CN100485377C - Glass-chip for flowing minisize electrolyzer and manufacturing method thereof - Google Patents
Glass-chip for flowing minisize electrolyzer and manufacturing method thereof Download PDFInfo
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- CN100485377C CN100485377C CNB2006100477374A CN200610047737A CN100485377C CN 100485377 C CN100485377 C CN 100485377C CN B2006100477374 A CNB2006100477374 A CN B2006100477374A CN 200610047737 A CN200610047737 A CN 200610047737A CN 100485377 C CN100485377 C CN 100485377C
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Abstract
A glass chip mobile micro electrolytic cell includes the electrode, micro-electrolytic cell channel, solution channel, solution inlet and outlet, cover piece and substrate, electrode channel, electrode positioning ridge, electrode doors. On the substrate or on the substrate and the cover are synchronously etched with a micro electrolytic cell channel and electrode channel, the connection part of the two channels forms the electrode positioning ridge. Use glass lithography method and the heat integration to make chip usually. Electrodes are lead in from the side of the chip and positioned in the electrode channel. The volume of the micro mobile cell is Nano litre grade so the reagent consumption is low. The electrodes are separated without film because of lamina flow action of the channel. Advantages: dismounting and changing electrode is convenient, chip can be repeatedly used and electrode configuration is agility.
Description
Technical field
The invention belongs to crossing domains such as MEMS (micro electro mechanical system) (MEMS), galvanochemistry, analyzing and testing and chemosynthesis, relate to the micro cell chip and preparation method thereof that flows.
Background technology
Micro-fluidic (Microfluidics) chip technology grows up on MEMS (micro electro mechanical system) (MEMS) and microelectronics processing basis, be intended to analytic system integrated to form micro-total analysis system (Micro-TAS), thereby reach system's microminiaturization, purposes such as the usefulness of raising system and saving reagent.Electrochemical detection method is because simple, sensitivity, and integrated easily, therefore tool forms the potentiality of micro-full analytical system, has obtained extensive studies and application as the electrochemical detector of chip electrophoresis.Electrochemical luminescence method receives much concern because of it is highly sensitive, and is particularly extensive in aspect application prospects such as biochemical analysis detection and environmental analyses.Carrying out little synthetic reaction on chip also is one of focus of micro-fluidic chip technology application, and wherein galvanochemistry is synthetic is a direction with important science and actual application prospect.
Common electro-chemical systems carries out in bigger container, and volume is usually more than the milliliter level.Often need increase stirring condition in order to improve mass transfer.In order to prevent working electrode and utmost point galvanochemistry product to be mixed mutually and interference, need special membrane material to isolate therebetween usually, guarantee the unobstructed of electric current simultaneously again.For the current potential that makes working electrode is controlled effectively, reduce voltage drop simultaneously, require to introduce contrast electrode also as far as possible near working electrode.
Micro-fluidic chip electrolytic cell yardstick is compared very little with common electrolysis pool volume, receiving upgrading usually.Solution can make horizontal mass transfer improve in flow process.Because working fluid duty many places are at laminar flow in the microchannel, and vertically mass transfer is very limited, can realize that therefore no film is isolated between electrode simultaneously.Therefore be that an important technology improves with electrolytic cell chipization and liquidation.
How to introduce microelectrode and accurately locate in chip microchannel is an important technology difficult problem that limits this technical development always.Adopt the microcell activation or electrode material is deposited to substrate surface, adopting photoetching to position again is a kind of method that often adopts.The chip with electrode that exists mostly is compound chip at present, for example the chip of polymkeric substance and the compound preparation of inorganic material.Base material processing such as employing polymkeric substance are relatively easy, but intensity is not good enough, and surface nature is generally hydrophobic, and unstable, easily absorb organic molecule (Anal Chem, 2005,77,1414).Glass is a kind of welcome base material, because its etching technics is simpler, and the physical strength height, transparent, electrical isolation and good heat conductivity.Existing method at glass surface processing microelectrode is mainly based on the surface deposition conductive material, for example spatters if various metals of evaporation or conductive oxide (for example ITO), again by method moulding such as photoetching.This method has higher precision, but the method complexity is loaded down with trivial details, and relies on Special Equipment especially.And the surface has the glass baseplate of electrode structure to be difficult to encapsulate the chip that the existing microchannel of formation has microelectrode again, though under the temperature conditions that is higher than the glass fusing point, can realize involution (Anal.Chem.2001,73,3282-3288), but cause the distortion of micro channel systems easily.The method of introducing electrode by the chip sides passage is also arranged, but electrode can only be introduced, can not guarantee the accurate location (LabChip, 2005,5,711) in the microchannel.Utilize the method for microchannel on the organic glass chip, to introduce thread metal electrode and can realize that the chip electricity leads detection (Electrophoresis 2002,23,3760), but method relates to the Special Equipment of high-aspect-ratio process technology and complex and expensive.Because galvanochemistry itself, electrode surface changes easily in electrolysis and testing process, and electrode is handled and upgraded also is a frequent operation.Membrane electrode can not be changed processing, and therefore relevant chip can only disposablely use usually.Can be convenient for changing and locate microelectrode little electrolysis chip no matter for research with use and all have very big Practical significance.
Summary of the invention
The weak point of introducing microelectrode and carrying out the accurate positioning method existence in chip microchannel at present existence the invention provides a kind of mobile micro cell glass-chip and preparation method thereof.
The present invention is base material with glass, on glass baseplate, form Micro Channel Architecture with general wet method photoetching and heat sealing method, microelectrode can be behind the chip involution by the electrode channel micro cell passage of packing into, need not special locating device, microelectrode can be changed, realized the chipization of electrolytic cell, liquidation has solved the interference problem between the electrode product when improving mass transfer.Can also make the chip electrochemical detection cell that is used for various objectives as required based on this method.
At first introduce the structure of chip, as shown in Figure 1.Chip comprises electrode 1, micro cell passage 2, and electrode channel 3, fluid sealant 4, electrode processing ridge 5, solution channel 6, solution imports and exports 7, cover plate 8, substrate 9, electrode imports and exports 10.Be carved with micro cell passage 2 and electrode channel 3 on the substrate 8 or on substrate 8 and the cover plate 9 simultaneously, micro cell passage 2 and electrode channel 3 junctions constitute electrode processing ridge 5, at the two ends of micro cell passage 2 solution channel 6 is arranged, the solution that chip surface or chip sides perforate formation are connected with solution channel imports and exports 7, the port of electrode channel 3 is that electrode imports and exports 10, and electrode is imported and exported 10 places and sealed with fluid sealant 4.
Wire electrode (metal or carbon fiber electrode) is introduced and is positioned at the electrode channel from chip sides through electrode channel; When making positioning of electrode, the ridge-like structure that etching forms keep electrode to be communicated with solution in the electrolytic cell passage; Electrolyte solution is imported and exported the hole by the chip normal direction, or by chip sides and external communications; The import or export of electrolyte solution has one or more; Electrolyte solution is by micro cell passage or electrode channel turnover micro cell.
The method for making of chip adopts the common glass photomask and the method for heat sealing to carry out.At first utilize figure to generate the software design mask graph, shown in Fig. 2 (a).Mask graph utilizes laser photocomposing machine to print to the mask that (low precision mask) formation is made up of printing opacity and lightproof part on the mylar, shown in Fig. 2 (b).Form mask for the high precision microstructure with pattern generator.For the microstructure more than 40 microns, print the black and white film mask with the laser photocomposing machine that resolution 3500dpi is above.Mask graph is transferred on the chromium plate glass substrate that scribbles optical cement by exposure machine.Optical cement removes the sacrifice layer of exposure after development and post bake processing, carry out the Micro Channel Architecture that etching forms to be needed in glass etching liquid.Remove all the other optical cements and sacrifice layer after etching is finished, punch with methods such as emery or ultrasound waves at the solution import and export.Glass surface to be sealed is carried out activation processing, fit in the deionization current, in muffle furnace, add heat sealing behind the hot blast drying.Fig. 2 (c) shown with Fig. 2 (b) shape mask glass carried out two positioning of electrode ridge structures that wet etching obtains, and can will introduce to such an extent that two wire electrodes are positioned at the both sides of micro cell by electrode channel.The location ridge is a raised structures parallel with electrode channel with the micro cell passage, and its height is less than the connection with maintenance electrode channel and micro cell passage of the degree of depth of micro cell passage and electrode channel; The degree of depth of micro cell passage and the diameter of ridge high difference in location less than wire electrode, thus with electric limit built in given position, shown in Fig. 1 (b).The degree of depth of micro cell passage and electrode channel and ridge height are controlled by mask size design and etching degree.
The introducing of electrode has two kinds of methods.A kind of is that the electrode channel outlet behind the alignment involution is carried out the etching reaming with glass etching liquid commonly used, makes to export into bell mouth shape, and electrode is introduced electrode channel by this mouth, as shown in Figure 3.Another kind method is, will be up and down during involution two staggered, the electrode channel outlet is exposed, electrode inserts electrode channel along the passage that exposes, as shown in Figure 4.Behind the positioning of electrode in the exit with fluid sealant (organic gel commonly used or wax) involution.When changeing electrode, add the heat abstraction sealing wax; Or in muffle furnace 450 degrees centigrade of following heating and decomposition organic gel; Or under spirit lamp flame, behind the heating burning-off fluid sealant chip is soaked in and soaked in the concentrated sulphuric acid washing lotion 1～24 hour, electrode is reinstalled or changed to back water cleaning with the method for introducing previously then.
The electrolytic cell chip that should flow has following characteristics:
1. flow and itself have the effect that improves electrode tangential direction mass transfer;
2. only for receiving upgrading, reagent consumption is few for miniature flow cell volume;
3. approaching to the utmost point and working electrode distance, voltage drop is little;
4. can form two electrode systems with reference with to the method for utmost point unification;
5. because doing available realization, the laminar flow of passage do not have the film isolation between the electrode;
6. the glass-chip electrolytic cell transparency is good, for condition has been created in Optical Electro-Chemistry research;
7. electrode dismounting and replacing are convenient, and chip is reusable;
8. the electrode flexible configuration is convenient.
Description of drawings
The little electrolysis chip structure of Fig. 1 synoptic diagram.(a) little electrolysis chip schematic top plan view; (b) micro cell schematic cross-section.
The little electrolysis chip of Fig. 2 mask graph.(a) mask graph layout; (b) electrolytic cell channel part mask amplifies CCD figure (10 show the speck mirror), and two lines in the passage are used for forming two electrode processing ridges in etching in the micro cell passage; (c) two electrode processing ridges that mask etching forms shown in the figure (b).
Fig. 3 chip sides corrosion reaming method electrode scheme of installation.
Subtegulum alternating method electrode scheme of installation on Fig. 4.(a) electrode channel is surveyed face figure; (b) electrode channel vertical view.
Fig. 5 micro cell chip photo.(a) micro cell chip photo, side reaming method installing electrodes, the outlet of epoxy glue enclosed electrode, chip has two imports and two outlets; (b) micro cell chip photo, will be up and down during involution two staggered, the electrode channel outlet is exposed, electrode inserts the micro cell passage along the channel outlet that exposes, with sealing with wax the composite electrode channel outlet, this chip has an import and an outlet; The electrolytic cell path partially CCD figure (10 show the speck mirror) of two parallel microelectrodes is housed (c).530 microns of micro cell channel widths, distance is 190 microns between two electrode processing ridges, 90 microns of channel depth, the location ridge is high 12 microns, 80 microns of electrode diameters.
Fig. 6 parallel double electrode chip is led the detection response curve as conductance detecting pool to the electricity of KCl.
Fig. 7 micro cell chip cyclic voltammogram, (a) three-electrode system wherein, two platinum electrodes in the micro cell passage are respectively as working electrode with to the utmost point, and the Ag/AgCl contrast electrode places outlet pond, 10mM K
3Fe (CN)
6The cyclic voltammogram of aqueous solution (CHI 760 electrochemical workstations mensuration); (b) two electrode system 10mM K
3Fe (CN)
6The cyclic voltammogram of aqueous solution, a platinum electrode in the passage is that another platinum electrode is as working electrode to the utmost point and contrast electrode simultaneously.
Fig. 8 micro cell galvanochemistry and electrochemiluminescence detect.(a) 0,16,32,64 wherein, the electrochemiluminescence of 125uM luminol solution is the stack of variation diagram in time; (b) 0,16,32,64, the stack of the cyclic voltammogram of 125uM luminol solution.Chip is placed magazine, and syringe pump driving solution passes through the micro cell passage with the flow of 3ul/min.Data are measured with micro-fluidic chip luminescent detection system (the auspicious wheat analytical instrument in Xi'an company) and electrochemical workstation (CHI760).
The fluorescence microscopy CCD photo (10 show the speck mirror, and fluorescein is a fluorescence indicator) of pH gradient does not wherein have electric field between (a) two electrodes in the mobile electrolytic cell of Fig. 9; (b) direction of an electric field from top to bottom; (c) direction of an electric field from top to bottom.
Among the figure: 1 electrode, 2 micro cell passages, 3 electrode channels, 4 fluid sealants, 5 electrode processing ridges, 6 electrolyte solution passages, 7 solution are imported and exported, 8 cover plates, 9 substrates, 10 electrodes are imported and exported.
Embodiment
Below to be described in detail as follows based on the photoetching of laser photocomposing machine printing mask and the concrete making step that the wet etching glass baseplate prepares the micro cell chip.
1. generate the mask pattern file of microchannel and electrode channel with CoreDraw or similar software design;
2. utilize laser photocomposing machine that graphic file is printed on the polyester film, form the black and white mask;
3. utilize the uv-exposure machine that mask graph is transferred to top positive optical cement (AZ4650) face of chromium plate glass (Changsha beautiful springtime, SG2506 type);
4. the glass substrate after the exposure is dipped in the 0.5% NaOH solution and developed 40～60 seconds, and graphic structure is exposed;
5. chip is transferred in the baking oven about 15 minutes of the baking time after 110 ℃, made optical cement film firm;
6. in the liquid that dechromises, shake gently down and soaked about 2 minutes, the chromium layer that exposes is removed, expose glass to be etched;
7.35 use HF-HNO under ℃
3-H
2Static etching is 1-160 minutes in O (volume ratio 1:2:7) solution, and etching time channel depth is as required determined;
8. soak with 2% NaOH and removed the optical cement of being had a surplus in 3 minutes;
9. spending chrome liquor all removes chromium layer on glass;
10. punch with admantine drill at the Path end point place;
11. ultrasound wave cleans the glass-chip after the punching, the glass chip that removal may exist in water;
12. will embathe surface organic matter with isopropyl alcohol behind the chip cleaning, drying, the back is in 100 ℃ of H
2SO
4-H
2O
2(7:3) handled 15 minutes to 2 hours in the solution;
13. in flow deionized water,, use the hot blast drying excessive moisture with after the sealing surface applying;
14. as above the glass-chip of Tie Heing places muffle furnace, slowly is warmed up to 420～450 ℃ from room temperature, keeps naturally cooling to room temperature after 3 hours;
15. the introducing electrode carries out the etching reaming with the electrode channel outlet behind the alignment involution with glass etching liquid, makes to export into bell mouth shape, electrode is introduced the micro cell passage by this mouth, enters micro cell passage appropriate location along electrode channel;
16. export with glue involution electrode channel.
Prepared chip comprises electrode 1, micro cell passage 2, solution channel 6, solution import and export 7, cover plate 8 and substrate 9, it is characterized in that also comprising electrode channel 3, electrode processing ridge 5, electrode import and export 10, be carved with micro cell passage 2 and electrode channel 3 on the substrate 9 or on substrate 9 and the cover plate 8 simultaneously, micro cell passage 2 and electrode channel 3 junctions constitute electrode processing ridge 5, and electrode 1 is positioned in the electrode channel 3; At the two ends of micro cell passage 2 solution channel 6 is arranged, the solution that chip surface or chip sides perforate formation are connected with solution channel 6 imports and exports 7, and the port of electrode channel 3 is that electrode imports and exports 10, and electrode is imported and exported 10 places and sealed with fluid sealant 4.Electrode processing ridge 5 is raised structures parallel with micro cell passage 2 and electrode channel 3, its height is less than the micro cell passage 2 and electrode channel 3 degree of depth, and the high difference of the degree of depth of micro cell passage 2 and electrode channel 3 and ridge is less than the diameter of wire electrode 1.
Fig. 5 has showed the making result of the little electrolysis chip of the glass with two parallel poles, and wherein (a) is with corrosion reaming method installing electrodes, (b) with staggered involution method installing electrodes.Two 80 microns Pt silk electrode is by the both sides of accurate in locating at the electrolytic cell passage of 90 microns of the degree of depth, shown in figure (c).
Fig. 6 has showed and utilizes micro cell shown in Figure 5 as the testing result of conductance detecting pool to KCl solution that test solution passes through with the 3uL/min flow.Show that this minisize detection tank can be used as miniature conductance detecting pool.
Fig. 7 for micro cell shown in Figure 5 as electrochemical investigating pond to K
3Fe (CN)
6Solution carries out the result of cyclic voltammetry scan.Wherein the left side is the result of three determination of electrode, and right figure is the result who measures with bipolar electrode.
Fig. 8 has showed the galvanochemistry and the electrochemiluminescence testing result of the luminol solution that carries out under the bipolar electrode system.Utilize the transparent characteristics of this chip electrolytic cell, can when carrying out Electrochemical Detection, collect luminous signal.
Fig. 9 is the fluorescence microscopy CCD photo (10 show the speck mirror, and fluorescein is a fluorescence indicator) that is used for showing mobile electrolytic cell pH gradient formation.Showed that the mobile electrolytic cell of this chip is used for dynamically producing at the electrolysis passage application of pH gradient.Apply voltage 1.8V between the electrode, produce by potentiostat.The 100mM pH9.2 sodium carbonate liquor of 1mM fluorescein, flow 3.0ul/min, high-pressure sodium lamp light source, blue color filter group.Fluorescein sends green fluorescence under blue-light excited in alkaline medium.Because pH reduced near the electrolytic reaction on the positive pole caused electrode, and produced the pH gradient at direction of an electric field under the effect in laminar flow flow field, therefore increased in the direction of an electric field fluorescence intensity.This variation that changes by the fluorescein fluorescence intensity shows.This test shows simultaneously in the chip electrolytic cell that flows and isolates owing to the laminar flow effect can realize not having film between the electrode product.This characteristic can be used for the chip free stream cataphoresis, and the chip electricity is synthetic, chip electrodialysis etc.
Claims (2)
1, a kind of mobile micro cell glass-chip, it comprises electrode (1), micro cell passage (2), solution channel (6), solution import and export (7), cover plate (8) and substrate (9), it is characterized in that upward or on substrate (9) and the cover plate (8) being carved with micro cell passage (2) and electrode channel (3) simultaneously at substrate (9), micro cell passage (2) and electrode channel (3) junction constitute electrode processing ridge (5), and electrode (1) is positioned in the electrode channel (3); At the two ends of micro cell passage (2) solution channel (6) is arranged, the solution that chip surface or chip sides perforate formation are connected with solution channel (6) is imported and exported (7), the port of electrode channel (3) is that electrode is imported and exported (10), and electrode is imported and exported (10) and located with fluid sealant (4) sealing; Electrode processing ridge (5) be one with micro cell passage (2) and the parallel raised structures of electrode channel (3), its height is less than the micro cell passage (2) and electrode channel (3) degree of depth, and the high difference of the degree of depth of micro cell passage (2) and electrode channel (3) and ridge is less than the diameter of wire electrode (1).
2, the preparation method of mobile micro cell glass-chip according to claim 1, it is characterized in that step is: adopt the method for common glass photomask and heat sealing to make chip, the degree of depth and ridge height by mask size design and etching extent control passage, make electrode processing ridge (5) parallel with electrode channel (3) with micro cell passage (2), its height is less than the micro cell passage (2) and electrode channel (3) degree of depth, and the high difference of the degree of depth of micro cell passage (2) and electrode channel (3) and ridge is less than the diameter of wire electrode (1); Adopt one of following two kinds of methods to introduce electrode: a kind of is that the electrode channel outlet behind the alignment involution is carried out the etching reaming with the glass etching liquid that contains HF, makes to export into bell mouth shape, and electrode is introduced electrode channel by this mouth; Another kind method is, will be up and down during involution two staggered, the electrode channel outlet is exposed, electrode inserts electrode channel along the passage that exposes.
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|---|---|---|---|
| CNB2006100477374A CN100485377C (en) | 2006-09-14 | 2006-09-14 | Glass-chip for flowing minisize electrolyzer and manufacturing method thereof |
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| CNB2006100477374A CN100485377C (en) | 2006-09-14 | 2006-09-14 | Glass-chip for flowing minisize electrolyzer and manufacturing method thereof |
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| CN100485377C true CN100485377C (en) | 2009-05-06 |
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| US9851327B2 (en) * | 2014-06-02 | 2017-12-26 | Maxim Integrated Products, Inc. | Photopatternable glass micro electrochemical cell and method |
| CN108152351B (en) * | 2017-12-22 | 2020-09-22 | 大连大学 | Micro-electrolysis cell for detecting formaldehyde and preparation method thereof |
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Non-Patent Citations (4)
| Title |
|---|
| Influence of the sample volume and the position of theelectrode and the capillary-end in the sample vial on theelectrokinetic injection in capillary electrophoresis. Theo de Boer等.Journal of Chromatography A.,Vol.788 . 1997 |
| Influence of the sample volume and the position of theelectrode and the capillary-end in the sample vial on theelectrokinetic injection in capillary electrophoresis. Theo de Boer等.Journal of Chromatography A.,Vol.788 . 1997 * |
| 微流控芯片免疫分析方法研究进展. 贾宏新等.分析化学，第33卷第10期. 2005 |
| 微流控芯片免疫分析方法研究进展. 贾宏新等.分析化学，第33卷第10期. 2005 * |
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