sensitivity impact
Fig. 5 is the graph of a relation (under 20 DEG C of conditions) between the voltage output of sensors A and B and ambient humidity.In Fig. 5, in air, voltage exports is environment temperature 20 DEG C, and during relative humidity 50%RH, regulator potentiometer makes sensor signal export is zero.
As can be seen from Fig. 5, for Al
2o
3for the sensors A sensor voltage output valve and all increase along with ambient humidity the sensitivity of 2000ppmLPG and increase in atmosphere of compensating element, when particularly humidity is greater than 60%RH, signal exports to be increased with humidity and has a larger increase.Within the scope of 20-80%RH, the relative error of sensitivity is within ± 15%.
It can also be seen that from Fig. 5, to In
2o
3-5%Zn-0.3%Pd-0.2%Pt is the sensor B sensor voltage output valve and increase along with ambient humidity the sensitivity of 2000ppmLPG and slowly increase in atmosphere of compensating element.Especially sensor B in atmosphere sensor voltage output valve hardly with humidity change and change, have extraordinary stability.Within the scope of 20-80%RH, the relative error of sensitivity is within ± 10%.
Because hot wire type sensor is made up of sensitive element and compensating element, two parts, when ambient humidity increases, water vapour not only makes sensitive element resistance reduce, also make the resistance of compensating element, reduce simultaneously, i.e. Δ Rc<0 and Δ Rs<0, Δ Rc and the impact of Δ Rs on sensitivity are partially offset, the impact that existence just because of compensating element, makes humidity on sensor output signal obtains certain compensation, thus makes sensor have the ability of excellent moisture-resistant degree interference.
A, B two kinds of sensors are compared, and sensor B has better moisture-resistant degree changing capability.This is because sensor B compensating element, adopts In
2o
3-5%Zn-0.3%Pd-0.2%Pt as compensative material, compensative material composition and sensitive material composition (In
2o
3-0.3%Pd-0.2%Pt) very close, compensative material and sensitive material have identical with hydrone interaction ability, thus effectively achieve the compensating action that compensating element, changes ambient humidity, and showing sensor B has better humidity self compensation ability.
Environment temperature and humidity can make a significant impact the gas-sensitive property of semiconductor gas sensor, and this is one of medium-term and long-term Problems existing of semiconductor type gas sensor.Semiconductor gas sensors material is porosint, easy adsorption moisture, (the J.Giber such as J.Giber, I.V.Perezel, J.berlinger, C, SensorandActuators, B, 18-19,1994,113-118) think that first the hydrone of absorption plays the effect of electron donor, then the hydrone adsorbed forms the effect that hydroxyl plays electronics acceptor, so have certain influence to the air-sensitive performance of gas sensor on gas sensitive surface.
Although this problem long-term existence, also there are some scholars to be studied (J.Pichlmaier, SensorsandActuators, B, 27,1995,286), still there is no good solution at present.Quan Baofu etc. are to SnO
2(Quan Baofu, Sun Liangyan, Wu Jiakun, sensing technology journal, 3,1996,13), γ-Fe
2o
3with zno-based (Quan Baofu, Sun Liangyan, Wu Jiakun, sensor technology, 3,1996,15) environmental temperature effect of gas sensor has done comparatively systematic research, and result shows that environment temperature can produce the principal character of sensor (aerial resistance Ra and sensitivity) obviously to be affected.(the Li Shuping such as Li Shuping, Wan Jigao, noble metal, 17(4), 1996,13) domestic MQS2C gas sensor temperature effect is studied, at finding environment temperature 45 DEG C, during relative humidity 93%RH, element is 6.32 to the sensitivity of 1000ppm butane, and under 35%RH condition, sensitivity is 15.12, during humidity change, its sensitivity differs more than 1 times.Yellow literal arts (yellow literal arts, electronic component and material, 13(3), 1994,35) humidity characteristic of the TGS-813 type inflammable gassensor of world-renowned Japanese Figaro (FIGARO) company is studied, when result shows that temperature is certain, relative humidity often increases by 30%, resistance decline 15-20%, under same humidity certain condition, temperature often increases by 20 DEG C, by 10-20% under resistance.(the ClaudeDelpha such as ClaudeDelpha, MaryamSiadat, MartineLumbreras, SensorsandActuatorsB, 109,1999,255) also Figaro TGS gas sensor moisture effect is studied, TGS-800, TGS-813 and TGS-832 tri-kinds of elements are when humidity is increased to 85%RH by 18%RH, and the relative error of sensitivity is all more than 50%.Visible humidity is very large on element sensitivity impact.
The hot wire type combustible gas sensor of the present invention's development is when humidity changes to 80%RH by 20%RH, and the relative error of sensitivity only has ± 10%, the ability that the hot wire type sensor of visible the present invention's development has excellent moisture-resistant degree to disturb.
4) temperature affects transducer sensitivity
Fig. 6 is the graph of a relation (under 50%RH condition) between the voltage output of sensors A and B and environment temperature.In Fig. 6, sensor is environment temperature 20 DEG C, regulates zero point during relative humidity 50%RH.
As seen from Figure 6, sensors A and B are within the scope of 0-60 DEG C, and sensor aerial voltage exporting change trend is identical, drift in ± 8mV within, visible drift is less.The drift that sensor drift that temperature causes is less than humidity and causes can be found simultaneously.
With Al
2o
3for compensating element, sensors A to the sensitivity of 2000ppmLPG relative error within the scope of-10 DEG C-80 DEG C be less than ± 10%, In
2o
3-5%Zn-0.3%Pd-0.2%Pt be the relative error that the sensor B temperature of compensating element, causes be less than ± 6%, visible light transducer B there is better resisting temperature jamming performance.This is because sensor B compensating element, has similar component to sensitive element on the one hand, may be because sensitive element has identical color with compensating element, in sensor B on the other hand, compensating element, and sensitive element have identical heat absorption capacity, and compensating element, has the ability of better compensate for ambient temperature variation.
Known by discussing above, with Al
2o
3sensors A for compensating element, has the ability of good environment resistant humiture change, with In
2o
3-5%Zn-0.3%Pd-0.2%Pt is the ability that compensating element, further increases the interference of sensor B environment resistant humiture.
5) sensor response recovery characteristics
Fig. 7 is with In
2o
3-5%Zn-0.3%Pd-0.2%Pt be the response of the sensor B of compensating element, and restorability figure (20 DEG C, under 50%RH condition).The response-recovery time is also the important indicator reflecting gas sensor performance quality.Response time refers to after sensor detects object gas, and the magnitude of voltage of output reaches 90% required time of stationary value in object gas from the stationary value air.After referring to that sensor departs from tested gas release time, the magnitude of voltage of output drops to 10% required time of saturation value in target atmosphere.As shown in Figure 7, the response time of sensor B to 2000ppmLPG is less than 10s, and release time is less than 30s, as seen its response and release time very short, the needs of practical application can be met.
To sum up the performance test results is visible, and in embodiment 1, the combination property of sensor (sensor B) is better than sensor performance in reference examples 1-2.
6) embodiment 1-5 combination property
In embodiment 1-5, sensor performance is in table 2.As shown in Table 2, chemical coprecipitation is adopted to prepare compensative material in embodiment 1-5, the sensitivity of gained sensor performance is all greater than 150mV, response time is less than 15s, release time is less than 30s, the peak response relative error that 20%-80%RH scope humidity causes is less than within the scope of 10%, 0-80 DEG C, and the peak response relative error that environment temperature causes is less than 5%.
Claims (6)
1. there is the In of environment epidemic disaster self compensation ability
2o
3base hot wire type semiconductor gas sensor, this gas sensor comprises sensitive element and compensating element, it is characterized in that: the sensitive material of sensitive element is the In adding noble metal
2o
3, the compensative material of compensating element, is the In adding noble metal and doping X
2o
3, wherein said X is at least one in Zn, Cu, Si, Al, Ca, Mg, and the noble metal in sensitive material and compensative material is at least one in Pd, Pt.
2. there is the In of environment epidemic disaster self compensation ability as claimed in claim 1
2o
3base hot wire type semiconductor gas sensor, is characterized in that: to account for the molar percent of sensitive material, and the addition of noble metal is 0.1-1.5mol%, and surplus is In
2o
3; To account for the molar percent of compensative material, the doping of X is 0.01-20mol%, and the addition of noble metal is 0.1-1.5mol%, and surplus is In
2o
3.
3. there is the In of environment epidemic disaster self compensation ability as claimed in claim 1 or 2
2o
3base hot wire type semiconductor gas sensor, is characterized in that sensitive element prepares by the following method: (1), take chemical precipitation method to prepare sensitive material; (2), sensitive material adds water furnishing slurry, spreads upon equably on Pt coil, then calcines at least 1h through 400-800 DEG C, obtained sensitive element.
4. there is the In of environment epidemic disaster self compensation ability as claimed in claim 3
2o
3base hot wire type semiconductor gas sensor, is characterized in that the chemical precipitation method preparation process of sensitive material is: be dissolved in the water by water-soluble indium salt, add watery hydrochloric acid, drips NH under stirring to solution
3h
2o is until pH=7, and separation, washing, drying, calcine at least 2h, obtain In for 400-800 DEG C
2o
3powder, then add noble metal mixed grinding, obtain sensitive material; Wherein, described water-soluble indium salt is In (NO
3)
3, InCl
3in at least one; Water-soluble indium salt in reaction raw materials and the In in sensitive material
2o
3all with In metering, in reaction raw materials, the mol ratio of water-soluble indium salt, noble metal equals In in sensitive material
2o
3, noble metal mol ratio.
5. there is the In of environment epidemic disaster self compensation ability as claimed in claim 1 or 2
2o
3base hot wire type semiconductor gas sensor, is characterized in that compensating element, prepares by the following method: (1), take chemical coprecipitation to prepare compensative material; (2), compensative material adds water furnishing slurry, spreads upon equably on Pt coil, then calcines at least 1h through 400-800 DEG C, obtained compensating element.
6. there is the In of environment epidemic disaster self compensation ability as claimed in claim 5
2o
3base hot wire type semiconductor gas sensor, is characterized in that the chemical coprecipitation preparation process of compensative material is: being added by the salt of X to dissolving completely in water-soluble indium salt solusion, dripping NH under stirring to solution
3h
2o is until pH=7, and separation, washing, drying, calcine at least 2h for 400-800 DEG C, the In of the X that must adulterate
2o
3powder, then add noble metal mixed grinding, obtain compensative material; Wherein, described water-soluble indium salt is In (NO
3)
3, InCl
3in at least one; Water-soluble indium salt in reaction raw materials and the In in compensative material
2o
3all with In metering, the salt of the X in reaction raw materials measures with X, and in reaction raw materials, water-soluble indium salt, the salt of X, the mol ratio of noble metal equal In in compensative material
2o
3, X, noble metal mol ratio.
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| CN106546637A (en) * | 2016-11-08 | 2017-03-29 | 吉林大学 | A kind of ethyl acetate gas sensor and preparation method thereof |
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| CN109164218A (en) * | 2018-11-12 | 2019-01-08 | 罕王微电子（辽宁）有限公司 | A kind of intelligence sensor |
| CN109932402A (en) * | 2019-04-23 | 2019-06-25 | 苏州纳格光电科技有限公司 | The preparation method of hot wire type gas sensors chip, sensor and sensor |
| CN113447531A (en) * | 2021-05-21 | 2021-09-28 | 西安电子科技大学芜湖研究院 | Indium oxide-based gas sensor manufacturing method and method for detecting methanol |
| CN113447531B (en) * | 2021-05-21 | 2024-04-16 | 西安电子科技大学芜湖研究院 | Indium oxide-based gas sensor manufacturing method and methanol detection method |
| CN113138210A (en) * | 2021-06-22 | 2021-07-20 | 电子科技大学 | Self-adaptive local Gaussian temperature and humidity compensation method for intelligent gas sensor |
| CN113138210B (en) * | 2021-06-22 | 2021-09-24 | 电子科技大学 | Self-adaptive local Gaussian temperature and humidity compensation method for intelligent gas sensor |
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