CN103500770B - A kind of infrared gas sensor of many gas detecting - Google Patents
A kind of infrared gas sensor of many gas detecting Download PDFInfo
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- CN103500770B CN103500770B CN201310500970.3A CN201310500970A CN103500770B CN 103500770 B CN103500770 B CN 103500770B CN 201310500970 A CN201310500970 A CN 201310500970A CN 103500770 B CN103500770 B CN 103500770B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- 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
- H01L31/14—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 the light source or sources being controlled by the semiconductor device sensitive to radiation, e.g. image converters, image amplifiers or image storage devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses the infrared gas sensor of a kind of many gas detecting, standard CMOS/MEMS technology is used to be prepared in same chip the source of infrared radiation and multiple thermopile sensors, each chip chamber is by the way of being thermally isolated wall, heat insulation raceway groove and vacuum wafer scale alignment package, it is achieved the reduction to the hot crosstalk between coplanar sensor.Use monolithic integration process method, multisensor is processed simultaneously, different narrow wave band filter plate is used to be assembled in multiple sensors of coplanar arrangement respectively, realize gas with various is carried out light splitting detection, while being substantially reduced processing cost, reduce hot crosstalk and power consumption, and further increase accuracy of detection.
Description
Technical field
The present invention relates to infrared gas sensor technical field, the infrared-gas of a kind of many gas detecting
Sensor.
Background technology
Developing into of technology of Internet of things is integrated, low-power consumption, the infrared gas sensor of low cost bring and widely should
Use demand.Industry and daily life realize dangerous materials gas, such as CO, CO2, NO, NO2, CH4Highly sensitive detection, permissible
It is avoided to reveal the significant damage that social property and public safety are caused.Improving the same of sensor detection performance and portability
Time, it is achieved multiple gases is contactless to be detected simultaneously, meets Internet of Things, the complex environment development to micro-infrared multi-gas sensor
Demand.Infrared gas sensor, with MEMS and the development of CMOS technology, is achieved the miniature of infrared optics gas detecting system
Change, compared with traditional gas sensor, recover in stability, power consumption, sensitivity, reliability, service life, the response that is exceedingly fast
And the aspect such as cost, there is significant advantage.
Rae System company proposed discrete infrared light supply, detector, air chamber are integrated in a TO in 20025Pipe
As the infrared gas sensor of miniaturization in shell, and can be used in detecting Hydrocarbon HC, carbon dioxide CO2, an oxygen
Change carbon CO and nitric oxide NO gas concentration, but and unrealized multiple gases detect simultaneously, multiple gases needs before detecting
Separate complexity and the cost adding detection.
Summary of the invention
The technical problem to be solved is to provide the infrared of a kind of many gas detecting for the deficiencies in the prior art
Gas sensor.
Technical scheme is as follows:
Present invention firstly provides the infrared gas sensor of a kind of many gas detecting, including four sensitive units, be respectively as follows: the
One sensitive unit (1), the second sensitive unit (2), the 3rd sensitive unit (3) and reference sensitivity unit (4), four sensitive units are distributed on nanometer
It is on the circumference in the center of circle that infrared light supply (6) is modified on surface, wherein arranges one between the first sensitive unit (1), the second sensitive unit (2)
The heat insulation raceway groove (5) of L-type, is also provided with the heat insulation raceway groove (5) of a L-type between the 3rd sensitive unit (3) and reference sensitivity unit (4)；
Four sensitive units and nano-sized surface modification infrared light supply (6) is peripheral realizes being thermally isolated each other, fall by wall (7) is thermally isolated
The impact of low grade fever crosstalk；The narrow band filter slice wave band of reference sensitivity unit cover the first sensitive unit (1), the second sensitive unit (2), the 3rd
Sensitive unit (3), computes and compensates for revising to the signal of other three sensors by reference sensitivity unit.
Described infrared gas sensor, described first sensitive unit (1), the second sensitive unit (2), the 3rd sensitive unit (3) and
Reference sensitivity unit (4) is distributed in the oval focus of light source (5).
The present invention also provides for the preparation technology of described nano-sized surface modification infrared light supply (6), and step is as follows:
(a), in the upper grown silicon nitride (62) of monocrystalline substrate (61), experiment condition: temperature 780 DEG C, 330mTorr,
Six2Cl2: 24sccm, NH3: 90sccm；
The deposit of (b), non-crystalline silicon (63): temperature is 270 DEG C, and gas ratio is respectively SIH4: 24%NH3: 55%N2:
5.2%RF:170；
C (), Al sputtering and annealing: magnetron sputtering Al, condition: air pressure 10mTorr, be passed through after Ar meets air pressure conditions, if
Putting RF is 8400W, and then at 450 DEG C, the 90min time makes annealing treatment；
(d), wet etching Al film: using conventional Al corrosive liquid, after corrosion, sample surfaces is left Al-Si compound
Grain；
(e), non-crystalline silicon dry etching: use Cl2180sccm, pressure 300mTorr, RF350W, He200sccm, temperature
35-40 DEG C, after having etched, form micro-shelter of surface metal silicide composition；
F (), the etching of front release aperture, prepare for release monocrystalline substrate: gas CHF37sccm, He100sccm,
SF630sccm, RF150W, pressure 400mTorr；The method using magnetron sputtering, the TiN of sputtering 40-50A is coated with metal silication
Thing and non-crystalline silicon outer layer, condition is Ar22.4sccm, N23.0sccm, pressure is 5e-3Torr, and power is 1000W, and vacuum is
8e-7Pa；
(g)、XeF2Front release silicon substrate, forms micro-cantilever and is supported infrared light supply, and condition is XeF24Torr,
N220mTorr, temperature is 20 DEG C.
The present invention also provides for the method that the signal of other three sensors is computed and compensated for revising by reference sensitivity unit,
Concretely comprise the following steps: the output signal of described infrared-gas concentration sensor is divided into the output signal U of reference sensitivity unitRef.With detection
The output signal U of passageAct., two output signal URef.、UAct. with the object gas absorbance to infrared lightThere is a following relation:
I0: incident intensity, i.e. infrared light supply be incident reference passage and sense channel after narrowband optical filter plate filters
Infrared light intensity, records the most under a nitrogen atmosphere；
Infrared light intensity after being absorbed by object gas in I: transmitted light intensity, i.e. infrared-gas concentration sensor sense channel
Degree；
Based on being confined to monochromatic Lambert-beer's law: I=IO exp(-εlCn) (2)
C: target gas levels；
ε: the object gas absorptance to infrared light；
L: object gas incidence light path；
N: revise constant, depends on light path and object gas composition；
Infrared light supply infrared light of incident sense channel after narrowband optical filter plate filters is inevitable in its wave-length coverage
There is the light in some wave-length coverages to be absorbed by object gas, i.e. there is non-absorbing wave band, therefore, formula (2) is converted to:
I=IO×((1-S)×e(-ΣεlC")+S) (3)
S: non-absorbing wave band accounts for the proportionality coefficient of sense channel directs optical wavelength range, characterizes non-absorbing wave band pair
Infrared-gas concentration sensor sense channel output signal UAct.Contribution；
α: exponential constant is relevant to the meansigma methods of ε l in Lambert-beer's law；
β: power constant, depends on the spectral characteristic of object gas；
In the case of object gas is non-existent, infrared-gas concentration sensor sense channel output signal UAct.With reference
Multi-channel output signal URef.Ratio be defined as infrared-gas concentration sensor zero-bit output ratio, represent by symbols Z,
I.e.
In the case of object gas is non-existent, infrared-gas concentration sensor sense channel output signal UAct.'s
Peak-to-peak value；
In the case of object gas is non-existent, infrared-gas concentration sensor is with reference to multi-channel output signal URef.
Peak-to-peak value；
In the presence of object gas, infrared-gas concentration sensor transmitted light intensity I and incident intensity I0Ratio
More relevant than Z, i.e. to the output of the zero-bit of infrared-gas concentration sensor
Then formula (5) can be exchanged into；
In formula (9), parameter alpha, β determine as follows；
First, the object gas relative absorbency Fa to infrared-gas concentration sensor infrared light is determined, i.e.
Then, based under the test status of same concentrations object gas, same determine that type infrared-gas concentration senses
The concordance of device infrared light relative absorbency Fa, chooses several infrared-gas concentration sensors, it is desirable to determine type for same,
And determine the concentrations tested ranged of object gas, in the concentrations tested ranged of object gas, set test point at equal intervals；Application
Each infrared-gas concentration sensor is tested one by one according to test point, records each infrared-gas concentration sensor dense with test
The infrared light relative absorbency Fa that angle value is corresponding, averaged, and according to test point gas concentration value and relative absorbency Fa
The corresponding relation of meansigma methods, draws 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-target gas levels C；
The meansigma methods of Y: dependent variable-infrared-gas concentration sensor infrared light relative absorbency Fa；
W:1-S, ignores and does not remember；
According to test result analysis the test result that records, formula (11) is carried out curve fitting, ask for parameter alpha and 3
Occurrence；
Parameter S in formula (9) can be drawn by formula (8):
C ": the full scale target gas levels of infrared-gas concentration sensor test；
When target gas levels full scale, infrared-gas concentration sensor sense channel output signal UAct.'s
Peak-to-peak value；
When target gas levels full scale, infrared-gas concentration sensor is with reference to multi-channel output signal URef.'s
Peak-to-peak value；
By related data: parameter alpha, β, S, Z bring in formula (9), i.e. can get infrared-gas concentration sensor and calculate gas
The object function of concentration, according to object function and the output signal U of infrared-gas concentration sensor reference passageRef.With inspection
Survey the output signal U of passageAct., obtain gas concentration C of the detected object gas of infrared-gas concentration sensor.
Further, the signal of other three sensors is computed and compensated for going back in the method revised by reference sensitivity unit
Including the compensation of environment parameter, specifically include temperature-compensating mechanism, humidity compensation mechanism and pressure compensation mechanism, particularly as follows:
Temperature-compensating mechanism is:
Introduce temperature compensation parameter λ, compensate infrared-gas concentration sensor internal object gas to infrared in conjunction with temperature relation
The absorbance of lightThe infrared-gas concentration sensor internal object gas absorbance to infrared light after definition temperature-compensating:
T: the real time temperature of external environment during test；
T0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output than Z
Signal Time ambient temperature；
λ: temperature compensation parameter；
Wherein, temperature compensation parameter λ determines as follows: application infrared-gas concentration sensor is at the target gas determined
Test under bulk concentration, change the temperature of external environment simultaneously, and ambient temperature sets a number of sampled point to external world,
Record the infrared-gas concentration sensor internal object gas corresponding with the ambient temperature sampled point absorbance to infrared lightI.e.According toValue carries out curve fitting with the corresponding relation of ambient temperature, asks for temperature compensation parameter
The occurrence of λ；
Formula (13) is brought in formula (9), i.e. can get the temperature compensated rear calculating gas of infrared-gas concentration sensor dense
The object function of degree:
Based on ideal gas concentration law, to the object function C after the most temperature compensatedCompensateCarry out secondary temperature-compensating, obtain
Infrared-gas concentration sensor calculate gas concentration final goal function:
Wherein, temperature T, T0Using standard temperature, unit is K；
Humidity compensation mechanism is:
In surface air, steam (H2O) content in an atmosphere is along with weather condition change the most greatly, H2O is in infrared suction
Receive wave band and have a lot of absorption band, so needing to carry out appropriateness compensation.On the basis of temperature-compensating, introduce humidity compensating parameter
The infrared-gas concentration sensor internal object gas absorbance to infrared light is compensated in conjunction with humidity relationAfter definition humidity compensates
The infrared-gas concentration sensor internal object gas absorbance to infrared light:
RH: the real-time humidity of external environment during test；
RH0；Test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output than Z
Signal Time external environment humidity；
Humidity compensating parameter；
Wherein, humidity compensating parameterDetermine as follows: application infrared-gas concentration sensor is at the target gas determined
Bulk concentration and at a temperature of test, change the humidity of external environment simultaneously, and ambient humidity set a number of to external world
Sampled point, records the infrared-gas concentration sensor internal object gas corresponding with the external environment humidity sampled point suction to infrared light
YieldI.e.According toValue carries out curve fitting with the corresponding relation of ambient humidity, asks for humidity and mends
Repay parameterOccurrence；
Formula (15) is brought in formula (9), i.e. can get infrared-gas concentration sensor calculating gas after humidity compensates dense
The object function of degree:
Wherein, humidity RH, RH0Use relative humidity；
Pressure compensation mechanism is:
Change due to pressure can cause the change of molecular motion, and then affects the absorbance of infrared light, thus temperature,
On the basis of humidity compensates, introduce pressure compensating parameter β, compensate in conjunction with temperature, humidity relation, infrared gas after definition pressure compensation
The concentration sensors internal object gas absorbance to infrared light:
(16)
P: the real-time pressure of external environment during test；
P0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output than Z
Signal Time external environment pressure；
β: pressure compensating parameter；
Wherein, pressure compensating parameter β determines as follows: application infrared-gas concentration sensor is at the target gas determined
Test under bulk concentration, temperature and humidity, change the pressure of external environment simultaneously, and environmental stress sets a fixed number to external world
The sampled point of amount, records the infrared-gas concentration sensor internal object gas corresponding with external environment pressure sampled point to infrared light
AbsorbanceI.e.According toValue carries out curve fitting with the corresponding relation of outside pressure, asks for pressure
The occurrence of compensating parameter β；
Formula (16) is brought in formula (9), i.e. can get infrared-gas concentration sensor calculating gas after pressure compensates dense
The object function of degree:
Wherein, pressure P, P0Using normal pressure, unit is；bar
According to final goal function and the output signal U of infrared-gas concentration sensor reference passageRef.Logical with detection
The output signal U in roadAct., obtain gas concentration C of the detected object gas of infrared-gas concentration sensor.
The method have the advantages that
1, use monolithic integration process method, multisensor is processed simultaneously, use different narrow wave band filter plate to divide
It is not assembled in multiple sensors of coplanar arrangement, it is achieved gas with various is carried out light splitting detection, is substantially reduced processing cost
Meanwhile, reduce hot crosstalk and power consumption, and further increase accuracy of detection.
2, employing is thermally isolated wall and groove structure is thermally isolated, and each detector is thermally isolated, and realizes many with this kind of technology
The single-chip integration manufacture of gas sensor, it is not necessary to it is packaged respectively.
3, MEMS/CMOS compatible technique is used to prepare infrared light supply, it is achieved with the coplanar Integrated manufacture of sensor.
4, use reference sensitivity unit that the probe unit assembling narrow-band filter plate is carried out signal analysis and compensating approach.
Accompanying drawing explanation
Fig. 1 is the structural representation of the infrared gas sensor of the many gas detecting of the present invention；
Fig. 2 is the processing technique principle schematic of nano-sized surface modification infrared light supply of the present invention；
Fig. 3 is nanostructured infrared light supply cone-shaped nano structure SEM electromicroscopic photograph；
Fig. 4 is nanostructured infrared light supply infrared emittance analysis of the present invention；
Fig. 5 is nanostructured 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 sensitive unit, 2 second sensitive units, 3 the 3rd sensitive units, 4 reference sensitivity units, 5 heat insulation raceway grooves, 6 Nanosurfaces are repaiied
Decorations infrared light supply, 61 silicon substrates, 62 silicon nitrides, 63 non-crystalline silicons, 64Al, 65TiN；7 are thermally isolated wall.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
The present invention is that the CMOS/MEMS technique not elaborated is prior art.
Embodiment 1
With reference to Fig. 1, in the infrared gas sensor of the many gas detecting shown in Fig. 1, including four sensitive units, respectively
For: the first sensitive unit 3 of sensitive unit of sensitive unit 1, second the 2, the 3rd and reference sensitivity unit 4, four sensitive units are distributed on nanometer table
It is on the circumference in the center of circle that infrared light supply 6 is modified in face, wherein arranges two heat insulation raceway grooves between the first sensitive unit 2 of sensitive unit 1, second
5, it is also provided with two same heat insulation raceway grooves 5 between the 3rd sensitive unit 3 and reference sensitivity unit 4；Four sensitive units and Nanosurface
Modify infrared light supply 6 periphery and realized being thermally isolated each other by wall 7 is thermally isolated, reduce the impact of hot crosstalk.
Utilize MEMS technology, single silicon chip is prepared four gas infrared sensors and MEMS infrared light supply simultaneously, its
In three sensors be respectively combined narrow-band filter plate, the specific wave of each sensor test gas is depended in the selection of filter plate
Section, the narrow band filter slice wave band of reference sensitivity unit covers (the first sensitive unit of sensitive unit 51, second of other three gas sensitization units
52, the 3rd sensitive unit 53), compute and compensate for revising to the signal of other three sensors by reference sensitivity unit.
Embodiment 2
The present embodiment provides a kind of nano-sized surface modification infrared light supply 6, as an object lesson, with reference to step in Fig. 2
(a)-(g), to the preparation technology of nano-sized surface modification infrared light supply 6 of the present invention, details are as follows:
(a), in monocrystalline substrate 61 grown silicon nitride 62, experiment condition；Temperature 780 DEG C, 330mTorr, SiH2Cl2；
24sccm, NH3: 90sccm；
The deposit of (b), non-crystalline silicon 63: temperature is 270 DEG C, and gas flow and ratio are respectively SIH4: 24%NH3: 55%
N2: 5.2%RF:170；
C (), Al sputtering and annealing: magnetron sputtering Al, condition: air pressure 10mTorr, be passed through after Ar meets air pressure conditions, if
Putting RF is 8400W, and then at 450 DEG C, the 90min time makes annealing treatment；
(d), wet etching Al film: using conventional Al corrosive liquid, after corrosion, sample surfaces is left Al-Si compound
Grain.
(e), non-crystalline silicon dry etching: use Cl2180sccm, pressure 300mTorr, RF350W, He200sccm, temperature
35-40 DEG C, after having etched, only it is left the metal silicide on surface.
F (), the etching of front release aperture, prepare for release monocrystalline substrate: gas CHF37sccm, He100sccm,
SF630sccm, RF150W, pressure 400mTorr.The method using magnetron sputtering, the TiN of sputtering 40-50A is coated with metal silication
Thing and non-crystalline silicon outer layer, concrete experiment condition is Ar22.4sccm, N23.0sccm, pressure is 5e-3Torr, and power is
1000W, vacuum is 8e-7Pa.
(g)、XeF2Front release silicon substrate, forms micro-cantilever and is supported infrared light supply, and condition is XeF24Torr,
N220mTorr, temperature is 20 DEG C.
In step (c), use metal-induced crystallization and prepare taper forest structure, utilize metal and silicon to dissolve each other former
Reason, forms metal silicide grain at boundary layer, in the process of metal wet etching, does not carry out silicon point and cleans, retain metal
Silicide particle is as sheltering that next step etches.The cone-shaped nano structure forming etching has carried out the shooting of SEM electromicroscopic photograph,
Cone structure surface area as shown in Figure 3 adds about 5 times, after its surface is carried out TiN sputtering, has carried out infrared emission
Rate is analyzed, and as shown in Figure 4, is higher than 70% emissivity at HCl and NO detection field, possesses neck in CH4, SO2, CO2 and NO2 detection
Territory is higher than 60% emissivity, and at 8-10 mu m waveband, there is the infrared emittance higher than 70%, XPS elementary analysis and Valence States
Analysis (table 1, table 2).Table 1 shows C, O, Si in common process, and the F that has an effect in metal-induced crystallization process and
Al, table 2 shows, after the infrared light supply processing of preparation, the chemicals being primarily present are AlFx, AlSix.And metal-induced crystallization mistake
The metal silicide produced in journey, is etched in preparation process completely.
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
Use Al-Si dissolve each other technology formed metal silicide, as micro-shelter to inject silicon perform etching, formed taper
Nanostructured, and at the TiN of its surface sputtering 40-50A, strengthen surface plasmon resonance effect, improve emissivity about 5% left
Right.Use deep silicon etching technology, it is achieved the front release of arrowband infrared light supply, reduce the thermal losses of light source heating process.For fall
The structural stress of the infrared light supply of the low suspension present invention, uses SiN to carry out directly as with heating layer (the present embodiment is non-crystalline silicon 3)
The dielectric layer of contact, reduces residual stress problems, has simulation example proving effect as shown in Figure 5.Phantom is to utilize
Comsol mutiphisics software, when research thermal source loads 0.2V voltage, under the influence of ohm heating effect, structural stress
Change, adding after silicon nitride medium layer, the maximum stress of arrowband infrared light supply is only 0.1299Gpa, it is ensured that structure
Stability.
Embodiment 3
1) method for processing concentration signal of infrared gas sensor
Gas detection method based on infrared optics principle has many kinds, and wherein double UV check method is the most conventional, should
Method can play reference wavelength ambient compensation effect, thus is effectively improved anti-interference and the stability of system.Based on light
The gas concentration calculating method learning principle also has many kinds, is presently mainly according to accuracy requirement determines concrete which kind of side of employing
Method calculates gas concentration.The present embodiment mainly elaborates the linear interpolation-data lookup table computational methods used in research process,
The method is relatively easy, and its result meets big multiple-alarm, the application demand of warning occasion, such as coal mine gas alarm
Deng.The precision of the method depends primarily on the data form situation of demarcation in advance, and the data segment of demarcation is the most, and test result is more
Accurately, concrete calculating is to first determine whether that the concentration value currently tested falls in which interval of each point demarcated in advance, then leads to
Cross interpolation method and substitute into calculating, there is computed in software and fast automatic calibration function simultaneously.
A kind of infrared-gas concentration sensor signal processing method, the output signal of described infrared-gas concentration sensor is divided
For the output signal U with reference to sensitive unitRef.Output signal U with sense channelAct., two output signal URef.、UAct.With target gas
The body absorbance to infrared lightThere is a following relation:
I0: incident intensity, i.e. infrared light supply be incident reference passage and sense channel after narrowband optical filter plate filters
Infrared light intensity, records the most under a nitrogen atmosphere；
Infrared light intensity after being absorbed by object gas in I: transmitted light intensity, i.e. infrared-gas concentration sensor sense channel
Degree；
Based on being confined to monochromatic Lambert-beer's law: I=IO exp(-εlCn) (2)
C: target gas levels；
ε: the object gas absorptance to infrared light；
L: object gas incidence light path；
N: revise constant, depends on light path and object gas composition；
It is considered that infrared light supply after narrowband optical filter plate filters the infrared light of incident sense channel in its wave-length coverage
Inside certainly exist the light in some wave-length coverages to be absorbed by object gas, i.e. there is non-absorbing wave band, therefore, by formula (2)
Be converted to:
I=IO×((1-S)×e(-ΣεlCn)+S) (3)
S: non-absorbing wave band accounts for the proportionality coefficient of sense channel directs optical wavelength range, characterizes non-absorbing wave band pair
Infrared-gas concentration sensor sense channel output signal UAct.Contribution；
α: exponential constant is relevant to the meansigma methods of ε l in Lambert-beer's law；
β: power constant, depends on the spectral characteristic of object gas；
In the case of object gas is non-existent, infrared-gas concentration sensor sense channel output signal UAct.With reference
Multi-channel output signal URef.Ratio be defined as infrared-gas concentration sensor zero-bit output ratio, represent by symbols Z,
I.e.
In the case of object gas is non-existent, infrared-gas concentration sensor sense channel output signal UAct.'s
Peak-to-peak value；
In the case of object gas is non-existent, infrared-gas concentration sensor is with reference to multi-channel output signal URef.
Peak-to-peak value；
In the presence of object gas, infrared-gas concentration sensor transmitted light intensity I and incident intensity I0Ratio
More relevant than Z, i.e. to the output of the zero-bit of infrared-gas concentration sensor
Then formula (5) can be exchanged into:
In formula (9), parameter alpha, β determine as follows:
First, the object gas relative absorbency Fa to infrared-gas concentration sensor infrared light is determined, i.e.
Then, based under the test status of same concentrations object gas, same determine that type infrared-gas concentration senses
The concordance of device infrared light relative absorbency Fa, chooses several infrared-gas concentration sensors, it is desirable to determine type for same,
And determine the concentrations tested ranged of object gas, in the concentrations tested ranged of object gas, set test point at equal intervals；Application
Each infrared-gas concentration sensor is tested one by one according to test point, records each infrared-gas concentration sensor dense with test
The infrared light relative absorbency Fa that angle value is corresponding, averaged, and according to test point gas concentration value and relative absorbency Fa
The corresponding relation of meansigma methods, draws test result analysis table；
Finally, according to formula (10) Selection of Function relational expression: Y=W × (1-exp (-α Xβ)) (11)
X: independent variable-target gas levels C；
The meansigma methods of Y: dependent variable-infrared-gas concentration sensor infrared light relative absorbency Fa；
W:1-S, ignores and does not remember；
According to test result analysis the test result that records, formula (11) is carried out curve fitting, ask for parameter alpha and β
Occurrence；
Parameter S in formula (9) can be drawn by formula (8):
C ": the full scale target gas levels of infrared-gas concentration sensor test；
When target gas levels full scale, infrared-gas concentration sensor sense channel output signal UAct.'s
Peak-to-peak value；
When target gas levels full scale, infrared-gas concentration sensor is with reference to multi-channel output signal URef.'s
Peak-to-peak value；
By related data: parameter alpha, β, S, Z bring in formula (9), i.e. can get infrared-gas concentration sensor and calculate gas
The object function of concentration, according to object function and the output signal U of infrared-gas concentration sensor reference passageRef.With inspection
Survey the output signal U of passageAct., obtain gas concentration C of the detected object gas of infrared-gas concentration sensor.
2) temperature-compensating mechanism
Under normal circumstances, the survey calculation result of gas concentration has relation, including one with gas indoor temperature in test process
Other ambient parameter a bit, gas concentration value is all had a direct impact by such as humidity, pressure etc., but it is maximum to belong to temperature impact, this
Inferring also according to the principle of thermo-responsive unit and obtain, therefore, it is the most necessary for taking appropriate action to compensation calculation result.
Requirement according to look-up method and accuracy relation, can obtain a kind of simple compensation by experience and experimental test data analysis
Measure.
Also include measuring temperature compensation in real time；Introduce temperature compensation parameter λ, compensate infrared-gas in conjunction with temperature relation
The concentration sensor internal object gas absorbance to infrared lightInfrared-gas concentration sensor internal object after definition temperature-compensating
The gas absorbance to infrared light:
T: the real time temperature of external environment during test；
T0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output than Z
Signal Time ambient temperature；
λ: temperature compensation parameter；
Wherein, temperature compensation parameter λ determines as follows: application infrared-gas concentration sensor is at the target gas determined
Test under bulk concentration, change the temperature of external environment simultaneously, and ambient temperature sets a number of sampled point to external world,
Record the infrared-gas concentration sensor internal object gas corresponding with the ambient temperature sampled point absorbance to infrared lightI.e.According toValue carries out curve fitting with the corresponding relation of ambient temperature, asks for temperature compensation parameter
The occurrence of λ；
Formula (13) is brought in formula (9), i.e. can get the temperature compensated rear calculating gas of infrared-gas concentration sensor dense
The object function of degree:
Based on ideal gas concentration law, to the object function C after the most temperature compensatedCompensateCarry out secondary temperature-compensating, obtain
Obtain infrared-gas concentration sensor and calculate the final goal function of gas concentration；
(14)
Wherein, temperature T, T0Using standard temperature, unit is K；
Humidity compensation mechanism is:
In surface air, steam (H2O) content in an atmosphere is along with weather condition change the most greatly, H2O is in infrared suction
Receive wave band and have a lot of absorption band, so needing to carry out appropriateness compensation.On the basis of temperature-compensating, introduce humidity compensating parameterThe infrared-gas concentration sensor internal object gas absorbance to infrared light is compensated in conjunction with humidity relationDefinition humidity is mended
Repay the rear infrared-gas concentration sensor internal object gas absorbance to infrared light:
RH: the real-time humidity of external environment during test；
RH0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output than Z
Signal Time external environment humidity；
Humidity compensating parameter；
Wherein, humidity compensating parameterDetermine as follows: application infrared-gas concentration sensor is at the target gas determined
Bulk concentration and at a temperature of test, change the humidity of external environment simultaneously, and ambient humidity set a number of to external world
Sampled point, records the infrared-gas concentration sensor internal object gas corresponding with the external environment humidity sampled point suction to infrared light
YieldI.e.According toValue carries out curve fitting with the corresponding relation of ambient humidity, asks for humidity and compensates
ParameterOccurrence；
Formula (15) is brought in formula (9), i.e. can get infrared-gas concentration sensor calculating gas after humidity compensates dense
The object function of degree:
Wherein, humidity RH, RH0Use relative humidity；
Pressure compensation mechanism is:
Change due to pressure can cause the change of molecular motion, and then affects the absorbance of infrared light, thus temperature,
On the basis of humidity compensates, introduce pressure compensating parameter β, compensate in conjunction with temperature, humidity relation, infrared gas after definition pressure compensation
The concentration sensors internal object gas absorbance to infrared light:
(16)
P: the real-time pressure of external environment during test；
P0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output than Z
Signal Time external environment pressure；
β: pressure compensating parameter；
Wherein, pressure compensating parameter β determines as follows: application infrared-gas concentration sensor is at the target gas determined
Test under bulk concentration, temperature and humidity, change the pressure of external environment simultaneously, and environmental stress sets a fixed number to external world
The sampled point of amount, records the infrared-gas concentration sensor internal object gas corresponding with external environment pressure sampled point to infrared light
AbsorbanceI.e.According toValue carries out curve fitting with the corresponding relation of outside pressure, asks for pressure
The occurrence of strong compensating parameter β；
Formula (16) is brought in formula (9), i.e. can get infrared-gas concentration sensor calculating gas after pressure compensates dense
The object function of degree:
Wherein, pressure P, P0Using normal pressure, unit is；bar
According to final goal function and the output signal U of infrared-gas concentration sensor reference passageRef.Logical with detection
The output signal U in roadAct., obtain gas concentration C of the detected object gas of infrared-gas concentration sensor.
3) concentration calculation software design
Fact proved, ir-absorbance, along with the change of gas concentration, is also done by the design of air chamber structure, electromagnetism simultaneously
Disturb, the mode of signal extraction is affected.Therefore, infrared light supply needs to be modulated by microprocessor, and combines Detection of Weak Signals side
Method and software processes improve detection performance, and Fig. 6 describes the flow chart of whole design.During calculating, ambient temperature is same
Sample needs to be acquired first, and it is used to calculate the foundation compensated.The method of its Signal acquiring and processing and look-up method
Similar, need to be tried to achieve by collection the output signal of two passages, and carry out the parameter being correlated with according to the output signal of this two passage
Calculate, such as carry out the calculating of zero-bit, span.
The algorithm of the present invention has the advantages that
1), the shadow of infrared-gas concentration sensor zero-bit output Determination result in the case of object gas is non-existent
Ring；
2), for the ambient temperature impact on infrared-gas concentration sensor testing result, implement twice temperature-compensating, use
To revise the testing result of infrared-gas concentration sensor.
3), the impact of temperature in perfect gas law is realized second compensation；Make the infrared-gas concentration sensor can be
Use under condition of different temperatures, overcome and change shadow to infrared-gas concentration sensor usability because of area and weather condition
Ring.
It should be appreciated that for those of ordinary skills, can be improved according to the above description or be converted,
And all these modifications and variations all should belong to the protection domain of claims of the present invention.
Claims (3)
1. the infrared gas sensor of gas detecting more than a kind, it is characterised in that include four sensitive units, be respectively as follows: first quick
Sense unit (1), the second sensitive unit (2), the 3rd sensitive unit (3) and reference sensitivity unit (4), four sensitive units are distributed on Nanosurface
Modifying infrared light supply (6) is on the circumference in the center of circle, wherein arranges a L-type between the first sensitive unit (1), the second sensitive unit (2)
Heat insulation raceway groove (5), be also provided with the heat insulation raceway groove (5) of a L-type between the 3rd sensitive unit (3) and reference sensitivity first (4)；Four
Sensitive unit and nano-sized surface modification infrared light supply (6) is peripheral realizes being thermally isolated each other by wall (7) is thermally isolated, reduces heat
The impact of crosstalk；The sensitive unit (1) of narrow band filter slice wave band covering first of reference sensitivity unit, the second sensitive unit (2), the 3rd sensitivity
Unit (3), computes and compensates for revising to the signal of other three sensors by reference sensitivity unit；Described nano-sized surface modification
The preparation technology of infrared light supply (6) is as follows:
(a), at the upper grown silicon nitride (62) of monocrystalline substrate (61), experiment condition: temperature 780 DEG C, 330mTorr, SiH2Cl2∶
24sccm, NH3∶90sccm；
The deposit of (b), non-crystalline silicon (63): temperature is 270 DEG C, and gas ratio is respectively SiH4: 24%NH3: 55%N2: 5.2%；
RF∶170W；
C (), Al sputtering and annealing: magnetron sputtering Al, condition: air pressure 10mTorr, be passed through after Ar meets air pressure conditions, arrange RF
For 8400W, at 450 DEG C, then carry out 90min annealing；
(d), wet etching Al film: using conventional Al corrosive liquid, after corrosion, sample surfaces is left Al-Si compound particle；
(e), non-crystalline silicon dry etching: use Cl2180sccm, pressure 300mTorr, RF 350W, He 200sccm, temperature 35-
40 DEG C, after having etched, form micro-shelter of surface metal silicide composition；
F (), the etching of front release aperture, prepare for release monocrystalline substrate: gas CHF37sccm, He 100sccm, SF6
30sccm, RF 150W, pressure 400mTorr；The method using magnetron sputtering, sputteringTiN be coated with metal silicide
With non-crystalline silicon outer layer, condition is Ar 22.4sccm, N23.0sccm, pressure is 5e-3Torr, power is 1000W, and vacuum is
8e-7Pa；
(g)、XeF2Front release silicon substrate, forms micro-cantilever and is supported infrared light supply, and condition is XeF24Torr, N2
20mTorr, temperature is 20 DEG C.
The infrared gas sensor of many gas detecting the most according to claim 1, it is characterised in that reference sensitivity unit is to it
The method that the signal of his three sensors carries out computing and compensating for revising is: the output signal of described infrared gas sensor is divided into
The output signal U of reference sensitivity unitRef.Output signal U with sense channelAct., two output signal URef.、UAct.With object gas
Absorbance to infrared lightThere is a following relation:
I0: incident intensity, i.e. infrared light supply be the incident infrared light with reference to passage with sense channel after narrowband optical filter plate filters
Intensity, records the most under a nitrogen atmosphere；
Infrared light intensity after being absorbed by object gas in I: transmitted light intensity, i.e. infrared-gas concentration sensor sense channel；
Based on being confined to monochromatic Lambert-beer's law: I=IOexp(-εlCn) (2)
C: target gas levels；
ε: the object gas absorptance to infrared light；
L: object gas incidence light path；
N: revise constant, depends on light path and object gas composition；
Infrared light supply infrared light of incident sense channel after narrowband optical filter plate filters certainly exists in its wave-length coverage
Light in some wave-length coverages will not be absorbed by object gas, i.e. there is non-absorbing wave band, therefore, formula (2) is converted to:
S: non-absorbing wave band accounts for the proportionality coefficient of sense channel directs optical wavelength range, characterizes non-absorbing wave band to infrared
Gas concentration sensor sense channel output signal UAct.Contribution；
α: exponential constant is relevant to the meansigma methods of ε l in Lambert-beer's law；
β: power constant, depends on the spectral characteristic of object gas；
In the case of object gas is non-existent, infrared-gas concentration sensor sense channel output signal UAct.With reference passage
Output signal URef.Ratio be defined as infrared-gas concentration sensor zero-bit output ratio, represent by symbols Z,
I.e. Z=U 'Act./U′Ref. (6)
U′Act.: in the case of object gas is non-existent, infrared-gas concentration sensor sense channel output signal UAct.Peak-
Peak value；
U′Ref.: in the case of object gas is non-existent, infrared-gas concentration sensor is with reference to multi-channel output signal URef.Peak-
Peak value；
In the presence of object gas, infrared-gas concentration sensor transmitted light intensity I and incident intensity I0Ratio with infrared
The zero-bit output of gas concentration sensor is correlated with than Z, i.e.
Then formula (5) can be exchanged into:
In formula (9), parameter alpha, β determine as follows:
First, the object gas relative absorbency Fa to infrared-gas concentration sensor infrared light is determined, i.e.
Then, based under the test status of same concentrations object gas, same determine that type infrared-gas concentration sensor is red
The concordance of outer smooth relative absorbency Fa, chooses several infrared-gas concentration sensors, it is desirable to determine type for same, and really
Set the goal the concentrations tested ranged of gas, sets test point in the concentrations tested ranged of object gas at equal intervals；Apply each red
Outer gas concentration sensor is tested one by one according to test point, records each infrared-gas concentration sensor and test concentrations value
Corresponding infrared light relative absorbency Fa, averaged, and average with relative absorbency Fa according to test point gas concentration value
The corresponding relation of value, draws test result analysis table；
Finally, according to formula (10) Selection of Function relational expression: Y=W × (1-exp (-α Xβ)) (11)
X: independent variable-target gas levels C；
The meansigma methods of Y: dependent variable-infrared-gas concentration sensor infrared light relative absorbency Fa；
W:1-S, ignores；
According to test result analysis the test result that records, formula (11) is carried out curve fitting, ask for the concrete of parameter alpha and β
Value；
Parameter S in formula (9) can be drawn by formula (8):
C ": the full scale target gas levels of infrared-gas concentration sensor test；
U″Act.: when target gas levels full scale, infrared-gas concentration sensor sense channel output signal UAct.Peak-peak
Value；
U″Ref.: when target gas levels full scale, infrared-gas concentration sensor is with reference to multi-channel output signal URef.Peak-peak
Value；
By related data: parameter alpha, β, S, Z bring in formula (9), i.e. can get infrared-gas concentration sensor and calculate gas concentration
Object function, according to object function and infrared-gas concentration sensor with reference to the output signal U of passageRef.Logical with detection
The output signal U in roadAct., obtain gas concentration C of the detected object gas of infrared-gas concentration sensor.
The infrared gas sensor of many gas detecting the most according to claim 2, it is characterised in that reference sensitivity unit is to it
The signal of his three sensors carries out also including in the method computing and compensating for revising the compensation of environment parameter, specifically includes temperature
Compensation mechanism, humidity compensation mechanism and pressure compensation mechanism, particularly as follows:
Temperature-compensating mechanism is:
Introduce temperature compensation parameter λ, compensate infrared-gas concentration sensor internal object gas to infrared light in conjunction with temperature relation
AbsorbanceThe infrared-gas concentration sensor internal object gas absorbance to infrared light after definition temperature-compensating:
T: the real time temperature of external environment during test；
T0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output signal than Z
U′Act.、U′Ref.Time ambient temperature；
λ: temperature compensation parameter；
Wherein, temperature compensation parameter λ determines as follows: application infrared-gas concentration sensor is dense at the object gas determined
Test under degree, change the temperature of external environment simultaneously, and ambient temperature sets a number of sampled point, record to external world
The infrared-gas concentration sensor internal object gas corresponding with the ambient temperature sampled point absorbance to infrared lightI.e.According toValue carries out curve fitting with the corresponding relation of ambient temperature, asks for the tool of temperature compensation parameter λ
Body value；
Formula (13) is brought in formula (9), i.e. can get the temperature compensated rear calculating gas concentration of infrared-gas concentration sensor
Object function:
Based on ideal gas concentration law, to the object function C after the most temperature compensatedCompensateCarry out secondary temperature-compensating, it is thus achieved that red
The final goal function of outer gas concentration sensor calculating gas concentration:
Wherein, temperature T, T0Using standard temperature, unit is K；
Humidity compensation mechanism is:
In surface air, steam (H2O) content in an atmosphere is along with weather condition change the most greatly, H2O is at INFRARED ABSORPTION ripple
Section has a lot of absorption band, so needing to carry out appropriateness compensation, on the basis of temperature-compensating, introduces humidity compensating parameterKnot
Close humidity relation and compensate the infrared-gas concentration sensor internal object gas absorbance to infrared lightDefinition humidity is red after compensating
The outer gas concentration sensor internal object gas absorbance to infrared light:
RH: the real-time humidity of external environment during test；
RH0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output signal than Z
U′Act.、U′Ref.Time external environment humidity；
Humidity compensating parameter；
Wherein, humidity compensating parameterDetermine as follows: application infrared-gas concentration sensor is dense at the object gas determined
Degree and at a temperature of test, change the humidity of external environment simultaneously, and ambient humidity set a number of sampling to external world
Point, records the infrared-gas concentration sensor internal object gas corresponding with the external environment humidity sampled point absorbance to infrared lightI.e.According toValue carries out curve fitting with the corresponding relation of ambient humidity, asks for humidity and compensates ginseng
NumberOccurrence；
Formula (15) is brought in formula (9), i.e. can get infrared-gas concentration sensor after humidity compensates, calculate gas concentration
Object function:
Wherein, humidity RH, RH0Use relative humidity；
Pressure compensation mechanism is:
Change due to pressure can cause the change of molecular motion, and then affects the absorbance of infrared light, so in temperature, humidity
On the basis of compensation, introducing pressure compensating parameter β, compensate in conjunction with temperature, humidity relation, after definition pressure compensates, infrared-gas is dense
The degree sensor internal object gas absorbance to infrared light:
P: the real-time pressure of external environment during test；
P0: test is for determining the infrared-gas concentration sensor zero-bit output infrared-gas concentration sensor output signal than Z
U′Act.、U′Ref.Time external environment pressure；
β: pressure compensating parameter；
Wherein, pressure compensating parameter β determines as follows: application infrared-gas concentration sensor is dense at the object gas determined
Test under degree, temperature and humidity, change the pressure of external environment simultaneously, and environmental stress sets a number of to external world
Sampled point, records the infrared-gas concentration sensor internal object gas corresponding with the external environment pressure sampled point suction to infrared light
YieldI.e.According toValue carries out curve fitting with the corresponding relation of outside pressure, asks for pressure and mends
Repay the occurrence of parameter beta；
Formula (16) is brought in formula (9), i.e. can get infrared-gas concentration sensor after pressure compensates, calculate gas concentration
Object function:
Wherein, pressure P, P0Using normal pressure, unit is bar；
According to final goal function and the output signal U of infrared-gas concentration sensor reference passageRef.With sense channel
Output signal UAct., obtain gas concentration C of the detected object gas of infrared-gas concentration sensor.
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| CN112082967B (en) * | 2020-09-18 | 2021-08-31 | 重庆大学 | Ultra-narrow band infrared thermal radiation light source and compact infrared gas sensor |
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| CN116973521B (en) * | 2023-09-21 | 2023-12-22 | 北京燕山时代仪表有限公司 | Temperature compensation method and device for gas detector and gas detector |
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| US5041723A (en) * | 1989-09-30 | 1991-08-20 | Horiba, Ltd. | Infrared ray detector with multiple optical filters |
| CN102183482A (en) * | 2011-02-23 | 2011-09-14 | 中国科学院安徽光学精密机械研究所 | Non-disperse infrared multi-component flue gas analyzer |
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