CN102313717A - Porous silicon micro-cavity biosensor and its preparation method - Google Patents

Porous silicon micro-cavity biosensor and its preparation method Download PDF

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CN102313717A
CN102313717A CN201110219656A CN201110219656A CN102313717A CN 102313717 A CN102313717 A CN 102313717A CN 201110219656 A CN201110219656 A CN 201110219656A CN 201110219656 A CN201110219656 A CN 201110219656A CN 102313717 A CN102313717 A CN 102313717A
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porous silicon
catoptron
bragg
microcavity
silicon microcavity
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CN102313717B (en
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荣国光
吴超
祝永新
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Shanghai Jiaotong University
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Abstract

The invention provides a porous silicon micro-cavity biosensor, a preparation method thereof and an optical detection system base on the sensor. The porous silicon micro-cavity biosensor comprises an upper Bragg reflector, a lower Bragg reflector and a defect layer clamped between the upper Bragg reflector and the lower Bragg reflector, The upper Bragg reflector and the lower Bragg reflector comprise five high porosity layers and low porosity layers which have cycle period and are alternatively arranged respectively, the thickness of the defect layer is two times of that of the high porosity layer. The invention has the advantages of high detection efficiency, simple composition, accurate detection and the like.

Description

Porous Silicon Microcavity biology sensor and preparation method thereof
Technical field
The present invention relates to the bio-sensing field, be specifically related to a kind of hyperchannel biology sensor, based on the optical detection system of this biology sensor and the preparation method of this biology sensor based on the porous silica microsphere cavity configuration.
Background technology
The biological substance detection technique plays crucial effect to the development of modern medical service technology, is the foundation of medical diagnosis on disease and treatment to the accurate mensuration of biomolecule type, content, also is vital link during medicine is developed.
At present, application Measurement for Biotechnique comparatively widely is to use certain molecule to carry out mark to biological sample, obtains to be labeled biomass density indirectly through measuring label content then.The shortcoming of this method is can receive bigger ground unrest to disturb, and reduced the reliability of signal, and biomolecule activity to be checked can be affected also.
Based on such reason, the biomolecule detection technology based on surface plasma body resonant vibration (SPR) of exempting from mark has also obtained certain applications.But the shortcoming of this mode is that SPR biomolecule detection appearance belongs to large-scale instrument, and preparation cost is high, and complicated operation needs the special reviewer of training.
Contrast above-mentioned traditional detection method, exempt from plurality of advantages such as the mark biology sensor has that selectivity is strong, analysis speed is fast, simple to operate, with low cost, sensitivity height.
Wherein, the biology sensor based on the porous silica microsphere cavity configuration has following advantage:
One, adopt optical means to detect, need not mark, can obtain conclusion rapidly through spectral signal analysis to microcavity;
Two, porous silicon has spongy structure, and specific surface area is big, and this increases the dynamic range that detects in specific detection; The more important thing is; Consider that SPR utilizes biomolecule and collapsing field effect, and biomolecule only in two dimensional surface with this collapsing field effect, Porous Silicon Microcavity is used the oscillating field and the biomolecule action of photonic crystal; And all can attaching biomolecules and oscillating field effect in the porosint three-dimensional surface, thereby have improved detection sensitivity;
Three, the porous silicon film refractive index can be regulated through changing its micromechanism;
Four, the porous silicon surface chemical property is easy to regulate, and realizes specific detection thereby can use various biomolecule to modify;
Five, porous silicon film is easy to the integrated sensor array that becomes, and obtains high throughput testing.
Biology sensor based on the porous silica microsphere cavity configuration is main with silicon base at present; For example publication number is that the Chinese invention patent that CN101710118A is discloses a kind of optical immunity detecting method based on porous silicon three-element structure microcavity; Its shortcoming is that such sensor utilization ratio is lower; Can only prepare a sensor on the silicon base, will together throw aside together with silicon base behind the sensor failure.In addition, in order to improve detection accuracy, usually need carry out repeated detection, this can use a large amount of sample sensor and solution to be measured equally, has caused waste to a certain extent, and under many circumstances, the amount that testing sample can supply detect is very limited.
Summary of the invention
To above-mentioned defective; The purpose of this invention is to provide a kind of Porous Silicon Microcavity biology sensor, based on the optical detection system of this sensor and the preparation method of this biology sensor; With the biomolecule monitoring equipment that solves prior art exist with high costs, complicated operation, the technical matters that detection accuracy is low.
For realizing above-mentioned purpose, the technical scheme below the present invention has adopted:
The present invention at first provides a kind of Porous Silicon Microcavity biology sensor; Comprise the Bragg catoptron, down the Bragg catoptron and be clipped in said go up between Bragg catoptron and the following Bragg catoptron defective once; The said Bragg catoptron of going up comprises high porosity rate layer and the low porosity rate layer that five loop cycle are alternately arranged respectively with following Bragg catoptron, and said defective Ceng Houdu is 2 times of said high porosity rate layer thickness.
According to the described Porous Silicon Microcavity biology sensor of preferred embodiment of the present invention, said high porosity rate layer is by 80mA/cm 2Electrolytic corrosion form, said low porosity rate layer is by 20mA/cm 2Electrolytic corrosion form.
The present invention provide again a kind of optical detection system based on above-mentioned biology sensor in; It comprises halogen light source, a plurality of sense channel that has the Porous Silicon Microcavity biology sensor; Computing machine, photoswitch, spectrometer and liquid fluid system; Light source that said Halogen lamp LED sends gets into said sense channel through division optical fiber, and the bright elder brother branch of said division optical fiber links to each other with each bifurcation fiber of said sense channel through adapter, and the reflected light of said Porous Silicon Microcavity biology sensor is transferred to said photoswitch by another branch of said bifurcation fiber; Said photoswitch is switching-over light path under said computer control; Select to get into the light signal of spectrometer, the data that said spectrometer will be handled behind the said light signal are sent to said computing machine, and computing shows testing result in said computing machine.
The present invention provides a kind of preparation method of above-mentioned Porous Silicon Microcavity biology sensor again, and this kind be the preparation method may further comprise the steps: step 1: prepare the Porous Silicon Microcavity film sample based on P type silicon chip; Step 2: preparation Porous Silicon Microcavity membrane array; Step 3: no sensing passage is carried out corresponding biological chemistry modification according to the detection demand.
According to the described preparation method of preferred embodiment of the present invention; Said step 1 further comprises: step 1.1: along the crystal orientation boron twin polishing silicon chip is cut into 2 centimetres of square samples that multiply by 2 centimetres; Use deionized water and 95% to analyze absolute alcohol solution flushing silicon chip sample successively, it is subsequent use to dry up sample with high pure nitrogen then; Step 1.2: the said sample of corrosion in the etching tank that teflon is processed; Step 1.3: how Control current density and time corrode sample under the computer control.
According to the described preparation method of preferred embodiment of the present invention, in said step 1.2 with aluminium flake as anode, platinum filament is as negative electrode, corrosive liquid is mixed by the analysis absolute alcohol of the pure hydrofluoric acid aqueous solution of 41.2% analysis and 95% volume ratio with 1:1.5.
According to the described preparation method of preferred embodiment of the present invention, said step 2 further comprises: step 2.1: apply 200mA/cm 2 Electric current 2 seconds, make the porous silica microsphere cavity configuration from substrate desquamation, process the porous silica microsphere colorimetric sensor films; Step 2.2: the Porous Silicon Microcavity colorimetric sensor films that makes is soaked in the pure solution of DMSO carried out wet oxidation in 5 hours; Step 2.3: the film after the oxidation was soaked in the capacity DI water 10 minutes, to remove residual DSMO solution; Step 2.4: on the glass substrate that cleans up, drip a series of PVFs (Formvar) solution droplets, solvent is 1, the 2-ethylene dichloride.Then the Porous Silicon Microcavity film after the oxidation is placed rapidly on the formvar solution, treat 1, after the evaporation of 2-ethylene dichloride, formvar just firmly sticks at the Porous Silicon Microcavity film on the substrate of glass.
Owing to adopted above technical scheme, make the present invention than prior art, have following advantage and good effect:
The first, the invention provides a kind of hyperchannel optics Porous Silicon Microcavity thin film bio transducer production method; Use is transplanted Porous Silicon Microcavity film on substrate of glass as senser element; Remaining silicon base can continue corrosion preparation Porous Silicon Microcavity film; Thereby improved the service efficiency of silicon chip, further reduced the detection cost;
The second, the present invention is according to the liquid flow cavity design of using, and the film sample that primary electrochemical erodes away can be divided into the littler sensor of a plurality of areas, and this has improved the service efficiency of sensor under the prerequisite that does not reduce signal intensity.The solution amount to be measured that the sensor unit that area is littler consumes has also still less been saved solution to be measured.
Three, closer to each other with once corroding the sensor performance that obtains; The harmonic peak position consistency; Can be used to flow through the pure buffer solution that does not contain test substance with wherein one the tunnel as reference channel, further improve the reliability that detects; Multi-channel detection makes and in the one-time detection operation, can obtain many group experimental datas, thereby improves detection efficiency.
Four, optical detection provided by the invention system is except being provided with reference channel, and hyperchannel can also be used for detecting different biomolecule simultaneously and can not interfere with each other, thereby improves detection efficiency.Especially at present medical research is found to diagnose the illness often needs the detection of multiple biomarker (biomarker) as foundation, needs comprehensive a plurality of biomarker content analysis to judge.Can use technical scheme of the present invention, the different detection passage is carried out different antigens, antibody molecule modification, once experiment just can detect a plurality of biomarkers.
Certainly, any one specific embodiment of embodiment of the present invention content might not reach above whole technique effect simultaneously.
Description of drawings
Fig. 1 is a Porous Silicon Microcavity biosensor structure synoptic diagram provided by the invention;
Fig. 2 is the top view of liquid flow cavity;
Fig. 3 is a hyperchannel optics detection system block diagram provided by the invention;
Fig. 4 is the preparation method's that provides of embodiment of the present invention a process flow diagram.
Embodiment
Below in conjunction with accompanying drawing several preferred embodiments of the present invention is described in detail, but the present invention is not restricted to these embodiment.The present invention contain any on marrow of the present invention and scope, make substitute, modification, equivalent method and scheme.Understand for the public is had completely the present invention, in the following preferred embodiment of the present invention, specified concrete details, and do not had the description of these details also can understand the present invention fully for a person skilled in the art.In addition, for fear of essence of the present invention is caused unnecessary obscuring, do not specify well-known method, process, flow process, element and circuit etc.
Porous Silicon Microcavity sensor construction as shown in Figure 1, as shown in Figure 1, it is by last Bragg catoptron 1, Bragg catoptron 2 and their folded defect layers 3 are formed down.Bragg catoptron 1,3 constitutes by high porosity rate layer 4, the low porosity rate layer 5 in five cycles.High porosity rate layer 4 is by 80mA/cm 2Current density corrosion form, low porosity rate layer 5 is by 20mA/cm 2Current density corrosion form, defect layer is two times of high porosity rate layer 4 thickness.The micro-cavity structure that makes applies 200mA/cm again 2Corrosion current it was broken away from 2 seconds from silicon base.The silicon base that exposes can be carried out the corrosion of porous silicon microcavity once more according to the method described above and got film, has improved the utilization factor to silicon chip, thereby has further reduced the detection cost.Next the microcavity film that makes is soaked among the DSMO and takes out after 5 hours.
Next by preparation liquid flow cavity shown in Figure 2.At first with the formvar drips of solution on microslide, again that the Porous Silicon Microcavity film sample is placed on it rapidly, treat solvent 1, after the 2-ethylene dichloride volatilization, film is just sticked on the microslide.Next to carry out chemical modification to the Porous Silicon Microcavity film according to the actual detected demand, the corresponding probe biomolecule of grafting.After modification finishes, liquid flow cavity is affixed on the Porous Silicon Microcavity film, gateway 11 is as the passage of solution turnover chamber to be measured, and two semicircles 12 are flow chamber, form two sense channels.Because the porous silicon film sample that corrosion obtains among the present invention for circular, so flow chamber also is designed to circle, thereby improves the effective usable floor area of sensor.All the other sense channels method according to this prepare.
As shown in Figure 3; Fig. 3 provided by the invention learns detection system and has comprised that it comprises halogen light source 31, a plurality of sense channel 35 that has Porous Silicon Microcavity biology sensor 351; Computing machine 39, photoswitch 37, spectrometer 38 and liquid fluid system 36; The light that is sent by Halogen lamp LED 31 light sources gets into each sense channel 35 simultaneously through division optical fiber 32; Its each branch uses adapter 33 to link to each other with a branch of bifurcation fiber 34, and light can pass to Porous Silicon Microcavity biology sensor 351 surfaces thus, and its reflected light is collected by bifurcation fiber 34 simultaneously and imported photoswitch into by bifurcation fiber 34 another branches; The signal switching-over light path that photoswitch 37 transmits according to computing machine 39 ends; Have only one road light signal to get into spectrometer 38 in the certain period of time, the data after spectrometer 38 is handled are sent into computing machine 39, and carry out computing demonstration testing result by computing machine 39 at last.
As shown in Figure 4, the present invention provides a kind of method for preparing above-mentioned Porous Silicon Microcavity biology sensor, comprising:
S401: prepare the Porous Silicon Microcavity film sample based on p type silicon chip;
S402: preparation Porous Silicon Microcavity membrane array;
S403: and different sensing passages is carried out corresponding biological chemistry modification according to the actual detected demand;
After accomplishing, build hyperchannel optics detection system Porous Silicon Microcavity thin film sensor array is carried out input.
Prepare the Porous Silicon Microcavity film sample based on p type silicon chip and comprise following operation again:
At first, silicon chip cutting; The silicon chip that uses be boron (100) twin polishing silicon chip as p type doped chemical.Be cut into 2 centimetres of square samples that multiply by 2 centimetres along < 110>crystal orientation.Use deionized water and 95% to analyze absolute alcohol solution flushing silicon chip sample successively, it is subsequent use to dry up sample with high pure nitrogen then;
The second, corrosion is carried out in the etching tank that teflon is processed.Aluminium flake is as anode, and platinum filament is as negative electrode, and corrosive liquid is mixed by the analysis absolute alcohol of the pure hydrofluoric acid aqueous solution of 41.2% analysis and 95% volume ratio with 1:1.5.
The 3rd, the current density and the time of corrosion are accurately controlled by computing machine.The porous silica microsphere cavity configuration by two Bragg mirror layers with and folded defect layer form.Bragg mirror layer is wherein formed by the porous silicon layer overlapping of the high and low porosity rate in some cycles, and current parameters is drawn by emulation and experiment.The 1-D photon crystal material that is perpendicular to silicon chip surface that galvanic corrosion obtains like this.The defect layer that is clipped in the middle can be introduced an extremely narrow harmonic peak in the middle of the high reflectance zone in the sensor reflectivity spectral line, it is the structure sensitive parameter, and the wavelength that harmonic peak is corresponding is influenced by the defect layer refractive index.Therefore, after the biomolecule to be detected that adds got in the defect layer, corresponding mobile can take place in harmonic peak, thereby can be according to the biomolecule concentration value that is added of how much judging of amount of movement.
Step S402 prepares the Porous Silicon Microcavity membrane array and comprises following operation:
1, applies 200mA/cm 2 Electric current 2 seconds, this can all corrode the silicon of bottom one deck of porous silica microsphere cavity configuration and silicon base intersection, thereby makes the porous silica microsphere cavity configuration from substrate desquamation, processes the Porous Silicon Microcavity film;
2, the Porous Silicon Microcavity film that makes is soaked in the pure solution of DMSO carried out wet oxidation in 5 hours.This is because the porous silicon surface that makes has a large amount of si-h bonds, and si-h bond is hydrophobic and unstable, thereby can cause difficult infiltration of the biomolecule WS and harmonic peak to drift about in time.And behind silicon surface oxidation, surface hydrophilic and highly stable, biomolecule solution are prone to get into arrival defect layer in the hole.Common high-temperature oxydation way is not suitable for porous silicon film, adopts the way of wet oxidation here, in DMSO, soaks into after 5 hours, and experiment shows, thinks that porous silicon surface is oxidized basically, and si-h bond is replaced by silicon oxygen bond;
3, the film after the oxidation was soaked in the capacity DI water 10 minutes, to remove residual DSMO solution;
4, on the glass substrate that cleans up, drip a series of 0.25% PVFs (formvar) solution droplets in certain sequence, solvent is 1, the 2-ethylene dichloride.Then the Porous Silicon Microcavity film after the oxidation is placed rapidly on the formvar solution.Treat 1, after the evaporation of 2-ethylene dichloride, formvar just firmly sticks at the Porous Silicon Microcavity film on the substrate of glass;
Afterwards, execution in step S403 carries out chemical modification to the porous silicon sensor again according to the actual detected needs.
After preparation is accomplished, liquid flow cavity is affixed on the Porous Silicon Microcavity film, and the liquid Vomitory is linked to each other with liquid fluid system, connect hyperchannel optics system again.
Use the division multimode optical fiber with light source white light demultiplexing; Branch of each minute light path use adapter and bifurcation fiber links to each other; Bifurcation fiber is transferred to sensor surface with the incident white light on the one hand; The light signal that reflects of pick-up transducers on the other hand, and another branch's input light path change-over switch through bifurcation fiber.The light path change-over switch is switched light path with certain frequency; It is output as a specific light path in a certain specific timeslice; The output of photoswitch is carried out real-time collection analysis as the input of fiber spectrometer to light signal, and through computer the result is shown.
Following brief description two application examples of the present invention.
Application examples one
Should be to use multichannel Porous Silicon Microcavity biology sensor to detect 24 base pair dna single chain molecules by use-case, it comprises:
At first, produce the Porous Silicon Microcavity sample according to the method for describing in the embodiment;
Afterwards, according to the method for describing in the embodiment Porous Silicon Microcavity is taken off from silicon base and to carry out wet oxidation, and use formvar to be affixed on the microslide;
At last, in Porous Silicon Microcavity, connect dna probe molecule, it comprises that specifically step is:
1. in Porous Silicon Microcavity film surface Dropwise 50 μ L concentration 2% APTES solution.Leave standstill and wash with DI water after 20 minutes and dry up, place 100 ℃ of environment bakings to take out in 10 minutes with nitrogen.
2. drip 2.5% the glutaraldehyde solution of 100 μ L in order at sample surfaces, the NaOH solution of the sodium cyanoborohydride of the 5mol/L of 1 μ L (sodium cyanoborohydride) and 1mol/L.In above-mentioned mixed liquor, soaked 2 hours.
3. the flushing of sample sensor HEPES damping fluid also was soaked in wherein 1 hour once more.Dry up with damping fluid flushing sample surfaces and with nitrogen more afterwards.
4. the connection of dna probe molecule should be carried out in 30 minutes of a last step aldehyde radicalization.The Porous Silicon Microcavity sample is soaked in the amido modified dna probe molecule damping fluid.Repeating step 3 afterwards.
5. next sample sensor was soaked 2 hours in 3mol/L monoethanolamine (ethanolamine).Repeating step 3 afterwards.
6. liquid flow cavity is affixed on the Porous Silicon Microcavity that disposes, and feed liquor is linked to each other with liquid fluid system with liquid outlet.
7. detect DNA, connect outside multiplex optical detection system, regulate peristaltic pump and slowly DNA damping fluid to be measured is pumped in the liquid flow cavity, treat that it all is full of promptly to stop, leaving standstill 1 hour after, pump into the capacity damping fluid again and wash and do not connect the DNA sample.This process whole process is by the spectrometer dynamically recording.Simultaneously, two parts part that liquid flow cavity divided is as sense channel, and another part only feeds damping fluid as the contrast passage in the whole testing process.
Application examples two
In should use-case, use multichannel Porous Silicon Microcavity biology sensor to detect Escherichia coli (E-Coli) born of the same parents outer intimate plain (Intimin-IBD)
At first, produce the Porous Silicon Microcavity sample according to the method for describing in the embodiment;
Afterwards, according to the method for describing in the embodiment Porous Silicon Microcavity is taken off from silicon base and to carry out wet oxidation, and use formvar to be affixed on the microslide;
Then, in Porous Silicon Microcavity, connect the tight plain antibody of transposition (translocation intimin receptor-intimin binding domain Tir-IBD), comprises that specifically step is:
1. in Porous Silicon Microcavity film surface Dropwise 50 μ L concentration 2% APTES solution.Leave standstill and wash with DI water after 20 minutes and dry up, place 100 ℃ of environment bakings to take out in 10 minutes with nitrogen.
2. sample is dipped in the HEPES damping fluid of 20mM, again 2.5% of Dropwise 50 μ L glutaraldehyde solution.Leave standstill after 30 minutes and take out, use the flushing of HEPES damping fluid, and dry up with nitrogen.
3. at the Tri-IBD solution of sample sensor surface Dropwise 50 μ L, left standstill 1 hour.Again sample was soaked in the HEPES damping fluid 20 minutes.Dry up with nitrogen afterwards.
4. Dropwise 50 μ L concentration is the glycine methyl ester of 1mol/L, leaves standstill 1 hour.Again sample was soaked in the HEPES damping fluid 20 minutes.Dry up with nitrogen afterwards.
5. liquid flow cavity is affixed on the Porous Silicon Microcavity that disposes, and feed liquor is linked to each other with liquid fluid system with liquid outlet.
6. detect Intimin-IBD.Connect outside multiplex optical detection system, regulate peristaltic pump and slowly Intimin-IBD damping fluid to be measured is pumped in the liquid flow cavity, treat that it all is full of promptly to stop, leaving standstill 1 hour after, pump into the capacity damping fluid again and wash the Intimin-IBD sample that does not connect.This process whole process is by the spectrometer dynamically recording.Simultaneously, two parts part that liquid flow cavity divided is as sense channel, and another part only feeds damping fluid as the contrast passage in the whole testing process.
The preferred embodiment of the present invention just is used for helping to set forth the present invention.Preferred embodiment does not have all details of detailed descriptionthe, does not limit this invention yet and is merely described embodiment.Obviously, according to the content of this instructions, can do a lot of modifications and variation.These embodiment are chosen and specifically described to this instructions, is in order to explain principle of the present invention and practical application better, thereby person skilled can be utilized the present invention well under making.The present invention only receives the restriction of claims and four corner and equivalent.

Claims (8)

1. Porous Silicon Microcavity biology sensor; It is characterized in that; Comprise the Bragg catoptron, down the Bragg catoptron and be clipped in said go up between Bragg catoptron and the following Bragg catoptron defective once; The said Bragg catoptron of going up comprises high porosity rate layer and the low porosity rate layer that five loop cycle are alternately arranged respectively with following Bragg catoptron, and said defective Ceng Houdu is 2 times of said high porosity rate layer thickness.
2. Porous Silicon Microcavity biology sensor as claimed in claim 1 is characterized in that, said high porosity rate layer is by 80mA/cm 2Electrolytic corrosion form, said low porosity rate layer is by 20mA/cm 2Electrolytic corrosion form.
A kind of optical detection system; It is characterized in that; Comprise halogen light source, a plurality of sense channel that has the Porous Silicon Microcavity biology sensor, computing machine, photoswitch, spectrometer and liquid fluid system, the light source that said Halogen lamp LED sends gets into said sense channel through division optical fiber; The bright elder brother branch of said division optical fiber links to each other with each bifurcation fiber of said sense channel through adapter; The reflected light of said Porous Silicon Microcavity biology sensor is transferred to said photoswitch by another branch of said bifurcation fiber, and said photoswitch is switching-over light path under said computer control, selects to get into the light signal of spectrometer; The data that said spectrometer will be handled behind the said light signal are sent to said computing machine, and computing shows testing result in said computing machine.
3. optical detection as claimed in claim 3 system; It is characterized in that; Said Porous Silicon Microcavity biology sensor comprise the Bragg catoptron, down the Bragg catoptron and be clipped in said go up between Bragg catoptron and the following Bragg catoptron defective once; The said Bragg catoptron of going up comprises high porosity rate layer and the low porosity rate layer that five loop cycle are alternately arranged respectively with following Bragg catoptron, and said defective Ceng Houdu is 2 times of said high porosity rate layer thickness.
4. the preparation method of a Porous Silicon Microcavity biology sensor is characterized in that, may further comprise the steps:
Step 1: prepare the Porous Silicon Microcavity film sample based on P type silicon chip;
Step 2: preparation Porous Silicon Microcavity membrane array;
Step 3: no sensing passage is carried out corresponding biological chemistry modification according to the detection demand.
5. preparation method as claimed in claim 5 is characterized in that, said step 1 further comprises:
Step 1.1: along the crystal orientation boron twin polishing silicon chip is cut into 2 centimetres of square samples that multiply by 2 centimetres, uses deionized water and 95% to analyze absolute alcohol solution flushing silicon chip sample successively, it is subsequent use to dry up sample with high pure nitrogen then;
Step 1.2: the said sample of corrosion in the etching tank that teflon is processed;
Step 1.3: how Control current density and time corrode sample under the computer control.
6. preparation method as claimed in claim 6 is characterized in that, in said step 1.2 with aluminium flake as anode, platinum filament is as negative electrode, corrosive liquid is mixed by the analysis absolute alcohol of the pure hydrofluoric acid aqueous solution of 41.2% analysis and 95% volume ratio with 1:1.5.
7. preparation method as claimed in claim 5 is characterized in that, said step 2 further comprises:
Step 2.1: apply 200mA/cm 2Electric current 2 seconds, make the porous silica microsphere cavity configuration from substrate desquamation, process the porous silica microsphere colorimetric sensor films;
Step 2.2: the Porous Silicon Microcavity colorimetric sensor films that makes is soaked in the pure solution of DMSO carried out wet oxidation in 5 hours;
Step 2.3: the film after the oxidation was soaked in the capacity DI water 10 minutes, to remove residual DSMO solution;
Step 2.4: on the glass substrate that cleans up, drip a series of PVFs (Formvar) solution droplets, solvent is 1, the 2-ethylene dichloride.
8. then the Porous Silicon Microcavity film after the oxidation is placed rapidly on the formvar solution, treat 1, after the evaporation of 2-ethylene dichloride, formvar just firmly sticks at the Porous Silicon Microcavity film on the substrate of glass.
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