CN110361436A - A kind of gradient stack-up array, preparation method and gas multi concentration detection method - Google Patents
A kind of gradient stack-up array, preparation method and gas multi concentration detection method Download PDFInfo
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Abstract
The invention belongs to semiconductor transducer gas sensitive detection fields, and specifically disclose a kind of gradient stack-up array, preparation method and gas multi concentration detection method, the gradient stack-up array includes at least two micropore filtering films/Semiconductor gas sensors film lamination device being sequentially arranged from top to bottom, and the aperture of the micropore filtering film on each micropore filtering film/Semiconductor gas sensors film lamination device is sequentially reduced from top to bottom；Preparation method includes: the micropore filtering film/Semiconductor gas sensors film lamination device for first preparing different pore size, is then sequentially arranged the micropore filtering film of different pore size/Semiconductor gas sensors film lamination device from top to bottom according to the descending rule in aperture；The gradient stack-up array of above-mentioned preparation method preparation can be used for the detection of gas multi concentration.The detection of each component concentration of known multicomponent gas can be achieved in the present invention, have many advantages, such as to detect quick and precisely, it is applied widely.
Description
Technical field
The invention belongs to semiconductor transducer gas sensitive detection fields, more particularly, to a kind of gradient stack-up array, preparation
Method and gas multi concentration detection method.
Background technique
Gas multi detection is a kind of inspection of classification and respective concentration that each component gas is distinguished by certain way
Survey mode is a kind of for monitoring ambient air quality, the highly important detection technique of chemical industry discharge.Its detect type and
Mode very abundant, traditional mode generally use the technologies such as gas-chromatography, ion mobility spectrometry, continuous spectrum absorption, are based on gas
Diffusion properties, ionization attribute or the spectral absorption attribute of body in spectrum of corresponding diffusion time, Ion transfer spatial spectrum, absorb light
Signal is unfolded in spectrum, to distinguish the corresponding type of each component gas and concentration in multicomponent.But using gas spectroscopy signal come
Various gases are separated there is certain limitation, especially because the heavy of detection device can not accomplish micromation, low-power consumption, more
Because its high cost limits its extensive use.
Semiconductor gas sensor, is that structure is most simple, the sensor that is most easily miniaturized, but its detection to all kinds of gases
It can not accomplish the highly selective of " one-to-one ".For realize multicomponent gas detection, at present more it is possible that be based on semiconductor
Gas Sensor Array adds mode identification technology, temperature modulation technology, carries out gas concentration amendment, few to component (can be no more than 4
Kind) atmosphere carry out gas component detection.And the bottleneck that this method encounters at present is, when (number of components is more than 4 to detected atmosphere
Kind) it is complex when, gas response test and pattern-recognition training workload and index of difficulty in multiple increase, influence to examine
The factor of survey process is more, and it is also relatively difficult to establish corresponding mathematical model.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of gradient stack-up arrays, preparation side
Method and gas multi concentration detection method, by design at least two by the micro porous filtration of bore diameter gradient stack-up array arrangement
Film/Semiconductor gas sensors film lamination device is based on the various sizes of gas molecule of molecule sieve effect gradient separations to realize, in turn
The detection for realizing the multicomponent gas concentration of complicated atmosphere, have many advantages, such as to detect quick and precisely, it is applied widely.
To achieve the above object, according to a first aspect of the present invention it is proposed a kind of gradient stack-up array, more for gas
The detection of concentration of component, the gradient stack-up array include at least two micropore filtering films/semiconductor being sequentially arranged from top to bottom
Air-sensitive film laminated device, and the aperture of the micropore filtering film on each micropore filtering film/Semiconductor gas sensors film lamination device from up to
Under be sequentially reduced.
As it is further preferred that the micropore filtering film/Semiconductor gas sensors film lamination device includes substrate, is deposited on base
The metal electrode of on piece, the Semiconductor gas sensors film being covered on metal electrode, the micro porous filtration being arranged on Semiconductor gas sensors film
Film and the packing material film being filled between the micropore crystal grain gap of micropore filtering film.
Second aspect according to the invention proposes a kind of preparation method of gradient stack-up array comprising following steps:
S1 prepares micropore filtering film/Semiconductor gas sensors film lamination device of different pore size:
S11 prepares Semiconductor gas sensors film, porous material dispersion is obtained dispersion liquid in the liquid phase, then by dispersion liquid
It is uniformly layered on Semiconductor gas sensors film, drying obtains micropore filtering film；
S12 is laid with packing material on micropore filtering film, and the melting temperature of the packing material is lower than porous material, then plus
Hot packing material makes its melting, and each of micropore filtering film is arrived in the infiltration under the driving effect of own face energy of the packing material of melting
In the gap of micropore crystal grain；
After packing material cooling and solidifying of the S13 wait melting, the packing material of micro porous filtration film surface is removed to expose micropore
The surface of crystal grain prepares micropore filtering film/Semiconductor gas sensors film lamination device with this；
S14 repeats step S11-S13 to prepare micropore filtering film/Semiconductor gas sensors film of at least two different pore sizes
Laminated device；
S2 by the micropore filtering film of the different pore size prepared/Semiconductor gas sensors film lamination device according to aperture by greatly to
Small rule is sequentially arranged from top to bottom, obtains gradient stack-up array with this.
As it is further preferred that the porous material is preferably zeolite structured micropore crystal grain powder, the packing material
Preferably low melting point silicate amorphous glass powder.
As it is further preferred that the thickness of the Semiconductor gas sensors film of preparation is preferably 1 μm -10 μm in step S11, system
The thickness of standby micropore filtering film is preferably 1 μm -2 μm, and drying temperature is preferably 120 DEG C -150 DEG C；In step S12, micropore mistake
The thickness for the packing material being laid on filter membrane is preferably 1 μm -2 μm, and the heating temperature of packing material is preferably 600 DEG C -800 DEG C.
As it is further preferred that the liquid phase is preferably deionized water in step S11, it is preferred to use micro- spray or droplet
Mode being laid on homogeneous dispersion on Semiconductor gas sensors film, the speed of laying is preferably the milli of 0.01 ml/min -0.05
Liter/min；In step S12, it is preferred to use packing material is laid on micropore filtering film by the mode of micro- spray or droplet, laying
Speed is preferably -0.05 ml/min of 0.01 ml/min.
As it is further preferred that in step S13, it is preferred to use wet-etching technology etches away micropore crystal grain film surface
Packing material.
The third aspect according to the invention proposes a kind of detection method of gas multi concentration, uses described
Gradient stack-up array is realized comprising following steps:
S1 is by test gas known to a certain concentration of component from top to bottom successively by each micropore in gradient stack-up array
Filter membrane/Semiconductor gas sensors film lamination device, to obtain the relational expression between the concentration of the component and response；
S2 obtains the relational expression between the corresponding response of other components concentration using the same method of step S1；
S3 is by contained component under test gas identical with test gas from top to bottom successively by gradient stack-up array
Each micropore filtering film/Semiconductor gas sensors film lamination device, and calculate and obtain the corresponding response of each component；
The corresponding response of each component is brought in the concentration of the component and the relational expression of response into the concentration for acquiring the component by S4,
With the detection of this each component concentration for completing gas.
As it is further preferred that step S1 specifically includes following sub-step:
S11 is by test gas known to a certain concentration of component from top to bottom successively by each micropore in gradient stack-up array
Filter membrane/Semiconductor gas sensors film lamination device, obtains the corresponding response of the concentration of component, that is, obtains one group of concentration and number of responses
According to；
S12 changes concentration of component, and repeats step S11, to obtain multiple groups concentration and response data；
S13 obtains the relational expression between the concentration and response of component according to multiple groups concentration and response data fitting.
As it is further preferred that the response obtains in the following way:
Firstly, acquiring each micropore filtering film/Semiconductor gas sensors film lamination device response Si, wherein i is micro- i-th
Hole filter membrane/Semiconductor gas sensors film lamination device, i=1,2 ..., n, n >=2；
Then, the corresponding gas group of each layer is determined according to the molecular size of component and the corresponding pore size of micropore filtering film
Point, and calculating the corresponding response of each component, wherein the corresponding response of smallest molecule size component is the bottom micropore mistake measured
Filter membrane/Semiconductor gas sensors film lamination device response Sn, the response of other components is using formula Si-Si+1It calculates.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
1. the gradient stack-up array of researching and designing of the present invention includes at least two micro porous filtrations being sequentially arranged from top to bottom
Film/Semiconductor gas sensors film lamination device, and the hole of the micropore filtering film on each micropore filtering film/Semiconductor gas sensors film lamination device
Diameter changes in gradient, can be based on the various sizes of gas of molecule sieve effect gradient separations point by the gradient stack-up array with this
Son is realized the detection of gas with multiple constituents of complicated atmosphere, is avoided to carry out spectroscopy expansion to gas response signal on molecular dimension
Simple profiling type identification is difficult to select suitable mathematical model and the very big problem of training burden.
2. the present invention detects multicomponent gas using based on micropore filtering film/Semiconductor gas sensors film gradient stack-up array
Concentration can accomplish micromation, low-power consumption, this functional application by gas detection is brought newly on various movable equipments
Possibility.
3. the present invention is laid with melting temperature in micropore grain films again by preparing micropore grain films first with porous material
Lower than the packing material of porous material, its melting is made by heating packing material with this, so that the packing material of melting is effective
It is filled in the intercrystalline gap of each micropore of micropore grain films, to prepare the continuous micropore filtering film of micropore filtering film
With Semiconductor gas sensors film lamination device, and then guarantee gradient stack-up array performance.
4. the present invention determines that optimal porous material and packing material, preferably porous material are after study with test
Zeolite structured micropore crystal grain powder, being preferably filled with material is low melting point silicate amorphous glass powder, and the two is having the same basic
Structural unit (i.e. TO4Tetrahedron), there is splendid wellability between the two, ensure that zeolite micropore crystal grain and silicic acid after infiltration
It is very close to each other and then obtain the film of continuous uniform between salt amorphous glass.
5. the present invention is fallen the glass etching of top layer using wet etching technique (belonging to MEMS technology) thus by micropore
The surface of crystal grain is exposed, and by MEMS technology mass production, cost is relatively low, therefore based on micropore filtering film/partly lead
The corresponding cost of gas multi detection method of the gradient stack-up array of body air-sensitive film is also relatively low, before having wide application
Scape.
Detailed description of the invention
Fig. 1 is micropore filtering film provided in an embodiment of the present invention/Semiconductor gas sensors membrane module structural schematic diagram；
Fig. 2 is the partial enlarged view of Fig. 1；
Fig. 3 is the schematic diagram of each layer gas response of acquisition provided in an embodiment of the present invention；
Fig. 4 is the cumulative response map by gas molecule auger Spread plane dimension.
In all the appended drawings, identical appended drawing reference is used to denote the same element or structure, in which:
201- substrate, 202- metal electrode, 203- Semiconductor gas sensors film, 204- micropore filtering film, 205- packing material film.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The embodiment of the invention provides a kind of gradient stack-up array for gas multi Concentration Testing, the gradient laminations
Array includes at least two micropore filtering films/Semiconductor gas sensors film lamination device being sequentially arranged from top to bottom, and at least two
The aperture of micropore filtering film on micropore filtering film/Semiconductor gas sensors film lamination device is sequentially reduced (i.e. in gradient from top to bottom
Variation), the spacing between each micropore filtering film/Semiconductor gas sensors film lamination device can be selected as needed without limitation.
As illustrated in fig. 1 and 2, micropore filtering film/Semiconductor gas sensors film lamination device includes substrate 201, is deposited on substrate 201
On metal electrode 202, the Semiconductor gas sensors film 203, the lamination that are covered on metal electrode 202 be arranged in Semiconductor gas sensors film
Micropore filtering film 204 on 203 and the packing material film 205 being filled between the micropore crystal grain gap of micropore filtering film 204.
The present invention also provides the preparation methods of gradient stack-up array comprising following steps:
S1 is firstly, first prepare micropore filtering film/Semiconductor gas sensors film lamination device of different pore size, specifically using such as
Lower step preparation:
S11 prepares Semiconductor gas sensors film, wherein the Semiconductor gas sensors film prepared has the broad spectrum response to gas special
Point, i.e. Semiconductor gas sensors film have response to gas to be screened, it is therefore an objective to when gas molecule is by can be with after micropore filtering film
Air-sensitive film generates reaction, it was demonstrated that it exists；
Specifically, semiconductor is prepared in deposit metal electrodes 202 on substrate 201 (such as ceramic substrate, silicon chip)
Device is generally prepared by the way of photoetching+sputtering, wherein photoetching (laser ablation) is in order to which forming meets function on substrate
The geometry of energy demand, sputtering (magnetron sputtering) is that metal electrode is deposited on substrate to etch geometrically；It is preferred that
, the optimum thickness of metal electrode 202 is 100nm, metal electrode layer in homogeneous thickness is obtained at this time, so that the electricity of metal electrode
It is just suitable to hinder, and when thinner, the power consumption of device becomes larger；Semiconductor devices deposit metal electrodes one side coating air-sensitive slurry at
Film obtains required Semiconductor gas sensors film 203, wherein air-sensitive slurry is metal oxide or passes through noble metal decorated metal oxygen
Compound semiconductor material, common are SnO2、WO3、In2O3Equal metal oxides system composition, specific manufacturing method is will to lead to
Metal-oxide semiconductor (MOS) powder made from chemical synthesis is crossed to mix by a certain percentage with terpinol organic solution as main component
It closes, then mixed liquor is placed in ball grinder progress ball milling and just obtains air-sensitive slurry, be that this will not be repeated here for the prior art；It again will be porous
Material dispersion obtains dispersion liquid in the liquid phase, then being layered on homogeneous dispersion on Semiconductor gas sensors film, and drying obtains micropore
Filter membrane 204.Specifically, determining each layer molecular screen material (i.e. porous material) according to the size of gas molecule each in mixed gas
Aperture, corresponding molecular screen material is then selected according to the aperture of molecular screen material, the micropore mistake in required aperture is prepared with this
Filter membrane.
S12 is laid with packing material on micropore filtering film, and the melting temperature of the packing material is lower than porous material, then plus
Hot packing material makes its melting, and each of micropore filtering film is arrived in the infiltration under the driving effect of own face energy of the packing material of melting
In the gap of micropore crystal grain；
After packing material cooling and solidifying of the S13 wait melting, the packing material of micro porous filtration film surface is removed, to expose micropore
The surface of crystal grain prepares the micropore filtering film/Semiconductor gas sensors film lamination device in required aperture with this；
S14 repeats step S11-S13 to prepare micropore filtering film/Semiconductor gas sensors film of at least two different pore sizes
Laminated device, aperture needed for each layer are determined according to the type of gas in mixed gas.
Specifically, preparing continuous micropore filtering film it is crucial that selecting suitable porous material and packing material, energy
It is enough meet the present invention claims porous material and packing material it is more, the present invention determines preferably porous material with test after study
Material is zeolite structured micropore crystal grain powder, such as X-type zeolite and y-type zeolite, and X-type zeolite and y-type zeolite are artificial synthesized boilings
Stone molecular sieve can directly be bought in the market, in X-type or y-type zeolite structure have β cage, octahedral zeolite cage and hexagonal prism cage, six
Square column cage i.e. hexagonal prism, the volume very little of hexagonal prisms, general molecule cannot be introduced into the micropore (nanoscale of hexagonal prisms
) not inner, only gas molecule can pass through, therefore can play the role of gas screening.Preferred packing material is low melting point silicate
Amorphous glass powder, average grain diameter is at 10 microns hereinafter, such as ZnO-B2O3-SiO2It is zinc borosilicate glass powder with low melting point, R2O-
Bi2O3-B2O3-SiO2It is beryllium zinc borosilicate glass powder with low melting point.Firstly, zeolite structured its thermal stability of micropore crystal grain good (one
As resistance to 800 DEG C or more), low melting point silicate amorphous glass by adjust component (such as content of B), it is available lower soft
Change point (600 DEG C or less), the temperature condition in molten state amorphous glass filling zeolite micropore crystal grain gap can be met；Secondly, eutectic
Size after point silicate amorphous glass powder melting is much larger than the size of micropore in zeolite structured micropore crystal grain, therefore packing material
It will not enter in the micropore of zeolite structured micropore grain itself after the melting of low melting point silicate amorphous glass powder, can only be filled in each
In gap between zeolite structured micropore crystal grain；Again, although there are hole in low melting point silicate amorphous glass powder particle,
Due to amorphous glass powder its structure be it is unordered, this hole configurations, which adds up, to be interrupted, and can not be formed continuous
Hole channel, and zeolite micropore crystal grain has well-regulated and single size hole, therefore finally obtained is that aperture is single
Micropore filtering film, without compound glass micropore and zeolite micropore the different filter membrane in aperture the case where；Finally, zeolite
Micropore crystal grain and low melting point silicate amorphous glass basic structural unit, that is, TO having the same4Tetrahedron, by the similar original that mixes
Reason ensure that after infiltrating between zeolite micropore crystal grain and silicate amorphous glass it is found that between the two with splendid wellability
The film very close to each other for obtaining continuous uniform.
After S2 prepares the micropore filtering film/Semiconductor gas sensors film lamination device in multiple and different apertures, then by each micropore
Filter membrane/Semiconductor gas sensors film lamination device is sequentially arranged from top to bottom according to the descending rule in aperture, can be obtained with this
Obtain required gradient stack-up array.
Specifically, the thickness of the Semiconductor gas sensors film of preparation is preferably 1 μm~10 μm, biggish specific surface is made it have
Product has quick response to gas.The thickness of the micropore filtering film of preparation is preferably 1 μm~2 μm, makees it to the screening of gas
With obvious, response rapidly, best performance.In order to enable the process of etching packing material is simple and easy, tile on micropore filtering film
Packing material thickness it is unsuitable blocked up, preferably 1 μm~2 μm.
Further, the drying temperature in step S11 is preferably 120 DEG C~150 DEG C, by obtaining micropore mistake after dry 3h
Filter membrane.The heating temperature of packing material is 600 DEG C to 800 DEG C in step S12, with this packing material amorphous glass powder is become
Molten state, and zeolitic material remains solid-state, since packing material is molten state, porous material is solid-state, the glass of molten state
Powder can infiltrate the gap between filling solid microporous crystal grain.
Further, liquid phase is preferably deionized water, so that porous material will not be polluted by other impurities, is preferably adopted
With micro- spray or mode being laid on homogeneous dispersion on Semiconductor gas sensors film of droplet, the speed of laying is 0.01ml/min-
0.05ml/min (ml/min), dispersion liquid can uniformly and fully be paved with Semiconductor gas sensors film under this speed.It is preferred that using
Packing material is laid on micropore filtering film by the mode of micro- spray or droplet, and the speed of laying is preferably 0.01ml/min-
0.05ml/min, packing material can be evenly laid out in micro porous filtration film surface under this speed.
More specifically, it is preferred to use wet etching technique etches away the packing material of micropore crystal grain film surface, and wet process is carved
Erosion technology is routine techniques, and this will not be repeated here, wherein etching agent selects HF+NH4F (0.5mol/L:0.5mol/L), etching temperature
50 DEG C, 1.5 μm/min of etching speed of degree, can be complete by the packing material in micro porous filtration film surface under the etch process parameters
It etches away, and does not damage filter membrane surface.
The gradient stack-up array realization gas multi Concentration Testing how to be designed using the present invention is carried out below detailed
Explanation.
Gradient stack-up array needed for S1 preparation:
Micropore filtering film/Semiconductor gas sensors film lamination is determined according to the number of components in the mixed gas to be measured of main constituent
The quantity of device, number of components contained in mixed gas are required micropore filtering film/Semiconductor gas sensors film lamination device
Quantity, then determined according to the molecular size of gas component in the mixed gas to be measured of main constituent each in gradient stack-up array
Micropore filtering film/Semiconductor gas sensors film lamination device aperture, aperture ratio wait for by component molecular size it is bigger, so
Component can effectively be sieved, prepare corresponding gradient stack-up array, such as known gaseous mixture to be measured further according to determining aperture
There are benzene (molecular size 5.85nm) and n-butanol (molecular size 5.6nm) in atmosphere, it is determined that two micropore filtering film/semiconductor gas
The aperture of quick film lamination device is respectively 6.45nm and 5.75nm；According still further to the descending mode in aperture by each micro porous filtration
Film/Semiconductor gas sensors film lamination device is sequentially arranged from top to bottom namely each micropore filtering film/Semiconductor gas sensors film lamination device
It sets gradually from top to bottom, and the aperture of the micropore filtering film on each micropore filtering film/Semiconductor gas sensors film lamination device is from upper
It is sequentially reduced under, wherein the aperture of the micropore filtering film of top layer/Semiconductor gas sensors film lamination device micropore filtering film is most
Greatly, the aperture of the micropore filtering film of the bottom/Semiconductor gas sensors film lamination device micropore filtering film is minimum；
S2 carries out test training to gradient stack-up array:
S21 successively passes through test identical with component contained by under test gas gas known to a certain concentration of component from top to bottom
Each micropore filtering film/Semiconductor gas sensors film lamination device in gradient stack-up array is crossed, to obtain component known to the concentration
Concentration and micropore filtering film/Semiconductor gas sensors film lamination device are to the relational expression between the response of the component；I.e. first with a concentration
Carry out test and obtain corresponding response, then carry out test with a concentration and obtain corresponding response, and so on available multiple groups
Then data are fitted the relational expression for calculating and obtaining between the corresponding response of the concentration of component according to multi-group data；
S22 is using the relational expression between the corresponding response of the concentration that the same method of step S21 can get other components；
S3 measures under test gas:
S31 is by contained component under test gas identical with test gas from top to bottom successively by gradient stack-up array
Each micropore filtering film/Semiconductor gas sensors film lamination device, and calculate and obtain the corresponding response of each component；
The corresponding response of each component is brought into the concentration of the component and the relational expression of response and acquires the dense of the component by S32
Degree, with the detection of this each component concentration for completing gas.
Specifically, the response respectively formed specifically obtains in the following way:
Firstly, acquiring each micropore filtering film/Semiconductor gas sensors film lamination device gas response Si(it is in certain size
The total cumulative response of each gas, i are i-th of micropore filtering film/Semiconductor gas sensors film lamination device, and i=1,2 ..., n, n is micro-
Hole filter membrane/Semiconductor gas sensors film lamination device total number, n >=2), gas response is that gas molecule passes through micro porous filtration
The response generated after film with Semiconductor gas sensors film, it is successively available by gradient since the bore diameter gradient of each micropore filtering film changes
The gas of each layer responds Si, the response of obtained signal is sequentially denoted as S1、S2、S3、……、Sn, wherein S1It is micro- for top layer
The response of hole filter membrane/Semiconductor gas sensors film lamination device, SnFor bottom micropore filtering film/Semiconductor gas sensors film lamination device
Response, as shown in figure 4, in figure, abscissa i, ordinate Si；
Then, the corresponding gas group of each layer is determined according to the molecular size of component and the corresponding pore size of micropore filtering film
Point, and calculating the corresponding response of each component, wherein the corresponding response of smallest molecule size component is the bottom micropore mistake measured
Filter membrane/Semiconductor gas sensors film lamination device response Sn, the response of other components is using formula Si-Si+1Calculate, i from 1 value to
N-1.
For example, as it is known that thering is benzene (molecular size 5.85nm), n-butanol (molecular size 5.6nm), ethyl alcohol (to divide in mixed gas
Sub- size 4.53nm), formaldehyde (molecular size 3.81nm) and hydrogen (molecular size 2.89nm), determine five micropore filtering films/
The aperture of Semiconductor gas sensors film lamination device is respectively 6.45nm, 5.75nm, 4.6nm, 4.11nm and 3.16nm, five micropore mistakes
Filter membrane/Semiconductor gas sensors film lamination device is from top to bottom successively arranged from big to small by aperture, and mixed gas is from top to bottom successively
By each micropore filtering film/Semiconductor gas sensors film lamination device, each micropore filtering film/Semiconductor gas sensors film lamination device is measured
Response is respectively S1~S5, then the response of the smallest hydrogen of molecular dimension is S5, the response of other gas components are as follows: the sound of formaldehyde
It should be S4-S5, the response of ethyl alcohol is S3-S4, the response of n-butanol is S2-S3, the response of benzene is S1-S2。
Specifically, response SiIt is a reduced value, generally refers to be passed through the initial of the resistance value of device and device after gas
The ratio of resistance value, such as i-th layer of micropore filtering film/Semiconductor gas sensors film lamination device, measured in the device first
Semiconductor gas sensors film initial resistivity value Ri, then gas molecule is by generating sound with Semiconductor gas sensors film after micropore filtering film
It answers, and measures the resistance value R of Semiconductor gas sensors film at this timeiThen ' calculates Si=Ri'/Ri。
In practical operation, gradient stack-up array can be put into air-sensitive test module, module is then connected into computer, with
The data that micropore filtering film in each micropore filtering film/Semiconductor gas sensors film lamination device measures are directly transferred to computer and are shown
Show on computers, specific value and corresponding gas response spectra including gas response are all displayed on computer, convenient for checking.
The following are specific embodiments:
Embodiment 1
Firstly, being determined according to the molecular size of gas component in the mixed gas of main constituent each micro- in gradient stack-up array
Hole filter membrane/Semiconductor gas sensors film lamination device aperture, each micropore filtering film/Semiconductor gas sensors film lamination device aperture
It is more bigger than the gas molecule size that it can be sieved, for example, have in known mixed atmosphere to be measured benzene (molecular size 5.85nm) and
N-butanol (molecular size 5.6nm), it is determined that two micropore filtering films/Semiconductor gas sensors film lamination device aperture is respectively
Then 6.45nm and 5.75nm prepares corresponding gradient stack-up array according to determining aperture:
S11 prepares Semiconductor gas sensors film: depositing platinum electrode on a silicon substrate by the way of photoetching+sputtering and is prepared into
To semiconductor devices, the one side coating stannic oxide air-sensitive slurry of platinum electrode is deposited on the semiconductor device using silk-screen printing
Material film forming obtains the Semiconductor gas sensors film with a thickness of 7 μm；By porous material (specifically select SSY (molecular sieve structure type code),
SSY is a kind of Y zeolite of business, handles dealumination complement silicon by ammonium fluosilicate, corresponding aperture is 5.75nm) it is dispersed in deionization
Dispersion liquid is obtained in aqueous phase, is sprayed on Semiconductor gas sensors film with 0.02ml/min speed by dispersion liquid is micro-, at a temperature of 130 DEG C
Drying obtains the micropore grain films with a thickness of 1.5 μm；
S12 is with the 0.02ml/min speed R that micro- spray average grain diameter is 8 microns in micropore grain films2O-Bi2O3-B2O3-
SiO2Beryllium borosilicate glass powder with low melting point packing material, with a thickness of 1.5 μm, packing material, which is heated to 700 DEG C, makes its melting,
The packing material of melting is under the driving effect of own face energy in the intercrystalline gap of each micropore of the infiltration to micropore grain films；
After packing material cooling and solidifying of the S13 wait melting, using filling out for wet etching technique removal micropore crystal grain film surface
Material is filled, micropore filtering film and Semiconductor gas sensors film lamination device that micro porous filtration membrane aperture is 5.75nm are prepared；
With step S11-S13 same step selection MOR, (MOR is a kind of modenite to S14, and corresponding aperture is
6.45nm) micropore filtering film/Semiconductor gas sensors film lamination device that preparation micro porous filtration membrane aperture is 6.45nm；
The micropore filtering film and Semiconductor gas sensors film lamination device that the micro porous filtration membrane aperture prepared is 6.45nm by S15
Micropore filtering film/Semiconductor gas sensors film lamination device that part and micro porous filtration membrane aperture are 5.75nm is sequentially arranged from top to bottom,
Gradient stack-up array is obtained, i.e. the setting of gradient stack-up array is MOR → SSY.
Then, gas multi Concentration Testing is carried out:
S21 by benzene concentration (such as 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm,
90ppm, 100ppm, ppm (parts per million) concentration be with Solute mass account for the part per million of complete soln quality come
The concentration of expression, also referred to as parts per million concentration) known to benzene and n-butanol mixed gas (it is test gas) from top to bottom
Successively by two micropore filtering films/Semiconductor gas sensors film lamination device in gradient stack-up array, rung with obtaining benzene concentration with it
Relationship between answering, specifically, when mixed gas is by first device (having MOR micropore filtering film), due to the limit in aperture
System, only benzene and n-butanol can pass through, therefore obtained response S1The response of the mixed gas of benzene and n-butanol, when pass through second
When a device (SSY), due to the limitation in aperture, only n-butanol can pass through, and respond S at this time2For the response of n-butanol, then benzene
Response is S1-S2, obtain the corresponding response of each known concentration one by one with this, acquisition benzene can be fitted according to concentration and corresponding response
Concentration and its relationship between responding, specific relationship can be fitted by computer fitting software, be existed for the prior art
This is not repeated；
S22 fits the concentration and its relationship between responding of n-butanol using the same method of step S21, likewise, just
The test concentrations of butanol are also 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm,
100ppm；
Contained component mixed gas to be measured identical with test gas is successively passed through gradient stack-up array by S23 from top to bottom
In two micropore filtering films/Semiconductor gas sensors film lamination device, and the corresponding response of each component is calculated, specifically, n-butanol
Response is S2, the response of benzene is S1-S2；
The corresponding response of each component is brought in the concentration of corresponding component and the relational expression of response into the tool for acquiring the component by S24
Bulk concentration, i.e., by S2The concentration that n-butanol is acquired in the relational expression brought between n-butanol concentration and response, by S1-S2It is dense to bring benzene into
The concentration that benzene is acquired in relational expression between degree and response, the detection of each component concentration is completed with this.
Embodiment 2
Firstly, being determined according to the molecular size of gas component in the mixed gas of main constituent each micro- in gradient stack-up array
There is benzene (molecular size in hole filter membrane/Semiconductor gas sensors film lamination device aperture, such as known mixed atmosphere to be measured
5.85nm), n-butanol (molecular size 5.6nm) and ethyl alcohol (molecular size 4.53nm), it is determined that three micropore filtering films/partly lead
The aperture of body air-sensitive film laminated device is respectively 6.45nm, 5.75nm and 4.6nm, is then prepared according to determining aperture corresponding
Gradient stack-up array:
S11 is deposited golden metal electrode on a silicon substrate by the way of photoetching+sputtering and semiconductor devices is prepared, and is used
The depositional mode of silk-screen printing deposits the one side coating tungstic acid air-sensitive slurry film forming of platinum electrode on the semiconductor device
Obtain the Semiconductor gas sensors film with a thickness of 1 μm；Porous material (is specifically selected into MFI, typical material is ZSM-5, and one kind is containing organic
The New-type Zeolite Molecular Sieves of amine cation, corresponding aperture are 4.6nm) it is dispersed in deionized water liquid phase and obtains dispersion liquid, with
0.01ml/min speed is by dispersion liquid droplet on Semiconductor gas sensors film, and drying obtains micro- with a thickness of 1 μm at a temperature of 120 DEG C
Hole grain films；
S12 is with the 0.01ml/min speed ZnO-B that droplet average grain diameter is 5 microns in micropore grain films2O3-SiO2Zinc
Borosilicate glass powder with low melting point packing material, with a thickness of 1 μm, packing material, which is heated to 600 DEG C, makes its melting, and melting is filled out
It fills in the intercrystalline gap of each micropore that material is infiltrated under the driving effect of own face energy to micropore grain films；
After packing material cooling and solidifying of the S13 wait melting, using filling out for wet etching technique removal micropore crystal grain film surface
Material is filled, micropore filtering film and Semiconductor gas sensors film lamination device that micro porous filtration membrane aperture is 4.6nm are prepared；
With step S11-S13 same step selection SSY, (SSY is also a kind of Y zeolite of business to S14, is by fluosilicic acid
Ammonium handles dealumination complement silicon, and corresponding aperture is 5.75nm) prepare micropore filtering film/half that micro porous filtration membrane aperture is 5.75nm
Conductor air-sensitive film laminated device；Selecting MOR with step S11-S13 same step, (MOR is a kind of modenite, to deserved hole
Diameter is 6.45nm) prepare micropore filtering film/Semiconductor gas sensors film lamination device that micro porous filtration membrane aperture is 6.45nm；
The micropore filtering film and Semiconductor gas sensors film lamination device that the micro porous filtration membrane aperture prepared is 6.45nm by S15
The micropore filtering film that part, micro porous filtration membrane aperture are 5.75nm/Semiconductor gas sensors film lamination device, micro porous filtration membrane aperture are
The micropore filtering film of 4.6nm/Semiconductor gas sensors film lamination device is sequentially arranged from top to bottom, obtains gradient stack-up array, i.e., terraced
Degree stack-up array is set as MOR → SSY → MFI.
Then, gas multi Concentration Testing is carried out:
S21 by benzene concentration (such as 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm,
90ppm, 100ppm) known to benzene, n-butanol and ethyl alcohol mixed gas (its for test gas) from top to bottom successively by ladder
Three micropore filtering films/Semiconductor gas sensors film lamination device in stack-up array is spent, to obtain benzene concentration and its pass between responding
System, specifically, when mixed gas is by first device (with MOR micropore filtering film), due to the limitation in aperture, benzene, just
Butanol and ethyl alcohol can pass through, therefore obtained response S1The response of benzene, n-butanol and ethyl alcohol mixed gas, when pass through second device
When part (SSY), due to the limitation in aperture, only n-butanol and ethyl alcohol can pass through, and respond S at this time2It is mixed for n-butanol and ethyl alcohol
The response of gas；When passing through third device when (MFI), only ethyl alcohol can pass through, and mixed gas is only left ethyl alcohol, at this time
Respond S3For the response of ethyl alcohol, the response of n-butanol is S2-S3, the response of benzene is S1-S2；Each concentration is tested once, with this
One by one obtain benzene each concentration (i.e. 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm,
100ppm) corresponding response can be fitted the concentration and its relationship between responding for obtaining benzene according to concentration and corresponding response；
S22 fits the concentration and its relationship between responding of n-butanol, ethyl alcohol using the same method of step S21, equally
, the test concentrations of n-butanol and ethyl alcohol are also 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm,
90ppm, 100ppm；
Contained component mixed gas to be measured identical with test gas is successively passed through gradient stack-up array by S23 from top to bottom
In three micropore filtering films/Semiconductor gas sensors film lamination device, and the corresponding response of each component is calculated, specifically, ethyl alcohol
To respond S3, the response of n-butanol is S2-S3, the response of benzene is S1-S2；
The corresponding response of each component is brought in the concentration of corresponding component and the relational expression of response into the tool for acquiring the component by S24
Bulk concentration, i.e., by S3The concentration that ethyl alcohol is acquired in the relational expression brought between concentration of alcohol and response, by S2-S3It is dense to bring n-butanol into
The concentration that n-butanol is acquired in relational expression between degree and response, by S1-S2Benzene is acquired in the relational expression brought between benzene concentration and response
Concentration, with the detection of this each layer each component concentration.
Embodiment 3
Firstly, being determined according to the molecular size of gas component in the mixed gas of main constituent each micro- in gradient stack-up array
There is benzene (molecular size in hole filter membrane/Semiconductor gas sensors film lamination device aperture, such as known mixed atmosphere to be measured
5.85nm), n-butanol (molecular size 5.6nm), ethyl alcohol (molecular size 4.53nm), formaldehyde (molecular size 3.81nm) and hydrogen
(molecular size 2.89nm), it is determined that five micropore filtering films/Semiconductor gas sensors film lamination device aperture be respectively 6.45nm,
Then 5.75nm, 4.6nm, 4.11nm and 3.16nm prepare corresponding gradient stack-up array according to determining aperture:
S11 is deposited platinum electrode on a ceramic substrate by the way of photoetching+sputtering and semiconductor devices is prepared, and is adopted
It is deposited with the one side coating indium sesquioxide air-sensitive slurry of golden metal electrode on the semiconductor device with the depositional mode of silk-screen printing
Material film forming obtains the Semiconductor gas sensors film with a thickness of 10 μm；By porous material (select APC, typical material is AIPO-C molecular sieve,
Belong to one of aluminium phosphate molecular sieve, pore size 3.16nm) it is dispersed in the liquid phase of deionized water and obtains dispersion liquid, with
0.05ml/min speed is sprayed on dispersion liquid is micro- on Semiconductor gas sensors film, and drying obtains micro- with a thickness of 2 μm at a temperature of 150 DEG C
Hole grain films；
S12 is with the 0.05ml/min speed R that droplet average grain diameter is 10 microns in micropore grain films2O-Bi2O3-B2O3-
SiO2Beryllium borosilicate glass powder with low melting point packing material, with a thickness of 2 μm, packing material, which is heated to 800 DEG C, makes its melting, melts
The packing material melted is under the driving effect of own face energy in the intercrystalline gap of each micropore of the infiltration to micropore grain films；
After packing material cooling and solidifying of the S13 wait melting, using filling out for wet etching technique removal micropore crystal grain film surface
Fill material, to expose the surface of micropore crystal grain, prepare micro porous filtration membrane aperture be 3.16nm micropore filtering film with partly lead
Body air-sensitive film laminated device；
With step S11-S13 same step selection ATN, (typical material is MAPO-39 molecular sieve to S14, belongs to magnesium phosphate
One kind of aluminum molecular screen, pore size 4.11nm) prepare micropore filtering film/half that micro porous filtration membrane aperture is 4.11nm
Conductor air-sensitive film laminated device；Selecting MFI with step S11-S13 same step, (typical material is ZSM-5, and one kind is containing organic
The New-type Zeolite Molecular Sieves of amine cation, corresponding aperture are 4.6nm) micro porous filtration membrane aperture is prepared as the micro- of 4.6nm
Hole filter membrane/Semiconductor gas sensors film lamination device；Selecting SSY with step S11-S13 same step, (SSY is also a kind of commodity
Y zeolite, be by ammonium fluosilicate handle dealumination complement silicon, corresponding aperture is 5.75nm) prepare micro porous filtration fenestra
Diameter is micropore filtering film/Semiconductor gas sensors film lamination device of 5.75nm；It is selected with step S11-S13 same step
MOR (MOR is a kind of modenite, is 6.45nm to deserved aperture) prepares the micropore that micro porous filtration membrane aperture is 6.45nm
Filter membrane/Semiconductor gas sensors film lamination device；
S15 is descending from upper by aperture by prepare five micropore filtering films/Semiconductor gas sensors film lamination device
Successively arrangement obtains gradient stack-up array under, i.e. the setting of gradient stack-up array is MOR → SSY → MFI → ATN → APC.
Then, gas multi Concentration Testing is carried out:
S21 by benzene concentration (such as 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm,
90ppm, 100ppm) known to benzene, n-butanol, ethyl alcohol, formaldehyde and hydrogen mixed gas (it is test gas) from top to bottom
Successively by five micropore filtering films/Semiconductor gas sensors film lamination device in gradient stack-up array, to obtain benzene concentration and its
Relationship between response, specifically, when mixed gas is by first device (having MOR micropore filtering film), benzene, n-butanol,
Ethyl alcohol, formaldehyde and hydrogen can pass through, therefore obtained response S1It is the mixed gas of benzene, n-butanol, ethyl alcohol, formaldehyde and hydrogen
Response；When mixed gas is by second device (having SSY micropore filtering film), due to the limitation in aperture, only n-butanol,
Ethyl alcohol, formaldehyde and hydrogen can pass through, therefore obtained response S2It is the response of the mixed gas of n-butanol, ethyl alcohol, formaldehyde and hydrogen；
When mixed gas is by third device (have MFI micropore filtering film), due to the limitation in aperture, only ethyl alcohol, formaldehyde with
Hydrogen can pass through, therefore obtained response S3It is the response of the mixed gas of ethyl alcohol, formaldehyde and hydrogen；When mixed gas passes through the 4th
When a device (having ATN micropore filtering film), due to the limitation in aperture, only formaldehyde and the hydrogen response that can pass through, therefore obtain
S4It is the response of the mixed gas of formaldehyde and hydrogen；When mixed gas is by the 5th device (having APC micropore filtering film),
The response S that can pass through due to the limitation in aperture, only hydrogen, therefore obtain5It is the response of hydrogen, i.e. the response of hydrogen is S5, formaldehyde
Response be S4-S5, the response of ethyl alcohol is S3-S4, the response of n-butanol is S2-S3, the response of benzene is S1-S2, each concentration surveys
Examination is primary, obtained one by one with this each concentration (i.e. 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm,
90ppm, 100ppm) corresponding response, concentration and its pass between responding for obtaining benzene can be fitted according to concentration and corresponding response
System；
S22 using the same method of step S21 fits the concentration of n-butanol, ethyl alcohol, formaldehyde and hydrogen and between it responds
Relationship, likewise, the test concentrations of n-butanol, ethyl alcohol and formaldehyde are also 10ppm, 20ppm, 30ppm, 40ppm, 50ppm,
60ppm, 70ppm, 80ppm, 90ppm, 100ppm, and the concentration of hydrogen is 500ppm-1000ppm, at interval of 10ppm test one
It is secondary；
Contained component mixed gas to be measured identical with test gas is successively passed through gradient stack-up array by S23 from top to bottom
In five micropore filtering films/Semiconductor gas sensors film lamination device, and the corresponding response of each component is calculated, specifically, hydrogen
Response is S5, the response of formaldehyde is S4-S5, the response of ethyl alcohol is S3-S4, the response of n-butanol is S2-S3, the response of benzene is S1-
S2；
The corresponding response of each component is brought in the concentration of corresponding component and the relational expression of response into the tool for acquiring the component by S24
Bulk concentration, i.e., by S5It brings into the relational expression between the concentration of hydrogen and response and acquires the concentration of hydrogen, by S4-S5Bring formaldehyde into
The concentration that formaldehyde is acquired in relational expression between concentration and response, by S3-S4It brings into the relational expression between the concentration of ethyl alcohol and response and asks
The concentration for obtaining ethyl alcohol, by S2-S3It brings into the relational expression between the concentration of n-butanol and response and acquires the concentration of n-butanol, by S1-S2
It brings into the relational expression between the concentration of benzene and response and acquires the concentration of benzene, the detection of each concentration of component is completed with this.
The present invention provides based on micropore filtering film/Semiconductor gas sensors film gradient stack-up array and detection of gas with multiple constituents
Method realizes and carries out spectroscopy expansion to gas response signal on molecular dimension, realizes the multicomponent gas inspection of complicated atmosphere
Survey the detection, it can be achieved that each component gas concentration of known multicomponent gas.Since this detection method is based on miniature semiconductor
Device, therefore can accomplish micromation, low-power consumption, for changing high cost, the wealthy family in current gas multi Concentration Testing field
The status of sill, field of gas detection, which is generalized to intelligent terminal, to have great significance.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of gradient stack-up array, the detection for gas multi concentration, which is characterized in that the gradient stack-up array includes
At least two micropore filtering films being sequentially arranged from top to bottom/Semiconductor gas sensors film lamination device, and each micropore filtering film/partly lead
The aperture of micropore filtering film on body air-sensitive film laminated device is sequentially reduced from top to bottom.
2. gradient stack-up array as described in claim 1, which is characterized in that the micropore filtering film/Semiconductor gas sensors film is folded
Layer device includes substrate (201), the metal electrode (202) being deposited on substrate (201), is covered on metal electrode (202)
Semiconductor gas sensors film (203), the micropore filtering film (204) being arranged on Semiconductor gas sensors film (203) and it is filled in micropore mistake
Packing material film (205) between the micropore crystal grain gap of filter membrane (204).
3. a kind of preparation method of gradient stack-up array, which comprises the steps of:
S1 prepares micropore filtering film/Semiconductor gas sensors film lamination device of different pore size:
S11 prepares Semiconductor gas sensors film, porous material dispersion is obtained dispersion liquid in the liquid phase, then by homogeneous dispersion
Be layered on Semiconductor gas sensors film, drying obtain micropore filtering film；
S12 is laid with packing material on micropore filtering film, and the melting temperature of the packing material is lower than porous material, and then heating is filled out
Filling material makes its melting, and each micropore of micropore filtering film is arrived in the infiltration under the driving effect of own face energy of the packing material of melting
In the gap of crystal grain；
After packing material cooling and solidifying of the S13 wait melting, the packing material of micro porous filtration film surface is removed to expose micropore crystal grain
Surface, micropore filtering film/Semiconductor gas sensors film lamination device is prepared with this；
S14 repeats step S11-S13 to prepare micropore filtering film/Semiconductor gas sensors film lamination of at least two different pore sizes
Device；
S2 is descending according to aperture by the micropore filtering film of the different pore size prepared/Semiconductor gas sensors film lamination device
Rule is sequentially arranged from top to bottom, obtains gradient stack-up array with this.
4. the preparation method of gradient stack-up array as claimed in claim 3, which is characterized in that the porous material preferably boils
Stone structure micropore crystal grain powder, the packing material are preferably low melting point silicate amorphous glass powder.
5. the preparation method of gradient stack-up array as claimed in claim 3, which is characterized in that in step S11, preparation is partly led
The thickness of body air-sensitive film is preferably 1 μm -10 μm, and the thickness of the micropore filtering film of preparation is preferably 1 μm -2 μm, and drying temperature is preferred
It is 120 DEG C -150 DEG C；In step S12, the thickness for the packing material being laid on micropore filtering film is preferably 1 μm -2 μm, fills material
The heating temperature of material is preferably 600 DEG C -800 DEG C.
6. such as the preparation method of the described in any item gradient stack-up arrays of claim 3-5, which is characterized in that in step S11, institute
Stating liquid phase is preferably deionized water, it is preferred to use homogeneous dispersion is laid on Semiconductor gas sensors film by the mode of micro- spray or droplet
On, the speed of laying is preferably -0.05 ml/min of 0.01 ml/min；In step S12, it is preferred to use micro- spray or droplet
Packing material is laid on micropore filtering film by mode, and the speed of laying is preferably -0.05 ml/min of 0.01 ml/min.
7. such as the preparation method of the described in any item gradient stack-up arrays of claim 3-6, which is characterized in that excellent in step S13
Choosing etches away the packing material of micropore crystal grain film surface using wet-etching technology.
8. a kind of detection method of gas multi concentration, which is characterized in that using such as the described in any item ladders of claim 1-2
It spends stack-up array to realize comprising following steps:
S1 is by test gas known to a certain concentration of component from top to bottom successively by each micro porous filtration in gradient stack-up array
Film/Semiconductor gas sensors film lamination device, to obtain the relational expression between the concentration of the component and response；
S2 obtains the relational expression between the corresponding response of other components concentration using the same method of step S1；
S3 is by contained component under test gas identical with test gas from top to bottom successively by each micro- in gradient stack-up array
Hole filter membrane/Semiconductor gas sensors film lamination device, and calculate and obtain the corresponding response of each component；
The corresponding response of each component is brought in the concentration of the component and the relational expression of response into the concentration for acquiring the component by S4, with this
Complete the Concentration Testing of gas each component.
9. the detection method of gas multi concentration as claimed in claim 8, which is characterized in that step S1 specifically includes as follows
Sub-step:
S11 is by test gas known to a certain concentration of component from top to bottom successively by each micro porous filtration in gradient stack-up array
Film/Semiconductor gas sensors film lamination device, obtains the corresponding response of the concentration of component, that is, obtains one group of concentration and response data；
S12 changes concentration of component, and repeats step S11, to obtain multiple groups concentration and response data；
S13 obtains the relational expression between the concentration and response of component according to multiple groups concentration and response data fitting.
10. the detection method of gas multi concentration as claimed in claim 8, which is characterized in that described in step S1 and S3
Response obtains in the following way:
Firstly, acquiring each micropore filtering film/Semiconductor gas sensors film lamination device response Si, wherein i is i-th of micro porous filtration
Film/Semiconductor gas sensors film lamination device, i=1,2 ..., n, n >=2；
Then, the corresponding gas component of each layer is determined according to the molecular size of component and the corresponding pore size of micropore filtering film,
And calculate the corresponding response of each component, wherein the corresponding response of smallest molecule size component is the bottom micro porous filtration measured
Film/Semiconductor gas sensors film lamination device response Sn, the response of other components is using formula Si-Si+1It calculates.
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