CN103500770A - Infrared gas sensor for detecting a variety of gases - Google Patents
Infrared gas sensor for detecting a variety of gases Download PDFInfo
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- H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
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Abstract
The invention discloses an infrared gas sensor for detecting a variety of gases. An infrared radiation source and a plurality of thermopile sensors are produced into the same chip by adopting the standard CMOS/MEMS (Complementary Metal Oxide Semiconductors/Micro-electromechanical Systems) process, and the thermal crosstalk between coplanar sensors is reduced by means of thermal isolation walls, thermal isolation channels and vacuum wafer level aligned packaging between the chips. A singlechip integration technique is adopted to simultaneously process a plurality of sensors, filters of different narrow bands are adopted to be respectively assembled on the coplanarly arranged sensors, consequently, different gases can be spectroscopically detected, the processing cost is greatly reduced, meanwhile, thermal crosstalk and power consumption are reduced, and moreover, the precision of detection is further increased.
Description
Technical field
The present invention relates to the infrared gas sensor technical field, the infrared gas sensor that in particular a kind of many gas detects.
Background technology
Developing into of technology of Internet of things is integrated, low-power consumption, infrared gas sensor has brought application demand widely cheaply.In industry and daily life, realize dangerous material gas, such as CO, CO
2, NO, NO
2, CH
4highly sensitive detection, can avoid it to reveal the significant damage that social property and public safety are caused.Improve the transducer detection performance and portable in, realize that multiple gases is contactless to detect simultaneously, meet Internet of Things, the complex environment growth requirement to micro-infrared multi-gas sensor.Infrared gas sensor is with the development of MEMS and CMOS technology, be achieved the microminiaturization of infrared optics gas detecting system, with traditional gas sensor, compare, at aspects such as stability, power consumption, sensitivity, reliability, useful life, the response recovery be exceedingly fast and costs, significant advantage is arranged.
Rae System company proposed discrete infrared light supply, detector, air chamber are integrated in to a TO in 2002
5as the infrared gas sensor of miniaturization, and can be used in detection of hydrocarbon HC, carbon dioxide CO in shell
2, carbon monoxide CO and nitric oxide NO gas concentration, but and unrealized multiple gases detect simultaneously, before multiple gases is detected, having needed to separate has increased the complexity and the cost that detect.
Summary of the invention
Technical problem to be solved by this invention is the infrared gas sensor that provides a kind of many gas to detect for the deficiencies in the prior art.
Technical scheme of the present invention is as follows:
The infrared gas sensor that at first the present invention provides a kind of many gas to detect, comprise four responsive units, be respectively: the first responsive unit (1), the second responsive unit (2), the 3rd responsive unit (3) and the responsive unit of reference (4), four responsive units are distributed on take on the circumference that nano-sized surface modification infrared light supply (6) is the center of circle, the heat insulation raceway groove (5) of a L-type wherein is set between the first responsive unit (1), the second responsive unit (2), the heat insulation raceway groove (5) of a L-type also is set between the 3rd responsive unit (3) and the responsive unit of reference (4); Four responsive units and nano-sized surface modification infrared light supply (6) is peripheral by hot divider wall (7), realizes heat isolation each other, reduce hot impact of crosstalking; The narrow band filter slice wave band of reference sensitivity unit covers the first responsive unit (1), the second sensitivity unit (2), the 3rd responsive unit (3), by the responsive first signal to other three transducers of reference, is calculated and compensate correction.
Described infrared gas sensor, the described first responsive unit (1), the second responsive unit (2), the 3rd responsive unit (3) and the responsive unit of reference (4) are distributed on the focus through the ellipse of light source (5).
The present invention also provides the preparation technology of described nano-sized surface modification infrared light supply (6), and step is as follows:
(a), at the upper grown silicon nitride (62) of monocrystalline substrate (61), experiment condition: 780 ℃ of temperature, 330mTorr, Six
2cl
2: 24sccm, NH
3: 90sccm;
(b), the deposit of amorphous silicon (63): temperature is 270 ℃, and gas ratio is respectively SIH
4: 24%NH
3: 55%N
2: 5.2%RF:170;
(c), Al sputter and annealing: magnetron sputtering Al, condition: air pressure 10mTorr, after passing into Ar and meeting air pressure conditions, it is 8400W that RF is set, and then 450 ℃ of lower 90min times, carries out annealing in process;
(d), wet etching Al film: adopt conventional Al corrosive liquid, the remaining Al-Si compound particle of sample surfaces after corrosion;
(e), amorphous silicon dry etching: adopt Cl
2180sccm, pressure 300mTorr, RF350W, He200sccm, temperature 35-40 ℃, micro-shelter that after etching completes, formation surface metal silicide forms;
(f), the etching of positive release aperture, for discharging monocrystalline substrate, prepare: gas CHF
37sccm, He100sccm, SF
630sccm, RF150W, pressure 400mTorr; Adopt the method for magnetron sputtering, the TiN clad metal silicide of sputter 40-50A and amorphous silicon skin, condition is Ar22.4sccm, N
23.0sccm pressure is 5e-3Torr, power is 1000W, and vacuum degree is 8e-7Pa;
(g), XeF
2the positive silicon substrate that discharges, form micro-cantilever infrared light supply supported, and condition is XeF
24Torr, N
220mTorr, temperature is 20 ℃.
The present invention also provides the responsive unit of reference the signal of other three transducers to be calculated and compensates the method for correction, and concrete steps are: the output signal of described infrared-gas concentration sensor is divided into the output signal U of the responsive unit of reference
ref.output signal U with sense channel
act., two output signal U
ref., U
act. with the absorptivity of object gas to infrared light
following relation is arranged:
I
0: incident intensity, i.e. infrared light supply incident after the narrowband optical filter plate filters, with reference to the infrared light intensity of passage and sense channel, generally records under condition of nitrogen gas;
I: transmitted light intensity, the infrared light intensity after being absorbed by object gas in infrared-gas concentration sensor sense channel;
Based on being confined to monochromatic Lambert-beer's law: I=I
oexp (ε lC
n) (2)
C: object gas concentration;
ε: the absorption coefficient of object gas to infrared light;
L: object gas incident light path;
N: revise constant, depend on light path and object gas composition;
The light that the infrared light of infrared light supply incident sense channel after the narrowband optical filter plate filters certainly exists in some wave-length coverages in its wave-length coverage can not absorbed by object gas, has non-absorption bands, therefore, formula (2) is converted to:
I＝I
O×((1-S)×e
(-ΣεlC")+S) (3)
S: non-absorption bands accounts for the proportionality coefficient of sense channel incident infrared light wavelength scope, has characterized non-absorption bands to infrared-gas concentration sensor sense channel output signal U
act.contribution;
α: exponential constant is relevant to the mean value of ε l in Lambert-beer's law;
β: the power constant, depend on the spectral characteristic of object gas;
In the non-existent situation of object gas, infrared-gas concentration sensor sense channel output signal U
act.with reference passage output signal U
ref.ratio be defined as the zero-bit output ratio of infrared-gas concentration sensor, by symbols Z, mean,
in the non-existent situation of object gas, infrared-gas concentration sensor sense channel output signal U
act.peak-to-peak value;
In the situation that the object gas existence, infrared-gas concentration sensor transmitted light intensity I and incident intensity I
0the zero-bit output of ratio and infrared-gas concentration sensor more relevant than Z,
Formula (5) can be exchanged into;
In formula (9), parameter alpha, β determine as follows;
At first, determine the relative absorptivity Fa of object gas to infrared-gas concentration sensor infrared light,
Then, under test status based at the same concentrations object gas, the consistency of the relative absorptivity Fa of same definite type infrared-gas concentration sensor infrared light, choose several infrared-gas concentration sensors, require as same definite type, and the concentrations tested ranged of definite object gas, uniformly-spaced set test point in the concentrations tested ranged of object gas; Applying each infrared-gas concentration sensor tests one by one according to test point, record the relative absorptivity Fa of infrared light that each infrared-gas concentration sensor is corresponding with the test concentrations value, averaged, and according to the test point gas concentration value corresponding relation with relative absorptivity Fa mean value, draw the test result analysis table;
Finally, according to formula (10) Selection of Function relational expression: Y=W * (1-exp (α X β)) (11)
X: independent variable-object gas concentration C;
Y: the mean value of dependent variable-relative absorptivity Fa of infrared-gas concentration sensor infrared light;
W:1-S, ignore and do not remember;
Test result according to test result analysis record, carry out curve fitting to formula (11), asks for the occurrence of parameter alpha and 3;
Through type (8) can draw parameter S in formula (9):
C ": the full scale object gas concentration of infrared-gas concentration sensor test;
when object gas concentration full scale, the infrared-gas concentration sensor is with reference to the passage output signal U
ref.peak-to-peak value;
By related data: parameter alpha, β, S, Z bring in formula (9), can obtain the target function that the infrared-gas concentration sensor calculates gas concentration, the output signal U according to target function and infrared-gas concentration sensor with reference to passage
ref.output signal U with sense channel
act., obtain the gas concentration C of infrared-gas object gas that concentration sensor detects.
Further, the compensation that also comprises environment parameter in the method for correction is calculated and is compensated by the responsive unit of reference to the signal of other three transducers, specifically comprises temperature-compensating mechanism, humidity compensate is machine-processed and the pressure compensation mechanism, is specially:
Temperature-compensating mechanism is:
Introduce temperature compensation parameter λ, the absorptivity in conjunction with temperature relation compensation infrared-gas concentration sensor internal object gas to infrared light
the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the definition temperature-compensating:
T: the real time temperature of external environment during test;
T
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time ambient temperature;
λ: temperature compensation parameter;
Wherein, temperature compensation parameter λ determines as follows: application infrared-gas concentration sensor is tested under definite object gas concentration, change the temperature of external environment simultaneously, and ambient temperature is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with the ambient temperature sampled point to infrared light
according to
the corresponding relation of value and ambient temperature carries out curve fitting, and asks for the occurrence of temperature compensation parameter λ;
Formula (13) is brought in formula (9), can obtain the target function of the temperature compensated rear calculating gas concentration of infrared-gas concentration sensor:
Based on ideal gas concentration law, to the target function C after temperature compensated
compensationcarry out the secondary temperature-compensating, obtain the final goal function that the infrared-gas concentration sensor calculates gas concentration:
Wherein, temperature T, T
0adopt normal temperature, unit is K;
Humidity compensate mechanism is:
In surface air, steam (H
2o) content in atmosphere is along with weather condition alters a great deal, H
2o has a lot of absorption bands at the INFRARED ABSORPTION wave band, so need to carry out the appropriateness compensation.On the basis of temperature-compensating, introduce the humidity compensate parameter
absorptivity in conjunction with humidity relation compensation infrared-gas concentration sensor internal object gas to infrared light
the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the definition humidity compensate:
RH: the real-time humidity of external environment during test;
RH
0; Test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time external environment humidity;
Wherein, humidity compensate parameter
determine as follows: application infrared-gas concentration sensor is tested at definite object gas concentration and temperature, change the humidity of external environment simultaneously, and ambient humidity is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with external environment humidity sampled point to infrared light
according to
the corresponding relation of value and extraneous humidity carries out curve fitting, and asks for the humidity compensate parameter
occurrence;
Formula (15) is brought in formula (9), can obtain the infrared-gas concentration sensor and calculate the target function of gas concentration after humidity compensate:
Wherein, humidity RH, RH
0adopt relative humidity;
The pressure compensation mechanism is:
Because the variation of pressure can cause the variation of molecular motion, and then affect the transmissivity of infrared light, so on the basis of temperature and humidity compensated, introduce pressure compensating parameter β, in conjunction with temperature, the compensation of humidity relation, the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the compensation of definition pressure:
(16)
P: the real-time pressure of external environment during test;
P
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time external environment pressure;
β: pressure compensating parameter;
Wherein, pressure compensating parameter β determines as follows: application infrared-gas concentration sensor is tested under definite object gas concentration, temperature and humidity, change the pressure of external environment simultaneously, and environmental stress is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with external environment pressure sampled point to infrared light
according to
the corresponding relation of value and outside pressure carries out curve fitting, and asks for the occurrence of pressure compensating parameter β;
Formula (16) is brought in formula (9), can obtain the infrared-gas concentration sensor and calculate the target function of gas concentration after the pressure compensation:
Wherein, pressure P, P
0adopt normal pressure, unit is; bar
Output signal U according to final goal function and infrared-gas concentration sensor with reference to passage
ref.output signal U with sense channel
act., obtain the gas concentration C of infrared-gas object gas that concentration sensor detects.
The present invention has following beneficial effect:
1, adopt the monolithic integrated technology process, multisensor is processed simultaneously, adopt different narrow wave band filter plate to be assembled in respectively coplanar a plurality of transducers of arranging, realization is carried out the light splitting detection to gas with various, when greatly cutting down finished cost, reduced that heat is crosstalked and power consumption, and further improved accuracy of detection.
2, adopt hot divider wall and hot isolation moat structure, each detector is carried out to the heat isolation, realize the integrated manufacture of monolithic of multi-gas sensor with this kind of technology, needn't be encapsulated respectively it.
3, adopt the MEMS/CMOS compatible technique to prepare infrared light supply, realize the coplanar integrated manufacture with transducer.
4, adopt the responsive unit of reference to carry out signal analysis and compensation correction to the probe unit of having assembled narrow wave band filter plate.
The accompanying drawing explanation
The structural representation of the infrared gas sensor that Fig. 1 is the many gas detections of the present invention;
The processing technology principle schematic that Fig. 2 is nano-sized surface modification infrared light supply of the present invention;
Fig. 3 is nanostructure infrared light supply cone-shaped nano structure SEM electromicroscopic photograph;
Fig. 4 is nanostructure infrared light supply infrared emittance of the present invention analysis;
Fig. 5 is nanostructure infrared light supply surface stress of the present invention emulation;
Fig. 6 is infrared-gas concentration sensor signal processing method flow chart of the present invention;
1 first responsive unit, 2 second responsive units, 3 the 3rd responsive units, the responsive unit of 4 references, 5 heat insulation raceway grooves, 6 nano-sized surface modification infrared light supplies, 61 silicon substrates, 62 silicon nitrides, 63 amorphous silicons, 64Al, 65TiN; 7 hot divider walls.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The present invention is prior art for the CMOS/MEMS technique do not elaborated.
With reference to figure 1, in the infrared gas sensor detected at the many gases shown in Fig. 1, comprise four responsive units, be respectively: the first responsive unit 3 of responsive unit the 2, the 3rd of responsive unit 1, second and responsive unit 4 of reference, four responsive units are distributed on take on the circumference that nano-sized surface modification infrared light supply 6 is the center of circle, wherein between the first responsive unit 2 of responsive unit 1, second, arrange between two responsive units 3 of heat insulation raceway groove 5, the three and the responsive unit 4 of reference two same heat insulation raceway grooves 5 also are set; Heat isolation is each other realized by hot divider wall 7 in four responsive units and nano-sized surface modification infrared light supply 6 peripheries, reduces hot impact of crosstalking.
Utilize the MEMS technology, prepare four gas infrared sensors and MEMS infrared light supply on single silicon chip simultaneously, wherein three transducers combine respectively narrow wave band filter plate, the specificity wave band of each sensor test gas is depended in the selection of filter plate, the narrow band filter slice wave band of the responsive unit of reference covers other three gas sensitization units (first the 51, second responsive unit 53 of sensitivity unit the 52, the 3rd of responsive unit), by the responsive first signal to other three transducers of reference, is calculated and compensate correction.
The present embodiment provides a kind of nano-sized surface modification infrared light supply 6, and as an object lesson, with reference to step (a)-(g) in figure 2, to the preparation technology of nano-sized surface modification infrared light supply 6 of the present invention, details are as follows:
(a), on monocrystalline substrate 61 grown silicon nitride 62, experiment condition; 780 ℃ of temperature, 330mTorr, SiH
2cl
2; 24sccm, NH
3: 90sccm;
(b), the deposit of amorphous silicon 63: temperature is 270 ℃, and gas flow and ratio are respectively SIH
4: 24%NH
3: 55%N
2: 5.2%RF:170;
(c), Al sputter and annealing: magnetron sputtering Al, condition: air pressure 10mTorr, after passing into Ar and meeting air pressure conditions, it is 8400W that RF is set, and then 450 ℃ of lower 90min times, carries out annealing in process;
(d), wet etching Al film: adopt conventional Al corrosive liquid, the remaining Al-Si compound particle of sample surfaces after corrosion.
(e), amorphous silicon dry etching: adopt Cl
2180sccm, pressure 300mTorr, RF350W, He200sccm, temperature 35-40 ℃, only be left surperficial metal silicide after etching completes.
(f), the etching of positive release aperture, for discharging monocrystalline substrate, prepare: gas CHF
37sccm, He100sccm, SF
630sccm, RF150W, pressure 400mTorr.Adopt the method for magnetron sputtering, the TiN clad metal silicide of sputter 40-50A and amorphous silicon skin, concrete experiment condition is Ar22.4sccm, N
23.0sccm pressure is 5e-3Torr, power is 1000W, and vacuum degree is 8e-7Pa.
(g), XeF
2the positive silicon substrate that discharges, form micro-cantilever infrared light supply supported, and condition is XeF
24Torr, N
220mTorr, temperature is 20 ℃.
In step (c), what adopt is that metal-induced crystallization prepares the taper forest structure, utilize metal and the silicon principle of dissolving each other, form the metal silication composition granule at boundary layer, process at the metal wet etching, do not gone silicon point to clean, retained metal silication composition granule sheltering as next step etching.The cone-shaped nano structure that etching is formed has carried out the SEM electromicroscopic photograph and has taken, cone structure surface area has as shown in Figure 3 increased by 5 times of left and right, after the TiN sputter is carried out in its surface, carried out the infrared emittance analysis, as shown in Figure 4, at HCl and NO detection field higher than 70% emissivity, at CH4, SO2, CO2 and NO2, detect and possess field higher than 60% emissivity, and at the 8-10 mu m waveband, existence is higher than 70% infrared emittance, XPS elementary analysis and Determination of Different Valence States (table 1, table 2).Table 1 has shown the C in the common process, O, and Si, and the F had an effect in the metal-induced crystallization process and Al, table 2 demonstration, after the infrared light supply processing of preparation, the main chemicals that exist are AlF
x, AlSi
x.And the metal silicide produced in the metal-induced crystallization process is etched in preparation process fully.
Table 1XPS elementary analysis
| Remove thickness (nm) | C | O | F | Al | Si |
| 2.1 | 7.8 | 37.1 | 6.2 | 3.2 | 45.8 |
Table 2XPS Determination of Different Valence States
Adopt the Al-Si technology of dissolving each other to form metal silicide, as micro-silicon of sheltering injecting, carry out etching, form cone-shaped nano structure, and, at the TiN of its surface sputtering 40-50A, strengthen surface plasmon resonance effect, improve approximately 5% left and right of emissivity.Adopt dark silicon etching technology, realize that the front of arrowband infrared light supply discharges, reduce the thermal losses of light source heating process.For reducing the structural stress of the infrared light supply of the present invention that suspends, adopt SiN as with heating layer (the present embodiment is amorphous silicon 3), carrying out the dielectric layer directly contacted, reduce residual stress problems, the simulation example proving effect is arranged as shown in Figure 5.Simulation model is to utilize comsol mutiphisics software, when the research thermal source loads 0.2V voltage, under the impact of ohm heating effect, the variation of structural stress, after adding the silicon nitride medium layer, the maximum stress of arrowband infrared light supply is only 0.1299Gpa, can guarantee the stability of structure.
Embodiment 3
1) method for processing concentration signal of infrared gas sensor
Gas detection method based on the infrared optics principle has many kinds, and wherein the dual wavelength detection method is comparatively commonly used, and the method can play the effect of reference wavelength ambient compensation, thereby effectively improves anti-interference and the stability of system.Gas concentration computational methods based on optical principle also have many kinds, are mainly at present to determine concrete which kind of method calculating gas concentration that adopts according to accuracy requirement.The present embodiment has mainly been set forth the linear interpolation that adopts in research process-data lookup table computational methods, and the method is relatively simple, and its result has met the application demand of large multiple-alarm, warning occasion, as coal mine gas alarm etc.The precision of the method depends primarily on the data form situation of prior demarcation, the data segment of demarcating is more, test result is just more accurate, concrete calculating is at first to judge the concentration value of current test drops on which interval of the each point of prior demarcation, then calculate by the interpolation method substitution, there is software simultaneously and calculate and fast automatic calibration function.
A kind of infrared-gas concentration sensor signal processing method, the output signal of described infrared-gas concentration sensor is divided into the output signal U with reference to responsive unit
ref.output signal U with sense channel
act., two output signal U
ref., U
act.with the absorptivity of object gas to infrared light
following relation is arranged:
I
0: incident intensity, i.e. infrared light supply incident after the narrowband optical filter plate filters, with reference to the infrared light intensity of passage and sense channel, generally records under condition of nitrogen gas;
I: transmitted light intensity, the infrared light intensity after being absorbed by object gas in infrared-gas concentration sensor sense channel;
Based on being confined to monochromatic Lambert-beer's law: I=I
oexp (ε lC
n) (2)
C: object gas concentration;
ε: the absorption coefficient of object gas to infrared light;
L: object gas incident light path;
N: revise constant, depend on light path and object gas composition;
Consider, the light that the infrared light of infrared light supply incident sense channel after the narrowband optical filter plate filters certainly exists in some wave-length coverages in its wave-length coverage can not absorbed by object gas, has non-absorption bands, therefore, formula (2) is converted to:
I=I
O×((1-S)×e
(-ΣεlCn)+S) (3)
S: non-absorption bands accounts for the proportionality coefficient of sense channel incident infrared light wavelength scope, has characterized non-absorption bands to infrared-gas concentration sensor sense channel output signal U
act.contribution;
α: exponential constant is relevant to the mean value of ε l in Lambert-beer's law;
β: the power constant, depend on the spectral characteristic of object gas;
In the non-existent situation of object gas, infrared-gas concentration sensor sense channel output signal U
act.with reference passage output signal U
ref.ratio be defined as the zero-bit output ratio of infrared-gas concentration sensor, by symbols Z, mean,
In the situation that the object gas existence, infrared-gas concentration sensor transmitted light intensity I and incident intensity I
0the zero-bit output of ratio and infrared-gas concentration sensor more relevant than Z,
Formula (5) can be exchanged into:
In formula (9), parameter alpha, β determine as follows:
At first, determine the relative absorptivity Fa of object gas to infrared-gas concentration sensor infrared light,
Then, under test status based at the same concentrations object gas, the consistency of the relative absorptivity Fa of same definite type infrared-gas concentration sensor infrared light, choose several infrared-gas concentration sensors, require as same definite type, and the concentrations tested ranged of definite object gas, uniformly-spaced set test point in the concentrations tested ranged of object gas; Applying each infrared-gas concentration sensor tests one by one according to test point, record the relative absorptivity Fa of infrared light that each infrared-gas concentration sensor is corresponding with the test concentrations value, averaged, and according to the test point gas concentration value corresponding relation with relative absorptivity Fa mean value, draw the test result analysis table;
Finally, according to formula (10) Selection of Function relational expression: Y=W * (1-exp (α X
β)) (11)
X: independent variable-object gas concentration C;
Y: the mean value of dependent variable-relative absorptivity Fa of infrared-gas concentration sensor infrared light;
W:1-S, ignore and do not remember;
Test result according to test result analysis record, carry out curve fitting to formula (11), asks for the occurrence of parameter alpha and β;
Through type (8) can draw parameter S in formula (9):
C ": the full scale object gas concentration of infrared-gas concentration sensor test;
when object gas concentration full scale, infrared-gas concentration sensor sense channel output signal U
act.peak-to-peak value;
By related data: parameter alpha, β, S, Z bring in formula (9), can obtain the target function that the infrared-gas concentration sensor calculates gas concentration, the output signal U according to target function and infrared-gas concentration sensor with reference to passage
ref.output signal U with sense channel
act., obtain the gas concentration C of infrared-gas object gas that concentration sensor detects.
2) temperature-compensating mechanism
Generally, in the measurement result of calculation of gas concentration and test process, the interior temperature of air chamber has relation, comprise some other environmental parameter, such as humidity, pressure etc. all has a direct impact gas concentration value, but belonging to temperature has the greatest impact, this also infers and obtains according to the principle of thermo-responsive unit, and therefore, it is very necessary taking adequate measures to compensate result of calculation.According to requirement and the accuracy relation of look-up method, can obtain a kind of simple indemnifying measure by experience and experimental test data analysis.
Also comprise real-time measurement temperature compensation; Introduce temperature compensation parameter λ, the absorptivity in conjunction with temperature relation compensation infrared-gas concentration sensor internal object gas to infrared light
the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the definition temperature-compensating:
T: the real time temperature of external environment during test;
T
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time ambient temperature;
λ: temperature compensation parameter;
Wherein, temperature compensation parameter λ determines as follows: application infrared-gas concentration sensor is tested under definite object gas concentration, change the temperature of external environment simultaneously, and ambient temperature is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with the ambient temperature sampled point to infrared light
according to
the corresponding relation of value and ambient temperature carries out curve fitting, and asks for the occurrence of temperature compensation parameter λ;
Formula (13) is brought in formula (9), can obtain the target function of the temperature compensated rear calculating gas concentration of infrared-gas concentration sensor:
Based on ideal gas concentration law, to the target function C after temperature compensated
compensationcarry out the secondary temperature-compensating, obtain the final goal function that the infrared-gas concentration sensor calculates gas concentration;
(14)
Wherein, temperature T, T
0adopt normal temperature, unit is K;
Humidity compensate mechanism is:
In surface air, steam (H
2o) content in atmosphere is along with weather condition alters a great deal, H
2o has a lot of absorption bands at the INFRARED ABSORPTION wave band, so need to carry out the appropriateness compensation.On the basis of temperature-compensating, introduce the humidity compensate parameter
absorptivity in conjunction with humidity relation compensation infrared-gas concentration sensor internal object gas to infrared light
the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the definition humidity compensate:
RH: the real-time humidity of external environment during test;
RH
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time external environment humidity;
Wherein, humidity compensate parameter
determine as follows: application infrared-gas concentration sensor is tested at definite object gas concentration and temperature, change the humidity of external environment simultaneously, and ambient humidity is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with external environment humidity sampled point to infrared light
according to
the corresponding relation of value and extraneous humidity carries out curve fitting, and asks for the humidity compensate parameter
occurrence;
Formula (15) is brought in formula (9), can obtain the infrared-gas concentration sensor and calculate the target function of gas concentration after humidity compensate:
Wherein, humidity RH, RH
0adopt relative humidity;
The pressure compensation mechanism is:
Because the variation of pressure can cause the variation of molecular motion, and then affect the transmissivity of infrared light, so on the basis of temperature and humidity compensated, introduce pressure compensating parameter β, in conjunction with temperature, the compensation of humidity relation, the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the compensation of definition pressure:
(16)
P: the real-time pressure of external environment during test;
P
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time external environment pressure;
β: pressure compensating parameter;
Wherein, pressure compensating parameter β determines as follows: application infrared-gas concentration sensor is tested under definite object gas concentration, temperature and humidity, change the pressure of external environment simultaneously, and environmental stress is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with external environment pressure sampled point to infrared light
according to
the corresponding relation of value and outside pressure carries out curve fitting, and asks for the occurrence of pressure compensating parameter β;
Formula (16) is brought in formula (9), can obtain the infrared-gas concentration sensor and calculate the target function of gas concentration after the pressure compensation:
Wherein, pressure P, P
0adopt normal pressure, unit is; bar
Output signal U according to final goal function and infrared-gas concentration sensor with reference to passage
ref.output signal U with sense channel
act., obtain the gas concentration C of infrared-gas object gas that concentration sensor detects.
3) concentration calculation software design
Fact proved, ir-absorbance, along with the variation of gas concentration, is also affected by the mode of the design of air chamber structure, electromagnetic interference, signal extraction simultaneously.Therefore, infrared light supply need to be modulated by microprocessor, and processes to improve the detection performance in conjunction with method for detecting weak signals and software, and Fig. 6 has described the flow chart of whole design.In computational process, at first ambient temperature need to be gathered equally, and it is for calculating the foundation of compensation.Method and the look-up method of its signals collecting and processing are similar, need to try to achieve by collection the output signal of two passages, and carry out relevant calculation of parameter according to the output signal of this two passage, such as the calculating of carrying out zero-bit, span.
Algorithm of the present invention has following beneficial effect:
1), the impact of infrared-gas concentration sensor zero-bit output Determination result in the non-existent situation of object gas;
2), the impact for ambient temperature on infrared-gas concentration sensor testing result, implement twice temperature-compensating, in order to revise the testing result of infrared-gas concentration sensor.
3), the impact of temperature in perfect gas law realized to second compensation; Make the infrared-gas concentration sensor to use under condition of different temperatures, overcome because of area and the change of the weather condition impact on infrared-gas concentration sensor usability.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection range of claims of the present invention.
Claims (5)
1. the infrared gas sensor that gas more than one kind detects, it is characterized in that, comprise four i.e. responsive units, be respectively: the first responsive unit (1), the second responsive unit (2), the 3rd responsive unit (3) and the responsive unit of reference (4), four responsive units are distributed on take on the circumference that nano-sized surface modification infrared light supply (6) is the center of circle, the heat insulation raceway groove (5) of a L-type wherein is set between the first responsive unit (1), the second responsive unit (2), the heat insulation raceway groove (5) of a L-type also is set between the 3rd responsive unit (3) and the responsive unit of reference (4); Four responsive units and nano-sized surface modification infrared light supply (6) is peripheral by hot divider wall (7), realizes heat isolation each other, reduce hot impact of crosstalking; The narrow band filter slice wave band of reference sensitivity unit covers the first responsive unit (1), the second sensitivity unit (2), the 3rd responsive unit (3), by the responsive first signal to other three transducers of reference, is calculated and compensate correction.
2. infrared gas sensor according to claim 1, it is characterized in that, the described first responsive unit (1), the second responsive unit (2), the 3rd responsive unit (3) and the responsive unit of reference (4) are distributed on the focus through the ellipse of light source (5).
3. infrared gas sensor according to claim 1, is characterized in that, the preparation technology of described nano-sized surface modification infrared light supply (6) is as follows:
(a), at the upper grown silicon nitride (62) of monocrystalline substrate (61), experiment condition: 780 ℃ of temperature, 330mTorr, SiH
2cl
2: 24sccm, NH
3: 90sccm;
(b), the deposit of amorphous silicon (63): temperature is 270 ℃, and gas ratio is respectively SIH
4: 24%NH
3: 55%N
2: 5.2%RF:170:
(c), Al sputter and annealing: magnetron sputtering Al, condition: air pressure 10mTorr, after passing into Ar and meeting air pressure conditions, it is 8400W that RF is set, and then 450 ℃ of lower 90min times, carries out annealing in process;
(d), wet etching Al film: adopt conventional Al corrosive liquid, the remaining Al-Si compound particle of sample surfaces after corrosion;
(e), amorphous silicon dry etching: adopt Cl
2180sccm, pressure 300mTorr, RF350W, He200sccm, temperature 35-40 ℃, micro-shelter that after etching completes, formation surface metal silicide forms;
(f), the etching of positive release aperture, for discharging monocrystalline substrate, prepare: gas CHF
37sccm, He100sccm, SF
630sccm, RF150W, pressure 400mTorr; Adopt the method for magnetron sputtering, the TiN clad metal silicide of sputter 40-50A and amorphous silicon skin, condition is Ar22.4sccm, N23.0sccm, pressure is 5e-3Torr, and power is 1000W, and vacuum degree is 8e-7Pa;
(g), XeF
2the positive silicon substrate that discharges, form micro-cantilever infrared light supply supported, and condition is XeF
24Torr, N
220mTorr, temperature is 20 ℃.
4. infrared gas sensor according to claim 1, it is characterized in that, the method that the responsive first signal to other three transducers of reference was calculated and compensated correction is: the output signal of described infrared-gas concentration sensor is divided into the output signal U of the responsive unit of reference
ref.output signal U with sense channel
act., two output signal U
ref., U
act.with the absorptivity of object gas to infrared light
following relation is arranged:
I
0: incident intensity, i.e. infrared light supply incident after the narrowband optical filter plate filters, with reference to the infrared light intensity of passage and sense channel, generally records under condition of nitrogen gas;
I: transmitted light intensity, the infrared light intensity after being absorbed by object gas in infrared-gas concentration sensor sense channel;
Based on being confined to monochromatic Lambert-beer's law: I=I
oexp (ε lC
n) (2)
C: object gas concentration;
ε: the absorption coefficient of object gas to infrared light;
L: object gas incident light path;
N: revise constant, depend on light path and object gas composition;
The light that the infrared light of infrared light supply incident sense channel after the narrowband optical filter plate filters certainly exists in some wave-length coverages in its wave-length coverage can not absorbed by object gas, has non-absorption bands, therefore, formula (2) is converted to:
I=I
O×((1-S)×e
(-ΣεlC″)+S) (3)
S: non-absorption bands accounts for the proportionality coefficient of sense channel incident infrared light wavelength scope, has characterized non-absorption bands to infrared-gas concentration sensor sense channel output signal U
act.contribution;
α: exponential constant is relevant to the mean value of ε l in Lambert-beer's law;
β: the power constant, depend on the spectral characteristic of object gas;
In the non-existent situation of object gas, infrared-gas concentration sensor sense channel output signal U
act.with reference passage output signal U
ref.ratio be defined as the zero-bit output ratio of infrared-gas concentration sensor, by symbols Z, mean,
in the non-existent situation of object gas, infrared-gas concentration sensor sense channel output signal U
act.peak-to-peak value;
In the situation that the object gas existence, infrared-gas concentration sensor transmitted light intensity I and incident intensity I
0the zero-bit output of ratio and infrared-gas concentration sensor more relevant than Z,
Formula (5) can be exchanged into:
In formula (9), parameter alpha, β determine as follows:
At first, determine the relative absorptivity Fa of object gas to infrared-gas concentration sensor infrared light,
Then, under test status based at the same concentrations object gas, the consistency of the relative absorptivity Fa of same definite type infrared-gas concentration sensor infrared light, choose several infrared-gas concentration sensors, require as same definite type, and the concentrations tested ranged of definite object gas, uniformly-spaced set test point in the concentrations tested ranged of object gas; Applying each infrared-gas concentration sensor tests one by one according to test point, record the relative absorptivity Fa of infrared light that each infrared-gas concentration sensor is corresponding with the test concentrations value, averaged, and according to the test point gas concentration value corresponding relation with relative absorptivity Fa mean value, draw the test result analysis table;
Finally, according to formula (10) Selection of Function relational expression: Y=W * (1-exp (α X
β)) (11)
X: independent variable-object gas concentration C;
Y: the mean value of dependent variable-relative absorptivity Fa of infrared-gas concentration sensor infrared light;
W:1-S, ignore and do not remember;
Test result according to test result analysis record, carry out curve fitting to formula (11), asks for the occurrence of parameter alpha and β;
Through type (8) can draw parameter S in formula (9);
C ": the full scale object gas concentration of infrared-gas concentration sensor test;
when object gas concentration full scale, infrared-gas concentration sensor sense channel output signal U
act.peak-to-peak value;
when object gas concentration full scale, the infrared-gas concentration sensor is with reference to the passage output signal U
ref.peak-to-peak value;
By related data: parameter alpha, β, S, Z bring in formula (9), can obtain the target function that the infrared-gas concentration sensor calculates gas concentration, the output signal U according to target function and infrared-gas concentration sensor with reference to passage
ref.output signal U with sense channel
act., obtain the gas concentration C of infrared-gas object gas that concentration sensor detects.
5. infrared gas sensor according to claim 4, it is characterized in that, the compensation that also comprises environment parameter in the method for correction is calculated and is compensated by the responsive unit of reference to the signal of other three transducers, specifically comprise that temperature-compensating is machine-processed, humidity compensate is machine-processed and the pressure compensation mechanism, be specially:
Temperature-compensating mechanism is:
Introduce temperature compensation parameter λ, the absorptivity in conjunction with temperature relation compensation infrared-gas concentration sensor internal object gas to infrared light
the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the definition temperature-compensating:
T: the real time temperature of external environment during test;
T
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time ambient temperature;
λ: temperature compensation parameter;
Wherein, temperature compensation parameter λ determines as follows: application infrared-gas concentration sensor is tested under definite object gas concentration, change the temperature of external environment simultaneously, and ambient temperature is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with the ambient temperature sampled point to infrared light
according to
the corresponding relation of value and ambient temperature carries out curve fitting, and asks for the occurrence of temperature compensation parameter λ;
Formula (13) is brought in formula (9), can obtain the target function of the temperature compensated rear calculating gas concentration of infrared-gas concentration sensor:
Based on ideal gas concentration law, to the target function C after temperature compensated
compensationcarry out the secondary temperature-compensating, obtain the final goal function that the infrared-gas concentration sensor calculates gas concentration:
Wherein, temperature T, T
0adopt normal temperature, unit is K;
Humidity compensate mechanism is:
In surface air, steam (H
2o) content in atmosphere is along with weather condition alters a great deal, H
2o has a lot of absorption bands at the INFRARED ABSORPTION wave band, so need to carry out the appropriateness compensation.On the basis of temperature-compensating, introduce the humidity compensate parameter
absorptivity in conjunction with humidity relation compensation infrared-gas concentration sensor internal object gas to infrared light
the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the definition humidity compensate:
RH: the real-time humidity of external environment during test;
RH
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time external environment humidity;
Wherein, humidity compensate parameter
determine as follows: application infrared-gas concentration sensor is tested at definite object gas concentration and temperature, change the humidity of external environment simultaneously, and ambient humidity is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with external environment humidity sampled point to infrared light
according to
the corresponding relation of value and extraneous humidity carries out curve fitting, and asks for the humidity compensate parameter
occurrence;
Formula (15) is brought in formula (9), can obtain the infrared-gas concentration sensor and calculate the target function of gas concentration after humidity compensate:
Wherein, humidity RH, RH
0adopt relative humidity;
The pressure compensation mechanism is:
Because the variation of pressure can cause the variation of molecular motion, and then affect the transmissivity of infrared light, so on the basis of temperature and humidity compensated, introduce pressure compensating parameter β, in conjunction with temperature, the compensation of humidity relation, the absorptivity of infrared-gas concentration sensor internal object gas to infrared light after the compensation of definition pressure:
(16)
P: the real-time pressure of external environment during test;
P
0: test is for determining that the output of infrared-gas concentration sensor zero-bit is than the infrared-gas concentration sensor output signal of Z
the time external environment pressure;
β: pressure compensating parameter;
Wherein, pressure compensating parameter β determines as follows: application infrared-gas concentration sensor is tested under definite object gas concentration, temperature and humidity, change the pressure of external environment simultaneously, and environmental stress is set the sampled point of some to external world, records the absorptivity of the infrared-gas concentration sensor internal object gas corresponding with external environment pressure sampled point to infrared light
according to
the corresponding relation of value and outside pressure carries out curve fitting, and asks for the occurrence of pressure compensating parameter β;
Formula (16) is brought in formula (9), can obtain the infrared-gas concentration sensor and calculate the target function of gas concentration after the pressure compensation:
Wherein, pressure P, P
0adopt normal pressure, unit is; bar
Output signal U according to final goal function and infrared-gas concentration sensor with reference to passage
ref.output signal U with sense channel
act., obtain the gas concentration C of infrared-gas object gas that concentration sensor detects.
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