CN1470867A - Electrochemical detection-micro fluid control chip,and manufacturing method and regeneratnig method thereof - Google Patents
Electrochemical detection-micro fluid control chip,and manufacturing method and regeneratnig method thereof Download PDFInfo
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Abstract
Microflow controlled channels are formed by aligning the silicone rubber dimethyl silicone polymer substrate containing micro channels with the electrode bars on the slide glass. The interval between the exit of micro channel and the detection electrode is 20-60 micros. Electrochemistry testing mode is styletable test. Width of micro channel is 20-100 micros. The invention uses commercial chromium plate glass as the material. The glass hard template is produced through photoetching and wet eroding techniques and utilized in moulding PDMS so as to obtain micro channels and soft template, which are needed for preparing the chip and electrode. The said glass hard template can be used repeatedly. Thus, the sizes of PDMS micro channels produced are uniform with good shape repeatability.
Description
Technical field
The present invention relates to a kind of Electrochemical Detection-micro-fluidic chip.
The invention still further relates to the method for making of above-mentioned Electrochemical Detection-micro-fluidic chip.
The invention still further relates to the renovation process of above-mentioned Electrochemical Detection-micro-fluidic chip.
Background technology
Micro-fluidic chip is the analytical technology of a novelty, different with the situation of conventional analysis instrument function singleness, it is integrated in one only on the chip of several centimeter square with numerous analysis process such as sample collecting, pre-service, separation, detection etc., can finish from actual sample in a short period of time to the overall process that obtains analysis result, required sample size, consumption reagent, generation discarded object are less than conventional analysis far away, can be implemented in real-time, on-the site analysis under various condition.Because of its outstanding advantage, obtain numerous researchers' concern.The chip manufacturing material is a lot, and quartz, glass, organic polymer etc. are arranged.Early stage work glass or the quartz materials of using more, the glass-chip commercial as Canadian Micralyne company makes, via photoetching, wet etching, steps such as elevated temperature heat bonding (the Anal Chem that is made, 2001,73,4079-4086), the technological process complexity, the manufacturing conditions harshness, the cost height costs an arm and a leg.On the other hand, detecting device also is the emphasis of research as an important component part of this system.Electrochemical detector because simple in structure, cost is low, highly sensitive, easy plurality of advantages such as integrated and develop into a kind of important detection method on the micro-fluidic chip.At present, the making of electrochemical detection electrode commonly used is adopted is vacuum coating-photoetching-corroding method in the electronics industry, electrochemical gaging device on the capillary electrophoresis chip that is integrated in micro-manufacturing is disclosed as patent 97197445.4, at evaporation one deck platinum layer on glass, obtain little pattern of platinum electrode through photoetching process, the glass of the microchannel that makes of light lithographic method with another sheet is thermal bonding at high temperature, obtains containing the Electrochemical Detection-micro-fluidic chip of integrated platinum electrode.This method is made the overall flow complexity; to the equipment requirements height; and need through elevated temperature heat bonding step; electrode material must be able to tolerate the high temperature more than 600 degrees centigrade; under this condition, also must prevent the oxidation of electrode material,, then must adopt inert atmosphere protection some more active metal electrode material; further strengthened the expense of equipment and operation, and it is not high to make whole success ratio.
Summary of the invention
The objective of the invention is to design a kind of Electrochemical Detection-micro-fluidic chip;
Another object of the present invention provides the method for making of said chip;
Another purpose of the present invention provides the renovation process of said chip.
The present invention realizes above-mentioned purpose like this:
High polymer material is more and more paid attention to because it is with low cost, making is easy, wherein uses wider with silicon rubber dimethyl silicone polymer (PDMS).The present invention is a material with commercial chromium plate glass, produces the glass hard template by photoetching and wet corrosion technique, is used for the molded of PDMS, makes the soft template of forming the required microchannel of micro-fluidic chip and being used to make electrode.This glass hard template can be used in operation repeatedly, the little channel dimensions homogeneous of the PMDS of making, shape favorable reproducibility.
The present invention has chosen and has needed the active catalytic particle to induce the electroless plating reaction that could take place in making the electrode operation.Characteristics a little less than utilizing the glass flat surfaces to the particle adhesion, in overwhelming majority zone, can't the enough catalysed particulates of load, electroless plating can't be carried out; At regional area, under the help of the PDMS soft template that contains little pattern, can carry out optionally roughening treatment to microslide, so that the enough surface area particle of inducing in conjunction with activation to be provided, the electroless plating of carrying out then, it is smooth that only this fractional load has the electroless plating reaction of activation particle, deposited thus as the required layer electrodes of Electrochemical Detection.
Utilize PDMS can with the characteristic of flat surfaces reversible keying, the PDMS that is manufactured with little raceway groove is fitted to containing the microslide of having made microelectrode, form the electrophoresis microchannel, form micro-fluidic chip thus.
Electrochemical Detection adopts the styletable detecting pattern, and electrochemical detection electrode can effectively reduce the influence of electrophoretic separation high pressure to Electrochemical Detection apart from electrophoresis microchannel endpiece 20-60 micron, has avoided the process of the making high pressure isolation ground connection of trouble again.
Micro-fluidic chip-electrochemical detection system that this method makes is few to equipment requirements, the committed step of operation at room temperature can be finished, the success ratio height, can be used for the making of multiple material electrode, the gained coating adhesion is strong, and after the electrode inactivation, can regenerate through electroless plating again, life cycle is long, and is widely applicable.
Concrete operations are as follows
1) method of molding is made the hard template that the PDMS soft template is used to make microfluidic channel and soft template and is made by photoetching process, and adopting the chromium plate glass that scribbles photoresist is starting material.Draw micro-fluidic chip stream and electrode pattern and it is printed on the cushion compound, the width of electrophoresis path generally between the 20-100 micron, electrode working portion width 20-100 micron, the coupling part is wideer, the 200-500 micron is so that be connected preferably between working electrode and the Electrochemical Detection instrument.Pattern passes through the uviol lamp exposure projections to the optical cement layer, develop again, with 150-200 grams per liter ammonium ceric nitrate, 30-50 milliliter/rise acetic acid or 120-180 grams per liter ammonium ceric nitrate, 10-20 milliliter/rise salpeter solution to remove the chromium layer that exposes, with residual optical cement and chromium layer is shielding, use 12-30 grams per liter hydrofluorite, 20-30 grams per liter ammonium fluoride or 10-20 grams per liter hydrofluorite, 10-20 grams per liter salpeter solution to glass corrosion 15-25 minute, produce little pattern, obtain hard template.In the moulding process PDMS monomer is mixed in 10: 1 ratio with hardening agent,, remove the gas that produces in the cross-linking reaction, be poured into again on the glass hard template,, make its curing 60-70 degree centigrade of heating 1.5-2 hour through the vacuum pump vacuumize degassing.After finishing, crosslinked PDMS layer is peeled off from hard template, the soft template that promptly obtains the required little raceway groove of micro-fluidic chip and make electrode, channel end is with the card punch punching of 2-5 millimeter, as liquid storage tank.
2) microslide is got in the selectivity alligatoring, through with chromic acid lotion or volume ratio being 3: 1 H
2SO
4/ H
2O
2Washing lotion is cleaned, and cleans with deionized water, and dries.The PDMS soft template that makes and microslide are fitted, thereby form as the microchannel of electrode pattern, drip the sodium silicate solution of a small amount of 2-4% at the channel end liquid storage tank, solution enters the microchannel under capillary action, and it is full of, the removal redundant solution.Substrate was left standstill 6-8 hour together with the PDMS room temperature, allow solution air dry in the passage.Throw off the PDMS template, sodium silicate is stayed on the substrate, and substrate is placed in the heating furnace 150-250 degree centigrade of heating 20-40 minute, makes this part sodium silicate curing molding, takes out the alligatoring part that promptly obtains as electrode shape.
3) the electroless plating electroless plating adopts 10-20 grams per liter stannous chloride, be sensitizer sensitization 2-5 minute, for preventing the oxidation of stannous ion, can add small amount of hydrochloric acid and tin metal particle, 1-3 grams per liter silver nitrate, dropping ammonia is activator activation 2-4 minute to producing the precipitation silver-colored ammonium salt solution of configuration that disappears again, is catalytic center with the silver-colored particle that generates, and carries out electroless copper.Between sensitization/silver-colored ammonium activation/electroless copper step, microslide is adsorbed on the small amount of residual particle of smooth surface through deionized water supersound washing 10-20 second with removal.Copper facing is containing 5-8 gm/litre copper sulphate, 2.5-3 grams per liter nickel chloride, 28-35 milliliter/rise in the solution of formalin, 6-12 grams per liter NaOH, 20-35 grams per liter sodium potassium tartrate tetrahydrate, under the situation of constantly stirring, carry out electroless copper, 30-45 minute, obtain copper film as the soft template pattern, thickness 100-300 nanometer, this copper film can be used as the copper electrode that Electrochemical Detection is used.
Further, the copper layer that can make is the basis, use is by 2.5-3.5 grams per liter gold sodium sulfide, 15-20 grams per liter sodium sulphite, 40-60 milliliter/rise the gold plating liquid that formalin is formed, under the situation of constantly stirring, with copper is catalyzer, proceed chemical gilding thereon, can obtain the golden film of thick approximately 150-300 nanometer in 20-40 minute, can be used as the gold electrode of Electrochemical Detection.
4) micro-fluidic chip-electrochemical detection system PDMS substrate that will contain little raceway groove aligns with electrode strip on the microslide at microscopically, form reversible keying, form micro-fluidic-Electrochemical Detection chip, distance is at the 20-60 micron between outlet of control electrophoresis path and the detecting electrode, and Electrochemical Detection is the styletable detecting pattern.
5) behind the electrode inactivation, open the PDMS layer, the microslide top electrode is removed, after cleaning, carry out electroless plating again, electrode is regenerated, and electrode pattern is with original consistent with corrosive liquid.
Description of drawings
Fig. 1 is for making the mask plate pattern of electrophoresis microchannel, and wherein the right side is the enlarged diagram of infall passage
Fig. 2 be used to make microelectrode the pattern of soft template, its middle and lower part be in the middle of the enlarged diagram of outshot
Fig. 3 is the synoptic diagram of the micro-fluidic chip of composition, and the right side is the enlarged diagram of electrode and channel outlet part.
Embodiment
Embodiment 1
1, make PDMS microchannel and soft template
Draw microfluidic circuit figure and electrode shape respectively as Fig. 1 and Fig. 2 with vector plotting software (CorelDraw), (3000dpi) exports film to by the high definition laser photocomposing machine, get film, it is on glass to cover the chromium plate that is coated with optical cement, expose through uviol lamp, after the development of 0.6% sodium hydroxide solution, 180 grams per liter ammonium ceric nitrates, 40 milliliters/rise acetum to dechromise 55 seconds, clean clean, place 1.7% hydrofluorite, in the 2.3% ammonium fluoride damping fluid, speed with 0.7 micron per minute is corroded the glass part that exposes, and obtains little pattern of projection, the required glass template corrosion of micro-fluidic chip passage 20 minutes, be used to make the corrosion 3 minutes of electrode soft template, corrosion finishes, and removes unnecessary optical cement with 2% sodium hydroxide solution, and the liquid that dechromises is removed the chromium layer.The glass template is cleaned, and dries.Be used for dark 15 microns of the microchannel of electrophoretic separation, top the widest part is 60 microns, and 40 microns at the narrowest place, bottom is used to make dark 2 microns of the soft template microchannel of microelectrode.
PDMS monomer and crosslinking chemical stirred evenly with 10: 1 abundant mixing, outgased under vacuum, generated to there being gas, potpourri is poured into the glass template surface, and places baking oven, and 65 degrees centigrade were heated 2 hours.After being cooled to room temperature, carefully use blade cuts PDMS, and it is peeled off from the glass template, promptly obtain little raceway groove of PDMS and soft template.Stamp the hole of 2.5mm diameter as liquid storage tank at channel end with card punch.
2, make integrated Electrochemical Detection copper electrode
Get the microslide of cleaning once chromic acid lotion, deionized water, in the terminal PDMS soft template that contains the little pattern of electrode that covers step 1 preparation of one, PDMS and glass reversible keying, form the microchannel, add 2% sodium silicate solution from the liquid storage tank of accomplishing fluently, solution is full of whole passage automatically under capillary action.Room temperature is placed and was dried in 6 hours.Throw off the PDMS soft template, obtain sodium silicate coating, microslide is placed in the heating furnace 170 degrees centigrade of heating 30 minutes as required electrode pattern at glass surface.After being chilled to room temperature, washed with de-ionized water is clean, be dipped in 15 grams per liter stannous chlorides, 10 milliliters/rise concentrated hydrochloric acid, and added in the sensitized solution that a small amount of tin grain forms 3 minutes, after fully cleaning with deionized water, ultrasonic cleaning 10 seconds, place by 1.5 grams per liter silver nitrates, dropping ammonia was soaked 3 minutes to producing in the precipitation silver ammino solution that disappearance is configured to again again, can see the part that originally was coated with sodium silicate and generate sepia silver particle, continuation is cleaned with deionized water, ultrasonic cleaning 10 seconds, microslide is placed 1: 1 of firm mixing 6.0 gm/litre copper sulphate that contain, 3.0 grams per liter nickel chloride A solution and contain 32 milliliters/rise formalin, 10 grams per liter NaOH, in the B solution of 30 grams per liter sodium potassium tartrate tetrahydrates, under the situation of constantly stirring, carry out electroless copper, 45 minutes, obtain copper film as the soft template pattern, thickness is about 200 nanometers, and this copper film can be used as the copper electrode that Electrochemical Detection is used.
3, form micro-fluidic-Electrochemical Detection chip and practical application
Alignd with the microslide that contains electrochemical detection electrode in the PDMS microchannel, make electrode be arranged in the detection cell of micro-fluidic chip, apart from 40 microns of split tunnel outlets, as shown in Figure 3, both fit, PDMS and smooth slide surface reversible keying form the electrophoresis microchannel, and Electrochemical Detection is the styletable detecting pattern.This chip can be under strong alkaline condition, and directly the ampere method is used for the compartment analysis of glucide or amino acids material
4, the processing again behind the electrode inactivation
Behind the electrode inactivation, microslide can be peeled off with PDMS, electrode part copper layer is with 1: 1: 2 hydrochloric acid/hydrogen peroxide/water solution corrosion 3 minutes, after cleaning up, by sensitization as previously mentioned, induce, the electroless plating step, can obtain and the former electrode pattern of basically identical.The PDMS layer cleaned dry, both bondings that align are again reformulated Electrochemical Detection-micro-fluidic chip.
Embodiment 2
1, make PDMS soft template and microchannel chromium plate glass after using the mask plate photoetching, develop with 0.6% sodium hydroxide solution, 160 grams per liter ammonium ceric nitrates, 20 milliliters/rise salpeter solution to dechromise, clean clean, place 15 grams per liter hydrofluorite, in the 15 grams per liter salpeter solutions, speed with 0.8 micron per minute is corroded the glass part that exposes, obtain little pattern of projection, the required glass template of micro-fluidic chip passage corrosion 15 minutes is used to make the corrosion 2 minutes of electrode soft template, and corrosion finishes, remove unnecessary optical cement with 20 grams per liter sodium hydroxide solutions, the liquid that dechromises is removed the chromium layer.The glass template is cleaned, and dries.PDMS precursor that mixes and hardening agent are poured on the template through vacuum outgas, and reaction 1.5 hours is heating and curing under 70 degrees centigrade.Peel off the PDMS layer, be used for dark 12 microns of the microchannel of electrophoretic separation, top the widest part is 60 microns, 45 microns at the narrowest place, bottom.Be used to make dark 1.5 microns of the soft template microchannel of microelectrode
2, make integrated gold electrode: getting a microslide, is 3: 1 H through volume ratio
2SO
4/ H
2O
2Washing lotion, deionized water are cleaned, and cover the PDMS soft template thereon, via aforesaid alligatoring, sensitization, induce, the copper facing step, generate copper film, but the copper facing step was only carried out thick 150 nanometers of copper film 25 minutes as electrode shape.This microslide is placed by 2.8 grams per liter gold sodium sulfides, 16 grams per liter sodium sulphites, 50 milliliters/rise in the gold plating liquid of formalin composition, under the situation of constantly stirring, with copper is catalyzer, proceed chemical gilding thereon, can obtain the golden film of thick approximately 200 nanometers in 30 minutes, can be used as the gold electrode of Electrochemical Detection.
3, form micro-fluidic chip electrochemical detection system and application thereof
The PDMS layer that contains the electrophoresis microchannel forms reversible keying with to contain the microslide card of having made electrode tight, and the distance of gold electrode and channel exit is controlled at 50 microns.This chip can be under neutrallty condition, and directly the ampere method detects the pyrocatechol material, also can be under the meta-alkalescence condition, and pulse ampere method is used for separating and detecting carbohydrate and amino acid.
4, the processing again behind the electrode inactivation
Behind the electrode inactivation, microslide can be peeled off with PDMS, be eroded layer electrodes with chloroazotic acid, by sensitization as previously mentioned, induce, the electroless plating step, can obtain and the former gold electrode pattern of basically identical.The PDMS layer cleaned dry, both bondings that align are again reformulated Electrochemical Detection-micro-fluidic chip.
Claims (8)
1, a kind of Electrochemical Detection-micro-fluidic chip, to contain the silicon rubber dimethyl silicone polymer substrate of little raceway groove aligns with electrode strip on the microslide, form microfluidic channel, distance is the 20-60 micron between microchannel outlet and the detecting electrode, and Electrochemical Detection is the styletable detecting pattern.
2, Electrochemical Detection-micro-fluidic chip as claimed in claim 1 is characterized in that, the width of described microfluidic channel is the 20-100 micron, and electrode working portion width is the 20-100 micron, and the coupling part width is the 200-500 micron.
3, a kind of method for preparing claim 1 or 2 described Electrochemical Detection-micro-fluidic chips, its key step is:
A) make silicon rubber dimethyl silicone polymer soft template: the hard template that is used to make microfluidic channel and soft template is made by photoetching process, the chromium plate glass that employing scribbles photoresist is starting material, draw micro-fluidic chip stream and electrode pattern and it is printed on the cushion compound, with it is mask plate, exposure, develop, with 150-200 grams per liter ammonium ceric nitrate, 30-50 milliliter/rise acetic acid or 120-180 grams per liter ammonium ceric nitrate, 10-20 milliliter/rise salpeter solution to remove the chromium layer that exposes, with residual optical cement and chromium layer is shielding, use 12-30 grams per liter hydrofluorite, 20-30 grams per liter ammonium fluoride or 10-20 grams per liter hydrofluorite, 10-20 grams per liter salpeter solution to glass corrosion 15-25 minute, produce little pattern, obtain hard template;
Silicon rubber dimethyl silicone polymer monomer is mixed in 10: 1 ratio with hardening agent,, remove the gas that produces in the cross-linking reaction, be poured into again on the glass hard template,, make its curing 60-70 degree centigrade of heating 1.5-2 hour through the vacuum pump vacuumize degassing; After finishing, crosslinked silicon rubber dimethyl silicone polymer layer is peeled off from hard template, the soft template that promptly obtains the required little raceway groove of micro-fluidic chip and make electrode, channel end is with the card punch punching of 2-5 millimeter, as liquid storage tank;
B) selectivity alligatoring: silicon rubber dimethyl silicone polymer soft template and microslide that step a makes are fitted, form microfluidic channel, drip the sodium silicate solution of a small amount of 2-4% at the channel end liquid storage tank, solution enters microfluidic channel under capillary action, and it is full of, remove redundant solution;
Substrate was left standstill 6-8 hour together with silicon rubber dimethyl silicone polymer room temperature, make solution air dry in the passage; Throw off silicon rubber dimethyl silicone polymer template, sodium silicate is stayed on the substrate, with substrate in heating furnace 150-250 degree centigrade the heating 20-40 minute, make this part sodium silicate curing molding;
C) electroless plating: it is sensitizer sensitization 2-5 minute that electroless plating adopts stannous ion, and silver-colored ammonium salt solution is activator activation 2-4 minute, is catalytic center with the silver-colored particle that generates, and carries out electroless copper;
Copper facing is containing 5-8 gm/litre copper sulphate, 2.5-3 grams per liter nickel chloride, 28-35 milliliter/rise in the solution of formalin, 6-12 grams per liter NaOH, 20-35 grams per liter sodium potassium tartrate tetrahydrate, stirred 30-45 minute, obtain copper film as the soft template pattern, thickness 100-300 nanometer, this copper film are the copper electrode that Electrochemical Detection is used;
D) micro-fluidic chip-electrochemical detection system: will contain the silicon rubber dimethyl silicone polymer substrate of little raceway groove and align, and form reversible keying, and form Electrochemical Detection-micro-fluidic chip with electrode strip on the microslide.
4, method as claimed in claim 3 is characterized in that, described sensitizer is a 10-20 grams per liter stannous chloride.
As claim 3 or 4 described methods, it is characterized in that 5, described sensitizer is to add hydrochloric acid and tin metal particle in stannous chloride.
6, method as claimed in claim 3 is characterized in that, described activator is a 1-3 grams per liter silver ammonium salt solution.
7, method as claimed in claim 3, it is characterized in that, the described copper layer of step c is the basis, use is by 2.5-3.5 grams per liter gold sodium sulfide, 15-20 grams per liter sodium sulphite, 40-60 milliliter/the rise gold plating liquid that formalin is formed, stirred 20-40 minute, with copper is catalyzer, obtains the golden film of thick 150-300 nanometer, can be used as the gold electrode of Electrochemical Detection.
8, a kind of method that the described electrode of above-mentioned each claim is regenerated behind the electrode inactivation, is opened silicon rubber dimethyl silicone polymer layer, with corrosive liquid the microslide top electrode is removed, and after cleaning, carries out electroless plating again.
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