CN106093004A - Super-hydrophobic molecule enrichment concentrates chip and its preparation method and application - Google Patents

Super-hydrophobic molecule enrichment concentrates chip and its preparation method and application Download PDF

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CN106093004A
CN106093004A CN201610392384.5A CN201610392384A CN106093004A CN 106093004 A CN106093004 A CN 106093004A CN 201610392384 A CN201610392384 A CN 201610392384A CN 106093004 A CN106093004 A CN 106093004A
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chip
silicon
super
hydrophobic molecule
concentrates
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CN106093004B (en
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何璇
刘渝
罗毅威
王慧
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Institute of Chemical Material of CAEP
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures

Abstract

The invention discloses a kind of super-hydrophobic molecule enrichment and concentrate chip and its preparation method and application, described preparation method comprises the following steps: the silicon chip cleaned up is carried out tackified finish, and by photoresist uniform gluing to silicon chip, then toasts;The silicon chip after baking and the pattern on photolithography plate are carried out pre-para-position and automatic aligning operation again, para-position carries out exposure-processed after completing, then development treatment is carried out, subsequently silicon chip is carried out deep silicon etching process, then by magnetron sputtering crystal film Au is injected on the silicon chip of silicon pillar array structure and obtains mould material;The graphite cleaned up as positive pole, is placed in the chip that electrodeposit reaction in electrodeposit liquid obtains having nanometer silver silicon pillar array structure as negative pole, mould material, clean by clean water after taking-up, then dry up with pure argon.The super-hydrophobic molecule enrichment of preparation concentrates chip and has hypersensitive, fast-response, the advantage of low solvent loss rate.

Description

Super-hydrophobic molecule enrichment concentrates chip and its preparation method and application
Technical field
The present invention relates to the preparation method of a kind of super-hydrophobic chip, be specifically related to a kind of super-hydrophobic molecule enrichment and concentrate core Sheet and its preparation method and application.
Background technology
Surface enhanced raman spectroscopy (Surface Enhanced Raman Scattering, call SERS in the following text) technology, be 20 century 70s find, a kind of new type of high sensitivity spectral analysis technique full-fledged after the nineties.SERS technology Basis be that the raman spectral signal of material molecule is at the specific metal nano material (nanoparticle such as gold, silver, copper etc. (Nanoparticles, NPs) surface can be greatly enhanced (106~1010Times).In brief, SERS technology is prominent excellent Put and show three aspects: 1) there is high sensitivity, unimolecule SERS analyzes wide coverage;2) with infrared spectrum phase Seemingly, may be used for material qualitative analysis, i.e. except how many problems can be answered, it is also possible to the SERS spectra according to material is true Surely what is;3) can realize portable and not sacrifice analytical performance.Additionally, SERS spectra half-peak breadth is only about 1nm, multiple point It is not susceptible to interference between material when analysis thing detects simultaneously.
At present, the relevant report of SERS base material preparation method is mainly based upon constructing and metal nano of micro-nano structure Materials synthesis and the SERS substrate that develops and detection method.But, although SERS technology obtains good development, Metal Substrate system For also reaching its maturity, but there is also a problem: the preparation process of the metallic matrix of general high enhancer is more complicated, Seek the necessary large scale stable homogeneous of active matrix pattern, and the size of single nanotopography is in nanometer scale, the most several nanometers During magnitude, strong local electromagnetic field could be produced, thus cause strong SERS effect.But, prevailing experimental conditions is difficult to operation With regulation and control, it is difficult to synthesize several nanometer scale and the homogeneous metal nano material of structure in common lab.In recent years, along with electricity The development of sub-information technology, photoetching technique becomes preparation SERS substrate, builds a kind of important method of nano-array.This technology can To obtain highly homogeneous nano-array, thus obtain the SERS signal of high efficiency high stable.Its stability is current other technologies The most incomparable.
But, current SERS technology has certain difficulty for the determinand detection of super low concentration, and reason is: (1) molecule Under super low concentration, solution excessively dilutes, and transfers to molecule adsorption efficiency during SERS substrate surface the lowest, and readily diffuses into base The regional of bottom material, is often difficult to during actual detection obtain signal quickly and accurately, adds difficulty for actual detection. (2) in actual detection, determinand often exists with solution state, and solution needs its volume, concentration, and quantity of solvent is carried out precisely Determine.Being soaked in solution to be measured with SERS substrate, whole pretreatment process at least needs 30min the most again, and solvent is also required to Several milliliters are arrived hundreds of milliliter, waste time and energy.
At present, the detection technique for super low concentration material mostly there are disadvantages that, it is impossible to is fully achieved Expected Results, Meet the demand of detection in real work.Therefore, developing highly sensitive, fast-response, low solvent consumes, the SERS detection that trace is lossless Technology, it appears particularly important.
Summary of the invention
It is an object of the invention to provide a kind of hypersensitive, fast-response, the super-hydrophobic molecule of low solvent loss rate is enriched with dense Shrinking chip, this chip can solve the problem that current simple process cannot obtain highly sensitive substrate.
It is a further object to provide a kind of super-hydrophobic molecule enrichment and concentrate the preparation method of chip.
A further object of the present invention is to provide a kind of super-hydrophobic molecule enrichment and concentrates the chip application at SERS.
In order to reach above-mentioned technique effect, the present invention takes techniques below scheme:
A kind of super-hydrophobic molecule enrichment concentrates the preparation method of chip, comprises the following steps:
Step A: the silicon chip cleaned up is carried out tackified finish, and by photoresist uniform gluing to silicon chip, then enters Row baking;Silicon chip after baking and the pattern on photolithography plate carry out pre-para-position and automatic aligning operation again, and para-position completes laggard Row exposure-processed, then carries out development treatment, it is thus achieved that all silicon chips of one array architecture pattern, and silicon chip carries out deep silicon quarter subsequently Erosion processes, and obtains the silicon chip of homogeneous silicon pillar array structure, then by magnetron sputtering, crystal film Au is injected in silicon pillar array structure Silicon chip on obtain mould material;
Step B:1~the silver nitrate aqueous solution of 3g/L and 3~5g/L aqueous citric acid solutions are the ratio of 1:1 according to volume ratio Phase mix homogeneously, obtains electrodeposit liquid;Using the graphite that cleans up as negative pole, mould material, as positive pole, is placed in described In electrodeposit liquid, electrodeposit reaction obtains the chip with nanometer silver silicon pillar array structure, clean by clean water after taking-up, then Dry up with pure argon, obtain described super-hydrophobic molecule enrichment and concentrate chip.
Further technical scheme is, in the silicon chip of described silicon pillar array structure, silicon post and the gap of silicon post are 2~5 micro- Rice;Silicon column length is 10~50 microns;The described pattern magnitude on photolithography plate is not less than 2.0cm × 2.0cm.
Further technical scheme is, a diameter of the 0.5 of described graphite~0.6cm, a length of the 3 of graphite~6cm.
Further technical scheme is that the electric current of described magnetron sputtering is 25~35mA, and the time of magnetron sputtering is 80 ~100s.
Further technical scheme is that described electrodeposit reaction is current response 2~6 under electric current is 200~800mA Hour.
The invention provides that the preparation method that the super-hydrophobic molecule enrichment described in employing concentrates chip is prepared is super Hydrophobic molecule enrichment concentrates chip, and it is square or the nanometer silver silicon post of hexagon uniform array lattice structure arrangement, institute The nanometer silver silicon post stated is uniformly to wrap up nanometer silver on silicon post, and nanometer silver is the lamellar structure of 1~2 micron, and nanometer silver silicon post is Highly 12~55 microns, the regular column of a diameter of 2~5 microns, the gap between nanometer silver silicon post is 8~12nm.
Further technical scheme is, described super-hydrophobic molecule enrichment concentrates chip and has super-hydrophobic effect, with water Contact angle >=140 °.
Present invention also offers described super-hydrophobic molecule enrichment and concentrate the chip application at SERS, including following step Rapid: to concentrate the citric acid cleaning of chip surface totally with plasma cleaning instrument by remaining in super-hydrophobic molecule enrichment, then will The super-hydrophobic molecule enrichment cleaned up concentrates chip and puts on the table, takes 3~5 microlitre testing liquids and drops in chip surface, Stand 5~8 minutes, the vestige stayed after observing droplet evaporation, with confocal laser Raman spectrometer, drop is enriched with enrichment region Territory is focused gathering, and carries out SERS detection.
Further technical scheme is, testing liquid is for being dissolved in water or water-fast explosive, organic pollution, organic One in dyestuff, drug molecule.
Further technical scheme is, when described testing liquid is water-fast liquid, to carry out testing liquid Acidifying or alkalization become soluble-salt and detect.
The present invention will be further explained below.
The preparation method of the present invention utilizes photoetching and the preparation of deep silicon etching technology to have the silicon chip of homogeneous continuous pattern change. Described photoetching is the figure on photolithography plate to be carried out 1:1 be precisely transferred on silicon chip.In order to ensure the silicon of silicon pillar array structure In sheet, silicon column length is 10~50 microns, and in deep silicon etching processes, the degree of depth of deep silicon etching is 10~50 microns.
The silver nitrate aqueous solution of 1~3g/L and 3~5g/L aqueous citric acid solutions mix mutually according to the ratio that volume ratio is 1:1 Uniformly, electrodeposit liquid is obtained.According to a preferred embodiment of the invention, described electrodeposit liquid be 2g/L silver nitrate aqueous solution and 4g/L aqueous citric acid solution is according to the ratio phase mix homogeneously that volume ratio is 1:1.In electrodeposit reaction, the volume of electrodeposit liquid is 10~60 milliliters.
The present invention compared with prior art, has a following beneficial effect:
1, the method for the present invention utilizes photoetching process to combine deep silicon etching technology, etches receiving of certain arrangement mode on silicon chip Rice silicon post array, with silicon post array as template, prepares Au nanometer seed, simply electricity by the non-solvent magnetron sputtering method of physics Chemical deposition assemble nanometer silver silicon post array chip.Nanometer silver silicon post array prepared by the method, has super-hydrophobic effect, should Surface is more than 140 degree with the contact angle of water.This super-hydrophobic effect has the effect of enrichment method to determinand.I.e. along with aqueous solvent Evaporation, solute molecule has been stayed chip surface, and has slowly been enriched with, and is concentrated to a region the least, has ultimately formed super dense One point of contracting.Utilize raman microspectroscopy spectrum that enrichment method point is carried out Sample acquisition, strengthen at the SERS of this chip and concentrate Under the dual function of enrichment, overdelicate detection signal can be obtained.
2, nano material prepared by traditional handicraft as SERS substrate for detection molecules time, determinand is often with solution shape State exists, and solution needs its volume, concentration, and quantity of solvent precisely determines.It is soaked in be measured molten the most again with SERS substrate In liquid, whole pretreatment process at least needs 30min, and solvent is also required to several milliliters and arrives hundreds of milliliter, wastes time and energy.And be somebody's turn to do The low-concentration liquid of chip detection, its volume only needs 3-5 microlitre, and pretreatment time is only the time of this 3-5 microliters of water volatilization, I.e. about 5-10 minute, it is possible to the effective problem solving at present the detection of low concentration material to be existed, it is a kind of hypersensitive, rings soon Should, the method for testing of low solvent loss rate, there is good actual application value.
3, during the present invention prepares nanometer silver silicon post array surface enhancing Raman scattering substrate, the nanometer silver silicon post of vertical growth Array has the hierarchy of three-dimensional, can produce higher needle point effect, and nano array structure can effectively generation etc. uniformly Ion resonance, silver nanoparticle good stability, there is the effect of collaborative enhancing, high-sensitive SERS effect can be obtained.Meanwhile, by knot Close condensation and concentrate effect, can preferably be enriched with testing molecule so that it is navigate to produce the region of strong local electric field, thus Obtain overdelicate detectivity.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the silicon chip of the equal one array architecture pattern of spacing 2 microns × 2 microns in embodiment 1;
Fig. 2 be in embodiment 1 etching depth be 30 microns, silicon intercolumniation be the homogeneous silicon post array junctions of 2 microns × 2 microns The SEM figure of the silicon chip of structure;
Fig. 3 is the SEM figure of the chip of nanometer silver silicon pillar array structure in embodiment 1;
The molecule enrichment that Fig. 4 is super-hydrophobic in embodiment 1 concentrates chip surface and water contact angle test figure;
The molecule enrichment that Fig. 5 is super-hydrophobic in embodiment 1 concentrates the chip hypersensitive detection figure to R6G;
The molecule enrichment that Fig. 6 is super-hydrophobic in embodiment 1 concentrates the chip hypersensitive detection figure to NTO;
Fig. 7 is the SEM figure of the silicon chip of the equal one array architecture pattern of spacing 4 microns × 4 microns in embodiment 2;
Fig. 8 be in embodiment 2 etching depth be 10 microns, silicon intercolumniation be the homogeneous silicon post array junctions of 4 microns × 4 microns The SEM figure of the silicon chip of structure;
Fig. 9 is the SEM figure of the chip of nanometer silver silicon pillar array structure in embodiment 2;
The molecule enrichment that Figure 10 is super-hydrophobic in embodiment 2 concentrates chip surface and water contact angle test figure;
The molecule enrichment that Figure 11 is super-hydrophobic in embodiment 2 concentrates the chip hypersensitive detection figure to R6G;
Figure 12 is the SEM figure of the silicon chip of the equal one array architecture pattern of spacing 2 microns × 2 microns in embodiment 3;
Figure 13 be in embodiment 3 etching depth be 10 microns, silicon intercolumniation be the homogeneous silicon post array of 2 microns × 2 microns The SEM figure of the silicon chip of structure;
Figure 14 is the SEM figure of the chip of nanometer silver silicon pillar array structure in embodiment 3;
The molecule enrichment that Figure 15 is super-hydrophobic in embodiment 3 concentrates chip surface and water contact angle test figure;
The molecule enrichment that Figure 16 is super-hydrophobic in embodiment 3 concentrates the chip hypersensitive detection figure to R6G.
Detailed description of the invention
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
Step one: the preparation of template
The silicon chip cleaned up is carried out tackified finish, and by photoresist uniform gluing to silicon chip, then toasts; Silicon chip after baking and the pattern on photolithography plate carry out pre-para-position and automatic aligning operation again, and para-position is exposed place after completing Reason, then carries out development treatment, it is thus achieved that pattern is the silicon chip (figure of the equal one array architecture pattern of spacing 2 microns × 2 microns 1), silicon chip carrying out deep silicon etching process subsequently, the deep silicon etching degree of depth is 30 microns, and having obtained etching depth is 30 microns, silicon Intercolumniation is the silicon chip (Fig. 2) of the homogeneous silicon pillar array structure of 2 microns × 2 microns, then crystal film Au is sprayed by magnetron sputtering Penetrating and obtain mould material on the silicon chip of silicon pillar array structure, the electric current of magnetron sputtering is 30mA, and the time of magnetron sputtering is 90s;
The enrichment of step 2, super-hydrophobic molecule concentrates the preparation of chip
The silver nitrate aqueous solution of 2g/L and 4g/L aqueous citric acid solution according to the ratio phase mix homogeneously that volume ratio is 1:1, Obtain electrodeposit liquid;Using the graphite that cleans up as negative pole, mould material, as positive pole, is placed in described electrodeposit liquid use The current response 2 of 200~800mA~obtain the chip (Fig. 3) with nanometer silver silicon pillar array structure for 6 hours, with clear after taking-up Water cleans up, then dries up with pure argon, obtains described super-hydrophobic molecule enrichment and concentrates chip.
Step 3: super-hydrophobic molecule enrichment concentrates the chip application at SERS
With plasma cleaning instrument by clean, to eliminate citric acid for the citric acid cleaning remaining in nanometer silver silicon post array surface The Raman signal interference to testing molecule.Verify the ultra-hydrophobicity (Fig. 4) of this substrate with contact angle instrument, can obtain its surface with The contact angle of water is 154 degree, belongs to the surface of superhydrophobic property.
The nanometer silver silicon post array chip cleaned up is kept flat on the table, takes 3-5 microlitre testing liquid rhodamine 6G (R6G) chip surface is dropped in, after standing 5-8 minute, the vestige stayed after observing droplet evaporation, use confocal laser Raman spectrum Drop enrichment concentrated area is focused gathering by instrument, carries out SERS detection (Fig. 5).
Step 4: the enrichment of super-hydrophobic molecule concentrates chip and detects the hypersensitive of water-insoluble explosive
When water-fast explosive NTO is carried out trace detection, it is contemplated that this quasi-molecule has the hydrogen that can protonate, therefore By alkalization so that it is react with NaOH, carried out hydrophilic synthesis.Become soluble-salt.This hydrophilic synthetic method is fitted For all, there is the indissoluble water substance of this feature.
The nanometer silver silicon post array chip cleaned up is kept flat on the table, takes 3-5 microlitre testing liquid explosive NTO Dropping in chip surface, after standing 5-8 minute, the vestige stayed after observing droplet evaporation, with confocal laser Raman spectrometer pair Drop enrichment concentrated area is focused gathering, and carries out SERS detection (Fig. 6).
Embodiment 2:
Step one: the preparation of template
The silicon chip cleaned up is carried out tackified finish, and by photoresist uniform gluing to silicon chip, then toasts; Silicon chip after baking and the pattern on photolithography plate carry out pre-para-position and automatic aligning operation again, and para-position is exposed place after completing Reason, then carries out development treatment, it is thus achieved that pattern is the silicon chip (figure of the equal one array architecture pattern of spacing 4 microns × 4 microns 7), silicon chip carrying out deep silicon etching process subsequently, the deep silicon etching degree of depth is 30 microns, and having obtained etching depth is 10 microns, silicon Intercolumniation is the silicon chip (Fig. 8) of the homogeneous silicon pillar array structure of 4 microns × 4 microns, then crystal film Au is sprayed by magnetron sputtering Penetrating and obtain mould material on the silicon chip of silicon pillar array structure, the electric current of magnetron sputtering is 30mA, and the time of magnetron sputtering is 90s;
The enrichment of step 2, super-hydrophobic molecule concentrates the preparation of chip
The silver nitrate aqueous solution of 2g/L and 4g/L aqueous citric acid solution according to the ratio phase mix homogeneously that volume ratio is 1:1, Obtain electrodeposit liquid;Using the graphite that cleans up as negative pole, mould material, as positive pole, is placed in described electrodeposit liquid use The current response 2 of 200~800mA~obtain the chip (Fig. 9) with nanometer silver silicon pillar array structure for 6 hours, with clear after taking-up Water cleans up, then dries up with pure argon, obtains described super-hydrophobic molecule enrichment and concentrates chip.
Step 3: super-hydrophobic molecule enrichment concentrates the chip application at SERS
With plasma cleaning instrument by clean, to eliminate citric acid for the citric acid cleaning remaining in nanometer silver silicon post array surface The Raman signal interference to testing molecule.Verify the ultra-hydrophobicity (Figure 10) of this substrate with contact angle instrument, its surface can be obtained It is 140 degree with the contact angle of water, belongs to the surface of superhydrophobic property.
The nanometer silver silicon post array chip cleaned up is kept flat on the table, takes 3-5 microlitre testing liquid rhodamine 6G (R6G) chip surface is dropped in, after standing 5-8 minute, the vestige stayed after observing droplet evaporation, use confocal laser Raman spectrum Drop enrichment concentrated area is focused gathering by instrument, carries out SERS detection (Figure 11).
Embodiment 3:
Step one: the preparation of template
The silicon chip cleaned up is carried out tackified finish, and by photoresist uniform gluing to silicon chip, then toasts; Silicon chip after baking and the pattern on photolithography plate carry out pre-para-position and automatic aligning operation again, and para-position is exposed place after completing Reason, then carries out development treatment, it is thus achieved that pattern is the silicon chip (figure of the equal one array architecture pattern of spacing 2 microns × 2 microns 12), silicon chip carrying out deep silicon etching process subsequently, the deep silicon etching degree of depth is 30 microns, and having obtained etching depth is 10 microns, silicon Intercolumniation is the silicon chip (Figure 13) of the homogeneous silicon pillar array structure of 2 microns × 2 microns, then crystal film Au is sprayed by magnetron sputtering Penetrating and obtain mould material on the silicon chip of silicon pillar array structure, the electric current of magnetron sputtering is 30mA, and the time of magnetron sputtering is 90s;
The enrichment of step 2, super-hydrophobic molecule concentrates the preparation of chip
The silver nitrate aqueous solution of 2g/L and 4g/L aqueous citric acid solution according to the ratio phase mix homogeneously that volume ratio is 1:1, Obtain electrodeposit liquid;Using the graphite that cleans up as negative pole, mould material, as positive pole, is placed in described electrodeposit liquid use The current response 2 of 200~800mA~obtain the chip (Figure 14) with nanometer silver silicon pillar array structure for 6 hours, with clear after taking-up Water cleans up, then dries up with pure argon, obtains described super-hydrophobic molecule enrichment and concentrates chip.
Step 3: the enrichment of super-hydrophobic molecule concentrates the SERS application of chip
With plasma cleaning instrument by clean, to eliminate citric acid for the citric acid cleaning remaining in nanometer silver silicon post array surface The Raman signal interference to testing molecule.Verify the ultra-hydrophobicity (Figure 15) of this substrate with contact angle instrument, its surface can be obtained It is 150 degree with the contact angle of water, belongs to the surface of superhydrophobic property.
The nanometer silver silicon post array chip cleaned up is kept flat on the table, takes 3-5 microlitre testing liquid rhodamine 6G (R6G) chip surface is dropped in, after standing 5-8 minute, the vestige stayed after observing droplet evaporation, use confocal laser Raman spectrum Drop enrichment concentrated area is focused gathering by instrument, carries out SERS detection (Figure 16).
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only this Bright preferably embodiment, embodiments of the present invention are also not restricted to the described embodiments, it should be appreciated that people in the art Member can be designed that a lot of other amendments and embodiment, and these amendments and embodiment will fall in principle disclosed in the present application Within scope and spirit.

Claims (9)

1. the preparation method of a super-hydrophobic molecule enrichment concentration chip, it is characterised in that comprise the following steps:
Step A: the silicon chip cleaned up is carried out tackified finish, and by photoresist uniform gluing to silicon chip, then dries Roasting;Silicon chip after baking and the pattern on photolithography plate carry out pre-para-position and automatic aligning operation again, and para-position exposes after completing Optical processing, then carries out development treatment, it is thus achieved that all silicon chips of one array architecture pattern, carries out silicon chip at deep silicon etching subsequently Reason, is obtained the silicon chip of homogeneous silicon pillar array structure, then crystal film Au is injected in by magnetron sputtering the silicon of silicon pillar array structure Mould material is obtained on sheet;
Step B:1~the silver nitrate aqueous solution of 3g/L and 3~5g/L aqueous citric acid solutions are mixed mutually according to the ratio that volume ratio is 1:1 Close uniformly, obtain electrodeposit liquid;Using the graphite that cleans up as negative pole, mould material, as positive pole, is placed in described electricity and sinks In hydrops, electrodeposit reaction obtains the chip with nanometer silver silicon pillar array structure, clean by clean water after taking-up, then with pure Argon dries up, and obtains described super-hydrophobic molecule enrichment and concentrates chip.
Super-hydrophobic molecule enrichment the most according to claim 1 concentrates the preparation method of chip, it is characterised in that described In the silicon chip of silicon pillar array structure, silicon post is 2~5 microns with the gap of silicon post;Silicon column length is 10~50 microns;Described light Pattern magnitude on mechanical is not less than 2.0cm × 2.0cm.
Super-hydrophobic molecule enrichment the most according to claim 1 concentrates the preparation method of chip, it is characterised in that described The electric current of magnetron sputtering is 25~35mA, and the time of magnetron sputtering is 80~100s.
Super-hydrophobic molecule enrichment the most according to claim 1 concentrates the preparation method of chip, it is characterised in that described Electrodeposit reaction is current response 2~6 hours under electric current is 200~800mA.
5. one kind according to the super-hydrophobic molecule enrichment described in any one of claim 1-4 concentrate chip preparation method preparation and The super-hydrophobic molecule enrichment obtained concentrates chip, it is characterised in that it is square that described super-hydrophobic molecule enrichment concentrates chip Or the nanometer silver silicon post of hexagon uniform array lattice structure arrangement, described nanometer silver silicon post is uniformly to wrap up nanometer on silicon post Silver, nanometer silver is the lamellar structure of 1~2 micron, and nanometer silver silicon post is 12~55 microns, the rule of a diameter of 2~5 microns of height Whole column, the gap between nanometer silver silicon post is 8~12nm.
Super-hydrophobic molecule enrichment the most according to claim 5 concentrates chip, it is characterised in that described super-hydrophobic dividing Son enrichment concentrates chip and has super-hydrophobic effect, with contact angle >=140 ° of water.
7. the super-hydrophobic molecule enrichment described in claim 5-6 concentrates the chip application at SERS, it is characterised in that include with Lower step: concentrate the citric acid cleaning of chip surface totally, so by remaining in super-hydrophobic molecule enrichment with plasma cleaning instrument After the super-hydrophobic molecule enrichment cleaned up concentrated chip put on the table, take 3~5 microlitre testing liquids and drop in chip list Face, stands 5~8 minutes, the vestige stayed after observing droplet evaporation, concentrates drop enrichment with confocal laser Raman spectrometer Region is focused gathering, and carries out SERS detection.
Super-hydrophobic molecule enrichment the most according to claim 7 concentrates the chip application at SERS, it is characterised in that to be measured Liquid is the one being dissolved in water or water-fast explosive, organic pollution, organic dyestuff, drug molecule.
Super-hydrophobic molecule enrichment the most according to claim 7 concentrates the chip application at SERS, it is characterised in that work as institute When the testing liquid stated is water-fast liquid, testing liquid is acidified or alkalizes and become soluble-salt and carry out again Detection.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108895690A (en) * 2018-07-05 2018-11-27 南京大学 A kind of silicon-based semiconductor-metal nanometer composite material and preparation method thereof
CN109975270A (en) * 2019-04-12 2019-07-05 北京师范大学 A kind of silver nano flower-like periodic array SERS substrate and preparation method thereof
CN110170747A (en) * 2019-06-24 2019-08-27 吉林大学 A kind of bionic coupling catchments the preparation method on the anti-icing surface of aluminium alloy
CN112744783A (en) * 2021-01-06 2021-05-04 南京大学 Preparation method of super-hydrophobic and super-oleophobic surface with micro-nano composite structure
CN113620236A (en) * 2020-05-06 2021-11-09 中国科学院微电子研究所 Array preparation method of organic semiconductor material
CN114324290A (en) * 2021-12-27 2022-04-12 山东大学 Preparation method of bionic-based super-hydrophobic integrated chip, SERS platform and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101281133A (en) * 2008-05-12 2008-10-08 中国科学院合肥智能机械研究所 Preparation of surface reinforced Raman active substrate of large area micro-nano dendritical structure array
CN101475173A (en) * 2009-01-20 2009-07-08 吉林大学 Method for preparing super-hydrophobic antireflex micron and nano composite structure surface
CN103868909A (en) * 2014-03-14 2014-06-18 厦门大学 Mushroom array type surface enhanced Raman spectrum active substrate and preparation method thereof
CN103885300A (en) * 2014-03-19 2014-06-25 南京晶奥微光电技术有限公司 Hydrophobic surface photoetching process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101281133A (en) * 2008-05-12 2008-10-08 中国科学院合肥智能机械研究所 Preparation of surface reinforced Raman active substrate of large area micro-nano dendritical structure array
CN101475173A (en) * 2009-01-20 2009-07-08 吉林大学 Method for preparing super-hydrophobic antireflex micron and nano composite structure surface
CN103868909A (en) * 2014-03-14 2014-06-18 厦门大学 Mushroom array type surface enhanced Raman spectrum active substrate and preparation method thereof
CN103885300A (en) * 2014-03-19 2014-06-25 南京晶奥微光电技术有限公司 Hydrophobic surface photoetching process

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CHI-CHING CHANG ET AL.: "Surface-enhanced Raman scattering on a silver film-modified Au nanoparticle-decorated SiO2 mask array", 《RSC ADVANCES》 *
F. DE ANGELIS ET AL.: "Breaking the diffusion limit with super-hydrophobic delivery of molecules to plasmonic nanofocusing SERS structures", 《NATURE PHOTONICS》 *
F. GENTILE ET AL.: "Nanoporous- micropatterned- superhydrophobic surfaces as harvesting agents for few low molecular weight molecules", 《MICROELECTRONIC ENGINEERING》 *
FUGANG XU ET AL.: "Silver Nanoparticles Coated Zinc Oxide Nanorods Array as Superhydrophobic Substrate for the Amplified SERS Effect", 《J. PHYS. CHEM. C》 *
HAIBIN TANG ET AL.: "Arrays of Cone-Shaped ZnO Nanorods Decorated with Ag Nanoparticles as 3D Surface-Enhanced Raman Scattering Substrates for Rapid Detection of Trace Polychlorinated Biphenyls", 《ADV. FUNCT. MATER》 *
吴建刚等: "用于微流控芯片系统的超疏水表面的制备", 《微细加工技术》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108895690A (en) * 2018-07-05 2018-11-27 南京大学 A kind of silicon-based semiconductor-metal nanometer composite material and preparation method thereof
CN108895690B (en) * 2018-07-05 2019-06-25 南京大学 A kind of silicon-based semiconductor-metal nanometer composite material and preparation method thereof
CN109975270A (en) * 2019-04-12 2019-07-05 北京师范大学 A kind of silver nano flower-like periodic array SERS substrate and preparation method thereof
CN110170747A (en) * 2019-06-24 2019-08-27 吉林大学 A kind of bionic coupling catchments the preparation method on the anti-icing surface of aluminium alloy
CN113620236A (en) * 2020-05-06 2021-11-09 中国科学院微电子研究所 Array preparation method of organic semiconductor material
CN112744783A (en) * 2021-01-06 2021-05-04 南京大学 Preparation method of super-hydrophobic and super-oleophobic surface with micro-nano composite structure
CN112744783B (en) * 2021-01-06 2024-04-09 南京大学 Preparation method of super-hydrophobic and super-oleophobic surface with micro-nano composite structure
CN114324290A (en) * 2021-12-27 2022-04-12 山东大学 Preparation method of bionic-based super-hydrophobic integrated chip, SERS platform and application
CN114324290B (en) * 2021-12-27 2023-07-25 山东大学 Preparation method of bionic-based super-hydrophobic integrated chip, SERS platform and application

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