CN103353447A - Ionic liquid filling type porous silicon optical VOC sensor array and preparation method thereof - Google Patents
Ionic liquid filling type porous silicon optical VOC sensor array and preparation method thereof Download PDFInfo
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Abstract
The invention specifically relates to an ionic liquid filling type porous silicon optical VOC sensor array and a preparation method thereof, belonging to the field of manufacturing and detection technology for gas sensors. The sensor array is used for identification and detection of VOC. The array is composed of a plurality of gas-sensitive units with cross sensitivity response to VOC, each gas-sensitive unit is composed of an ionic liquid array filled in a nanometer porous silicon photonic crystal, and ionic liquid accounts for more than 80% of the porosity of a porous silicon layer. The optical VOC sensor array is used at normal temperature, so the operating temperature of the sensor is substantially reduced; the ionic liquid does not volatilize at normal temperature and is extremely stable; an optical signal of an array sensor can be obtained through CCD imaging, and accurate light intensity change data can be transmitted and obtained through an optical fiber and a micro fiber spectrometer; moreover, the signal response and the recovery speed ratio of the sensor array are obviously faster than those of other types of sensing materials, response time of the sensor array to VOC is 40 s, recovery time is no more than 1 min, and the sensor array has good anti-electromagnetic interference performance.
Description
Technical field
The invention belongs to gas sensor manufacturing and detection technique field, be specifically related to a kind of ionic liquid filled-type porous silicon optical sensing array and preparation method thereof, this sensor array can be used for identification and the detection of volatile organic gas (VOC).
Background technology
Volatile organic compounds (Volatile Organic Compounds is called for short VOC) is one of modal poisonous and harmful air pollutants.USDOE, EPA general administration and University of California once carried out environmental contaminants to the evaluation of life risk, found that VOC has tremendous influence to health.So the detection to VOC in the air has great importance for the life and health that ensures the people and safety.Both at home and abroad the research of VOC detection technique is more and more paid attention to.At present, usually use large-sized analytic instrument for the analyzing and testing of VOC, such as gas chromatograph or mass spectrometer, but the general expensive complexity of these instruments and inconvenient on-the site analysis.So study the study hotspot that portable and cheap gas sensor has become the gas sensor field.But the gas sensor ubiquity cross sensitivity of single sensing element, the problem of poor selectivity.High performance gas sensor array, and combine with mode identification technology and to form the deficiency that Electronic Nose Technology helps to solve existing gas sensor.As far back as nineteen eighty-two, British scholar Persuad and Dodd etc. utilize 3 SnO
2Gas sensor has carried out category analysis to volatile organic matters such as ether, ethanol, isojasmone, has started the beginning of Electronic Nose research.Along with the development of the new demand of gaseous detection applications and science and technology, developed the ripe electric nasus system of technology abroad, such as with the Neotronics System of Britain, the Alpha MOS system of France etc.
Gas sensor array is the core component of Electronic Nose Technology, and it is to be constituted by a plurality of different gas sensing units, perhaps makes by MEMS technology processing, has microminiaturization, portable, low-power consumption, the advantage such as integrated.The kind of gas sensing unit is a lot, can be divided into conductivity type according to its detection signal, surface acoustic wave type, mass type, galvanochemistry type, spectral type etc.Gas sensitive has inorganic, metal oxide, organic polymer and inorganic/organic composite material etc.Wherein, using maximum in the sensor array of commercialization Electronic Nose Technology is inorganic, metal oxide semiconductor-type sensor array and mass type QCM (Quartz Crystal Microbalance) sensor array.Inorganic, metal oxide semiconductor sensing array is with ZnO and SnO
2Be Typical Representative.Its gas sensing mechanism mainly is to utilize the grain boundary effect of metal oxide, has namely overcome the barrier potential between crystal interface after the adsorbed gas, and electric conductivity changes.The inorganic, metal oxide gas sensitive has highly sensitive, the advantages such as fast response time, but also have some deficiency, adjustability of structure high such as working temperature, material is poor, cause sensing unit abundant not, also has easily simultaneously the problem such as poison, sensing range is narrow.As far back as 1986, the Kowalski of Washington, DC university etc. studied the mass type QCM (Quartz Crystal Microbalance) sensor array based on polymkeric substance air-sensitive material first.In actual applications, the QCM (Quartz Crystal Microbalance) array-type sensor of mass type is simple to operate, highly sensitive, but its quality testing precision is subjected to quartz crystal stability, the precision of frequency measurement, the impact of the many factors such as oscillatory circuit interference.The preparation process of polymer array sensitive material is difficult to accurate control simultaneously, and the polymeric material of different batches is repeated relatively poor to the gas response.The advantages such as by contrast, optical gas sensor has simple in structure, and the interference performances such as anti-electromagnetism are strong, and response and resume speed are fast, still, the research of relevant optical gas sensor array is also fewer.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, proposed a kind of VOC optics Gas Sensor Array material with novel detection principle, and preparation method thereof and application process.It is fast that this optics Gas Sensor Array has detection speed, and preparation is simple, and the controllable property of material structure is good; cost is low, and long characteristics such as (good stabilities) of life-span are fit to large-scale production; combine with the pattern recognition analysis method, can be fast, accurately gas is identified.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
The present invention is a kind of ionic liquid filled-type porous silicon optics VOC sensor array, described array is made of a plurality of gas sensor units that VOC is had a cross sensitivity response, gas sensor unit is comprised of the ionic liquid array that is filled in the nanoporous silicon photonic crystal, and ionic liquid accounts for more than 80% of porous silicon layer porosity.
As a kind of improvement, the ionic liquid that gas sensor array of the present invention adopts be in glyoxaline ion liquid, pyridines ionic liquid, piperidines ionic liquid, pyrrolidines ionic liquid, morpholine class ionic liquid, the quaternary amines ionic liquid Huo quaternary phosphine class ionic liquid any one or multiple.
As a kind of improvement, gas sensor unit in the sensor array of the present invention to the detection principle of VOC is, when this gas sensitive is exposed to the air that contains VOC, but be filled in the ionic liquid fast Acquisition VOC in the duct, and generation volumetric expansion, form little drop at the nano-structure porous silicon photon crystal surface, and the density of drop or big or small relevant with the concentration of VOC, drop has scattering effect to light so that the reflection of Porous silicon photonic Crystal structures or interference light intensity descend.
As a kind of improvement, optical sensing array of the present invention is to be made of 2-100 different porous silicon gas sensor unit, the kind of the ionic liquid of filling in the different gas sensor units is different, same VOC gas had cross sensitivity, be that formed little drop is different to the scattering of light ability behind each gas sensor unit contact VOC, cause that the Strength Changes of porous silicon maximum reflection interference peaks (optical strength) is different.Above-mentioned display is carried out adopting the pattern recognition analysis method that the optical detection result of sensor array is processed behind the optical imagery, can distinguish differentiation to different VOC.And can carry out quantitatively specific VOC according to optical strength.
As a kind of improvement, this sensor array of the present invention has microminiaturized characteristics, and the diameter of each gas sensor unit is 2mm in the array, as a slice only as the silicon base of a coin-size on can integrated 16 gas sensor units.
The present invention or a kind of method for preparing ionic liquid filled-type porous silicon optics VOC sensor array as claimed in claim 1, concrete preparation process is as follows:
(1) covers equably last layer SU-8 photoresist at P type boron-doping monocrystalline silicon surface with photoresist spinner, microarray layout on the mask is transferred on the optical cement layer by the principle of uv-exposure imaging;
(2) with the P type boron-doping monocrystalline silicon of above-mentioned SU-8 optical cement array as anode, platinum electrode is negative electrode, be that 40% hydrofluorite is as electrolytic solution for the ratio of 1:3-6 adds absolute ethyl alcohol and weight percent concentration by volume, carry out electrochemical etching, SU-8 optical cement microarray plays positioning action in the etching process, setting the strength of current fluctuation range is 12.5-75mA, be 5-20 second each cycle of fluctuation, the recurrent fluctuation number of times is 35-120 time, silicon chip after the etching is clean with alcohol flushing, dries up with nitrogen again; Silicon chip after the above-mentioned etching 400-600 ℃ of lower thermal oxidation or ozone Oxidation Treatment 1-2 hour, is formed the integrated porous silica microsphere array with reflection and light strainability;
(3) drip on the surface of porous silicon and be coated with the pure ionic liquid of 0.5-0.8 μ l, in high vacuum environment, leave standstill 1-3h or drip the mixed solution that is coated with ionic liquid and organic solvent and under normal pressure, leave standstill 1-3h, ionic liquid fully is penetrated in the porous silicon duct, obtain gas sensor unit, the porous silicon gas sensor unit of a plurality of different ionic liquid preparations consists of VOC optical sensing array.
The present invention is a kind of method for preparing ionic liquid filled-type porous silicon optics VOC sensor array as claimed in claim 1, and concrete preparation process is as follows:
(1) with p-type boron-doping monocrystalline silicon as anode, platinum electrode is negative electrode, be that 40% hydrofluorite is as electrolytic solution for the ratio of 1:3～6 adds absolute ethyl alcohol and weight concentration by volume, carry out electrolytic etching, setting the strength of current fluctuation range is 35～100mA, and be 5-9 second each cycle of fluctuation, and the recurrent fluctuation number of times is 30～75 times, after finishing, etching with ethanol cleaning silicon chip repeatedly, dries up with nitrogen again; Silicon chip after the above-mentioned etching 400-600 ℃ of lower thermal oxidation or ozone Oxidation Treatment 1-2 hour, is formed the porous silicon that the surface has reflection and light strainability;
(2) choose the PDMS of suitable size and prepare the hole array of a plurality of diameter 2mm with card punch, surface with plasma (ultraviolet light) activation PDMS, then carry out permanent involution with porous silicon, PDMS plays the role of positioning, and a slice porous silicon is separated into the sensing site of a plurality of arrays;
(3) drip on the surface of porous silicon and be coated with the pure ionic liquid of 0.5-0.8 μ l, in high vacuum environment, leave standstill 1-3h or drip the mixed solution that is coated with ionic liquid and organic solvent and under normal pressure, leave standstill 1-3h, ionic liquid fully is penetrated in the porous silicon duct, obtain gas sensor unit, the porous silicon gas sensor unit of several different ionic liquid preparations consists of VOC optical sensing array.
Below in conjunction with Figure of description technical scheme of the present invention is described in further detail: VOC optical sensing array detection sensor-based system of the present invention as shown in Figure 1.Mainly by light source 1, CCD photoelectric conversion module 2 is equipped with the computing machine 3 of data acquisition and mode identificating software, coupled fiber 4, and air intake valve 5, the valve 6 of giving vent to anger, and place the Gas Sensor Array chip 7 in gas communication pond to consist of.Using the method that described sensing material and sensor-based system detect VOC is: the illumination that light source 1 sends is mapped on the Gas Sensor Array chip 7, produce reflected light signal, this reflected light signal enters CCD photoelectric conversion module 2 by coupled fiber 4, in CCD photoelectric conversion module 2, be converted to electric signal, then input (data acquisition software) in the computing machine 3, utilize mode identificating software (such as SPSS, Matlab etc.) that the array detection result who gathers is analyzed, realize identification and analysis to unknown gas.
Compare with existing VOC sensor array technology, the present invention has following beneficial effect:
(1) the nanoporous silicon photonic crystal is the uniform high light reflectivity material of pore size, and the half-peak width of its reflection wavelength can be controlled in the 10nm, thereby resolution is high.It is large to have simultaneously specific surface area, the characteristics such as the high easily modification of surfactivity.
(2) this VOC optical sensing array processing is easy fast, is easy to control.The kind of ionic liquid is a lot, designing with adjustability of zwitterion structure is strong, be convenient to optimize selectivity and sensitivity to the VOC response, realize the maximum optimal combination of sensor array, greatly strengthen cross response sensitivity and Division identification effect to VOC.
(3) optics VOC sensor array of the present invention is used at normal temperatures, greatly reduces senor operating temperature; And ionic liquid is non-volatile at normal temperatures, and is extremely stable.The optical signalling of array-type sensor both can obtain by the CCD imaging simultaneously, also can and obtain accurately light intensity delta data by optical fiber and micro fiber spectrometer transmission.In addition, the signal response of such sensing material and resume speed are obviously faster than the sensing material of other types, to response time of VOC be 40s, be not more than 1min release time, and have very strong anti-electromagnetic interference (EMI).
(4) use the gas sensor unit volume in the VOC optical sensing array of the present invention little, only 16 kinds of different gas sensitives of structure can be integrated in as the selective porous silicon of a coin-size on, be conducive to the microminiaturization of sensor, integrated.
(5) to have a volume little for this optical sensing array, and the characteristics such as cost is low, the life-span is long, portability are fit to large-scale production and Site Detection.After imaging technique and mode identification technology combine, can greatly improve the analysis ability of sensor array to gaseous species.
Description of drawings
The structural representation of Fig. 1 VOC gas optical detection apparatus; Among the figure: the 1st, light source, the 2nd, CCD photoelectric conversion module, the 3rd, computing machine, the 4th, coupled fiber, the 5th, air intake valve, the 6th, the valve of giving vent to anger, the 7th, Gas Sensor Array chip;
The schematic appearance of Fig. 2 ionic liquid filled-type selective porous silicon chip;
The synoptic diagram of the reflection interference spectrum figure of Fig. 3 ionic liquid filled-type Porous Silicon Sensors and the relation of ethanol gas concentration; Along with the increase (20%, 60%, 100% relative saturation vapour concentration) of alcohol gas volumetric concentration, in the scattering power enhancing of this formed little drop in sensing chip surface, reflection interference light intensity drop-out value increases;
Little drop scatter-type porous silicon optical sensing array of 11 kinds of variety classes ionic liquid preparations of Fig. 4 compares synoptic diagram to the optical strength response of seven kinds of common VOC gases (ethanol, ethyl acetate, methylene chloride, butanone, normal hexane, triclene, toluene); Sort according to the response size of each sensor in the sensor array to the optical strength of VOC, each gas all corresponding specific big or small ordering can be identified this gas.
The porous silicon sensor array of Fig. 5 different ionic liquid preparation is carried out the loose point of the major component synoptic diagram that the PCA principal component analysis (PCA) obtains to the optical strength response results of 7 kinds of VOC.This optical sensing array can be distinguished different gas well, first three major component that analyze to obtain with PCA represented 11 sensing elements optic response data representative quantity of information 91.18%.
Embodiment
Case study on implementation 1
The invention discloses a kind of ionic liquid filled-type porous silicon optics VOC sensor array, this array by a plurality of be volatile organic compounds to VOC() gas sensor unit with cross sensitivity response consists of, gas sensor unit is comprised of the ionic liquid array that is filled in the nanoporous silicon photonic crystal.The first sensing microarray preparation process is:
(1) covers equably last layer SU-8 photoresist at P type boron-doping monocrystalline silicon surface with photoresist spinner, microarray layout on the mask is transferred on the optical cement layer by the principle of uv-exposure imaging;
(2) with the P type boron-doping monocrystalline silicon of above-mentioned SU-8 optical cement array as anode, platinum electrode is negative electrode, by volume for the ratio of 1:3-6 add absolute ethyl alcohol and weight percent concentration be 40% hydrofluorite as electrolytic solution, carry out electrochemical etching.SU-8 optical cement microarray plays positioning action in the etching process.Setting the strength of current fluctuation range is 12.5-75mA, and be 5-20 second each cycle of fluctuation, and the recurrent fluctuation number of times is 35-120 time, and the silicon chip after the etching is clean with alcohol flushing, dries up with nitrogen again; Silicon chip after the above-mentioned etching 400-600 ℃ of lower thermal oxidation or ozone Oxidation Treatment 1-2 hour, is formed the integrated porous silica microsphere array with reflection and light strainability;
(3) drip on the surface of porous silicon and be coated with the pure ionic liquid of 0.5-0.8 μ L, in high vacuum environment, leave standstill 1-3h or drip the mixed solution that is coated with ionic liquid and organic solvent and under normal pressure, leave standstill 1-3h, ionic liquid fully is penetrated in the porous silicon duct, obtains gas sensor unit.The porous silicon gas sensor unit that several different ionic liquid are filled consists of VOC optical sensing array (as shown in Figure 2).The ionic liquid kind can be glyoxaline ion liquid, pyridines ionic liquid, piperidines type ionic liquid, pyrrolidine type ionic liquid, morpholine type ionic liquid, quaternary amines ionic liquid or quaternary phosphine class ionic liquid etc.The optical sensing array is to be made of 2-100 different gas sensor unit.Gas sensor units different in the array produce discrepant response sensitivity to same VOC.Be that each gas sensor unit is caught VOC, and generation volumetric expansion, form little drop at the nano-structure porous silicon photon crystal surface, drop has scattering effect to light so that the reflection of Porous silicon photonic Crystal structures or interference light intensity descend, and the concentration of the drop-out value of intensity of reflected light and VOC is proportionate (as shown in Figure 3).Utilize the device shown in the accompanying drawing 1 can obtain different gas produces feature at ionic liquid filled-type porous silicon optical sensing array response fingerprint image (as shown in Figure 4).Adopt the pattern recognition analysis method that the VOC testing result data of sensor array are processed, can distinguish to different VOC differentiation (as shown in Figure 5)
Case study on implementation 2
A kind of preparation method of ionic liquid filled-type porous silicon optics VOC sensor array, method may further comprise the steps:
(1) with p-type boron-doping monocrystalline silicon as anode, platinum electrode is negative electrode, be that 40% hydrofluorite is as electrolytic solution for the ratio of 1:3～6 adds absolute ethyl alcohol and weight concentration by volume, carry out electrolytic etching, setting the strength of current fluctuation range is 35～100mA, and be 5-9 second each cycle of fluctuation, and the recurrent fluctuation number of times is 30～75 times, after finishing, etching with ethanol cleaning silicon chip repeatedly, dries up with nitrogen again; Silicon chip after the above-mentioned etching 400-600 ℃ of lower thermal oxidation or ozone Oxidation Treatment 1-2 hour, is formed the porous silicon that the surface has reflection and light strainability;
(2) choose the PDMS of suitable size and prepare the hole array of a plurality of diameter 2mm with card punch.With the surface of plasma (ultraviolet light) activation PDMS, then carry out permanent involution with porous silicon.PDMS plays the role of positioning, and a slice porous silicon is separated into the sensing site of a plurality of arrays;
(3) drip on the surface of porous silicon and be coated with the pure ionic liquid of 0.5-0.8 μ L, in high vacuum environment, leave standstill 1-3h or drip the mixed solution that is coated with ionic liquid and organic solvent and under normal pressure, leave standstill 1-3h, ionic liquid fully is penetrated in the porous silicon duct, obtains gas sensor unit.The porous silicon gas sensor unit that several different ionic liquid are filled consists of VOC optical sensing array.The ionic liquid kind can be glyoxaline ion liquid, pyridines ionic liquid, piperidines type ionic liquid, pyrrolidine type ionic liquid, morpholine type ionic liquid, quaternary amines ionic liquid or quaternary phosphine class ionic liquid etc.
(4) system of application VOC optical sensing array detection VOC of the present invention mainly is comprised of light source, VOC Gas Sensor Array material, photoelectric conversion module and computer data acquiring software and mode identification technology.It is as follows to use the method that described optics Gas Sensor Array material detects VOC: the illumination that light source sends is mapped on the Gas Sensor Array material, produce reflected light signal, this reflected light signal enters photoelectric conversion module by optical fiber, in photoelectric conversion module, be converted to electric signal, then input (data acquisition software) in the computing machine.When the Surface Contact VOC of Gas Sensor Array material, form the drop particle that light is had scattering effect at porous silicon surface, adopt tungsten light source and CCD detecting device, can observe catoptrical intensity and descend.The concentration of VOC proportional relation within the specific limits in the degree of light intensity decreasing and the air, along with the increase of VOC concentration, intensity of reflected light descends.Obtain porous silicon optical sensing array that 11 kinds of different ionic liquid fill to the response data of VOC gas (ethanol, ethyl acetate, methylene chloride, butanone, normal hexane, triclene, toluene) in 7 with the device shown in the accompanying drawing 1, then carry out principal component analysis (PCA) with data processing software SPSS, VOC distinguished distinguish (as shown in Figure 4), and with this building database.When unknown gas is detected, the response signal of unknown gas and the signal in the database can be compared, identify judgement.Experimental results show that the optics VOC sensor array that this embodiment prepares has the function that VOC is judged in quick identification.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (7)
1. ionic liquid filled-type porous silicon optics VOC sensor array, it is characterized in that, described array is made of a plurality of gas sensor units that VOC is had a cross sensitivity response, described VOC refers to volatile organic compounds, described gas sensor unit is comprised of the ionic liquid array that is filled in the nanoporous silicon photonic crystal, and ionic liquid accounts for more than 80% of porous silicon layer porosity.
2. ionic liquid filled-type porous silicon optics VOC sensor array according to claim 1, it is characterized in that, the ionic liquid in the described sensor array be in glyoxaline ion liquid, pyridines ionic liquid, piperidines ionic liquid, pyrrolidines ionic liquid, morpholine class ionic liquid, the quaternary amines ionic liquid Huo quaternary phosphine class ionic liquid any one or multiple.
3. ionic liquid filled-type porous silicon optics VOC sensor array claimed in claim 1, it is characterized in that, gas sensor unit in the described sensor array to the detection principle of VOC is, when this gas sensitive is exposed to the air that contains VOC, but be filled in the ionic liquid fast Acquisition VOC in the duct, and generation volumetric expansion, form little drop at the nano-structure porous silicon photon crystal surface, and the density of drop or size are relevant with the concentration of VOC, and drop has scattering effect to light so that the reflection of Porous silicon photonic Crystal structures or interference light intensity descend.
4. ionic liquid filled-type porous silicon optics VOC sensor array according to claim 1, it is characterized in that, described optical sensing array is to be made of 2-100 different porous silicon gas sensor unit, the kind of the ionic liquid of filling in the different gas sensor units is different, same VOC gas had cross sensitivity, be that formed little drop is different to the scattering of light ability behind each gas sensor unit contact VOC, the Strength Changes that causes porous silicon maximum reflection interference peaks (optical strength) is different, adopt the pattern recognition analysis method that the VOC testing result data of sensor array are processed, can distinguish differentiation to different VOC.
5. ionic liquid filled-type porous silicon optics VOC sensor array according to claim 1, it is characterized in that, this sensor array has microminiaturized characteristics, the diameter of each gas sensor unit is 2mm in the array, as a slice only as the porous silicon-base of a coin-size at the bottom of on can integrated 16 gas sensor units.
6. a method for preparing ionic liquid filled-type porous silicon optics VOC sensor array as claimed in claim 1 is characterized in that, concrete preparation process is as follows:
(1) covers equably last layer SU-8 photoresist at P type boron-doping monocrystalline silicon surface with photoresist spinner, the microarray layout on the mask is transferred on the optical cement layer by the principle of uv-exposure imaging;
(2) above-mentioned SU-8 optical cement is developed, expose the monocrystalline silicon microarray.And with this monocrystalline silicon microarray as anode, platinum electrode is negative electrode, be that 40% hydrofluorite is as electrolytic solution for the ratio of 1:3-6 adds absolute ethyl alcohol and weight percent concentration by volume, carry out electrochemical etching, in the etching process, the position of being protected by the SU-8 optical cement is not etched, and the monocrystalline silicon of expose portion is etched, setting the strength of current fluctuation range is 12.5-75mA, be 5-20 second each cycle of fluctuation, the recurrent fluctuation number of times is 35-120 time, and the silicon after the etching is clean with alcohol flushing, dries up with nitrogen again; Silicon chip after the above-mentioned etching 400-600 ℃ of lower thermal oxidation or ozone Oxidation Treatment 1-2 hour, is formed the integrated porous silica microsphere array with light reflection and light strainability;
(3) drip on the surface of porous silicon and be coated with the pure ionic liquid of 0.5-0.8 μ l, in high vacuum environment, leave standstill 1-3h or drip the mixed solution that is coated with ionic liquid and organic solvent and under normal pressure, leave standstill 1-3h, ionic liquid fully is penetrated in the porous silicon duct, obtains a gas sensor unit.After different kinds of ions liquid is penetrated into respectively each porous silicon dot matrix in the array, can obtain consisting of VOC optical sensing array by a plurality of gas sensor units.
7. a method for preparing ionic liquid filled-type porous silicon optics VOC sensor array as claimed in claim 1 is characterized in that, concrete preparation process is as follows:
(1) with p-type boron-doping monocrystalline silicon as anode, platinum electrode is negative electrode, be that 40% hydrofluorite is as electrolytic solution for the ratio of 1:3～6 adds absolute ethyl alcohol and weight concentration by volume, carry out electrolytic etching, setting the strength of current fluctuation range is 35～100mA, and be 5-9 second each cycle of fluctuation, and the recurrent fluctuation number of times is 30～75 times, after finishing, etching with ethanol cleaning silicon chip repeatedly, dries up with nitrogen again; Silicon chip after the above-mentioned etching 400-600 ℃ of lower thermal oxidation or ozone Oxidation Treatment 1-2 hour, is formed the porous silicon that the surface has reflection and light strainability;
(2) choose dimethyl silicone polymer (PDMS) film of suitable size and prepare the hole array of a plurality of diameter 2mm with card punch, surface with plasma (ultraviolet light) activation PDMS, then carry out permanent involution with porous silicon, PDMS plays the role of positioning, and a slice porous silicon is separated into the sensing site of a plurality of arrays;
(3) drip on the surface of porous silicon and be coated with the pure ionic liquid of 0.5-0.8 μ l, in high vacuum environment, leave standstill 1-3h or drip the mixed solution that is coated with ionic liquid and organic solvent and under normal pressure, leave standstill 1-3h, ionic liquid fully is penetrated in the porous silicon duct, obtain gas sensor unit, the porous silicon gas sensor unit of several different ionic liquid preparations consists of VOC optical sensing array.
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