CN101949946B - Method for producing photoelectrochemical microfluidic detection chip of three-electrode system - Google Patents

Method for producing photoelectrochemical microfluidic detection chip of three-electrode system Download PDF

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CN101949946B
CN101949946B CN2010102717400A CN201010271740A CN101949946B CN 101949946 B CN101949946 B CN 101949946B CN 2010102717400 A CN2010102717400 A CN 2010102717400A CN 201010271740 A CN201010271740 A CN 201010271740A CN 101949946 B CN101949946 B CN 101949946B
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electrode
micro
pdms
detection chip
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CN101949946A (en
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王宏志
穆庆辉
李耀刚
张青红
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Donghua University
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Donghua University
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Abstract

The invention relates to a method for producing a photoelectrochemical microfluidic detection chip of a three-electrode system. The method comprises the following steps: coating liquid polydimethylsiloxane (PDMS) on a glass sheet and curing the PDMS to form a substrate; forming a micro-channel and corresponding work electrode pool, reference electrode pool, counter electrode pool and import/export pool from a pre-designed pattern on the PDMS by using a laser engraving method; placing the work electrodes and connecting with leads; sealing another non-etched PDMS as a cover plate by oxygen plasma processing; and finally integrating the reference electrodes and the counter electrodes to produce the photoelectrochemical microfluidic detection chip of the three-electrode system. The production method is easy to operate; the size of the micro-channel is controllable; the sealing of the microfluidic chip is realized without additional adhesive; after the sealing, the bonding is firm without leakage; and the method is applicable to photoelectrochemical detection and has the advantages of little oxygen consumption, fast detection and high flexibility.

Description

The method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry
Technical field
The invention belongs to the making field of micro-fluidic detection chip, the method for making of the micro-fluidic detection chip of particularly a kind of three-electrode system Optical Electro-Chemistry.
Background technology
The micro-fluidic chip analysis of test system is the frontier development of the micro-total analysis system (Miniaturized Total Analysis Systems, μ TAS) of the appearance nineties in 20th century, and its developing direction is microminiaturization more, robotization, rapid and portability.The essential characteristic of micro-fluidic chip is that multiple monotechnics flexible combination, scale on the controlled small platform of integral body are integrated.Such benefit is significantly to shorten the sample preparation time, and detection resolution/sensitivity significantly improves and consumption and cost significantly reduce.More profound significance then is, it very likely makes integral device miniaturization, the family oriented of micro-fluidic chip, fundamentally changes the human existence quality.The motion of fluid has it to be different from the individual character of the fluid motion of one macro-scale in the micro-fluidic chip; Face body ratio like microfluid increases; The surface action that comprises surface tension, stickiness power, heat exchange etc. strengthens, and inertia force influence weakens, and the Reynolds coefficient diminishes; Edge effect increases, and three-dismensional effect becomes and can not ignore; In addition, because linear dimension reduces, the physical quantity gradient improves, and the expulsive force of heat and mass increases.These make the micro-fluidic chip test performance significantly surpass the test system under the macroscopic conditions.
The initial application of micro-fluidic chip is an analytical chemistry; Be used as a kind of platform of analytical chemistry; Its advantage comprises that consumption appearance amount is low, analysis speed fast, have high sensitivity and high resolving power, can also be sample preparation, separate, reaction etc. with analyze relevant process integration together, improve the efficient of analysis greatly.But the major defect that the making of micro-fluidic chip at present exists has: (1) is with high costs.Owing to will use used photoetching technique in the microelectronics industry usually, make and make the time that a micro-fluidic chip needs many special devices and labor that manufacturing process is very complicated.(2) sealing-in of micro-fluidic chip difficulty.In photoetching or little process, the substrate surface that constitutes microreactor can be destroyed usually, cause uneven, bad with anchor clamps or adhesive sealing-in effect, seepage takes place easily.
Summary of the invention
Technical matters to be solved by this invention provides the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry; The manufacturing process of this micro-fluidic chip is simple; Can produce the complicated micro-fluidic chip of stream; The size of microchannel can accurately be controlled, and the sealing-in of microreactor does not need extra adhesive; Material therefor PDMS is transparent, nontoxic, be easy to processing, and can see through the light of wavelength greater than 230nm, can be advantageously applied to biomedicine, makes things convenient for the realization of the photoelectrocatalysis reaction conditions of certain a little introducing ultraviolet light; Micro-fluidic chip is applied to Optical Electro-Chemistry detects, reagent dosage is few, and detection speed is fast, and is highly sensitive.
The method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry of the present invention comprises:
(1) liquid dimethyl silicone polymer (PDMS) and the supporting hardening agent mass ratio with 10: 1 are mixed, the method that adopts rotation to apply then is coated on PDMS on the glass sheet equably, makes it solidify to form substrate;
(2) use the laser engraving method, will pass through software (CorelDRAW 12) designed patterns in advance, on PDMS, form microchannel and corresponding work electrode cell, contrast electrode pond, electrode cell and import and export pond;
(3) in the working electrode pond of above-mentioned PDMS substrate, lay working electrode, and connect with lead;
(4) do not have above-mentioned PDMS substrate and another sheet the PDMS (as cover plate) of etching to use oxygen plasma treatment, then the treated side of two PDMS is pasted together, and, form permanent sealing-in in 80~150 ℃ of insulations 1~3 hour;
(5) the cooling back, is laid contrast electrode and to electrode, is connected import pond and outlet pond respectively with microtubule in the punching of the relevant position of cover plate with card punch, with the encapsulation of transparent epoxy resin glue, accomplishes the making of micro-fluidic detection chip.
PDMS (containing complete curing agent) model described in the step (1) is Sylgard 184 (Dow Corning Corporation comprises liquid host and hardening agent);
Glass sheet thickness described in the step (1) is 1~3mm.
The rotating speed that rotation described in the step (1) applies is 500~1000 rev/mins; Rotational time is 30~60 seconds.
Curing described in the step (1), its condition are 100~150 ℃ of solidification temperatures; 3~10 minutes set times.
What the laser engraving method described in the step (2) adopted is carbon dioxide laser, and used laser power is 12~20W, and carving speed is 40~70cm/s.
The degree of depth in microchannel described in the step (2) and pond is 0.2~0.5mm, and width is 0.2~5mm.
Working electrode described in the step (3) is the electrode that is covered with the nano titanium oxide active layer.
Oxygen plasma treatment condition described in the step (4): oxygen pressure 40~60Pa, irradiation power 100~200W, 1~3 minute processing time.
Contrast electrode described in the step (5) is the Ag/AgCl contrast electrode, is platinum filament to electrode; The microtubule material therefor is a teflon.
The present invention adopts the laser engraving method to make integrated three-electrode system to can be used for the micro-fluidic detection chip that Optical Electro-Chemistry detects usefulness first, and in this process, selects suitable manner and need not adhesive and just can obtain good to connect envelope and ne-leakage.
The present invention can control the width of microchannel through the mapping software design; Can optionally control the degree of depth of certain a part of microchannel through control laser power and carving speed.Select different technological conditions, can obtain having different depth, the micro-fluidic chip of different in width microchannel.In this micro-fluidic chip, the thickness of fluid has only the hundreds of micron, under this condition, carries out the photoelectrocatalysis reaction, and light can penetrate liquid layer at an easy rate and arrive catalyzer, can utilize luminous energy fully, improves catalytic efficiency.
Beneficial effect
(1) can and regulate used laser power and carving speed through software design, and then the yardstick of control microchannel;
(2) envelope that connects of micro-fluidic chip does not need extra cementing agent, and coheres after the sealing-in firmly, seepage can not take place;
(3) the micro-fluidic chip full impregnated is bright, can observe the go forward side by side optical detection of line correlation of inner case easily, especially can see through the light of wavelength greater than 230nm, can carry out easily must ultraviolet excitation light-catalyzed reaction;
(4) cost of manufacture of micro-fluidic chip is low, and it is few to expend time in.
Description of drawings
The micro-fluidic detection chip device of Fig. 1 synoptic diagram;
The micro-fluidic chip depiction of Fig. 2 mapping software design;
The shape of the micro-fluidic chip microchannel of Fig. 3 first step engraving;
Pattern as shown in Figure 2 (a) that Fig. 4 embodiment 1 carves on PDMS and the final micro-fluidic detection chip of accomplishing (b);
Ultraviolet light that Fig. 5 obtains in embodiment 1 and intensity thereof are to the figure that influences of photocurrent;
The bias voltage that applies at working electrode that obtains among Fig. 6 embodiment 1 is to the figure that influences of photocurrent.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The PDMS matrix and the hardening agent of liquid state is even with 10: 1 mixed of mass ratio.To be of a size of 25mm * 75mm, thickness is that the glass sheet of 1mm is adsorbed on the sol evenning machine rotating disk, is poured over PDMS on the glass sheet, with 1000 rev/mins rotating speed rotations 30 seconds.Then, place the glass sheet that is loaded with PDMS 120 ℃ environment insulation that PDMS is solidified.Figure according to Drawing Design is as shown in Figure 2, uses CO 2Laser carves passage on PDMS.At first carve part as shown in Figure 3, employed laser power is 12W, and carving speed is 50cm/s, and the gained channel depth is 0.2mm, and width is 0.2mm.Carve remainder then, employed laser power is 15W, and carving speed is 50cm/s, and the gained figure degree of depth is 0.3mm, and size is as shown in Figure 2.Engraving obtains the substrate shown in Fig. 4 a after accomplishing.The electrode that is covered with the nano titanium oxide active layer is placed in the working electrode pond as working electrode; And connect with lead; Not having the PDMS (as cover plate) of etching to put into oxygen plasma together with other a slice then handles; Treatment conditions: oxygen pressure 50Pa, irradiation power 150W, 2 minutes processing times.Immediately two treated sides are pasted together after the taking-up, and placed under 120 ℃ the temperature insulation 2 hours, just can obtain the passage of complete closed., lay contrast electrode and, be connected respectively to the import and export pond to the microtubule of teflon in the punching of the relevant position of cover plate with card punch, use the encapsulation of transparent epoxy resin glue, obtain the micro-fluidic chip that Optical Electro-Chemistry detects that can be used for shown in Fig. 4 b electrode.
NaH with the 1mol/L that contains finite concentration organism (like glucose) 2PO 4The WS comes active substance (titania) on the work for inspection electrode to organic photoelectrocatalysis performance.Three electrodes are connected with electrochemical workstation; Inject a solution into in the micro-fluidic chip with micro syringe pump; The injection flow velocity is 30 μ L/min; Working electrode apply certain intensity ultraviolet light (λ=365nm), and apply a bias voltage (0.1~0.6V), can detect the response condition of titania to organic photocatalytic degradation reaction pair ultraviolet light.As shown in Figure 5, having under the situation of UV-irradiation, three-electrode system detect photocurrent than much bigger under the situation that does not have UV-irradiation (Fig. 5 a), and can increase (Fig. 5 b) along with the increase of intensity of illumination.Fig. 6 shows that for using micro-fluidic detection chip to the linear volt-ampere scanning that working electrode records saturation current can increase along with the increase of ultraviolet light intensity.
Embodiment 2
The PDMS matrix and the hardening agent of liquid state is even with 10: 1 mixed of mass ratio.To be of a size of 25mm * 75mm, thickness is that the glass sheet of 2mm is adsorbed on the sol evenning machine rotating disk, is poured over PDMS on the glass sheet, with 800 rev/mins rotating speed rotations 45 seconds.Then, place the glass sheet that is loaded with PDMS 100 ℃ environment insulation that PDMS is solidified.Figure according to Drawing Design is as shown in Figure 2, uses CO 2Laser carves passage on PDMS.At first carve part as shown in Figure 3, employed laser power is 15W, and carving speed is 50cm/s, and the gained channel depth is 0.3mm, and width is 0.5mm.Carve remainder then, employed laser power is 15W, and carving speed is 40cm/s, and the gained figure degree of depth is 0.35mm, and size is as shown in Figure 2.Engraving is placed in the electrode that is covered with the nano titanium oxide active layer in the working electrode pond as working electrode, and connects with lead after accomplishing; Do not have the PDMS (as cover plate) of etching to put into oxygen plasma together with other a slice then and handle treatment conditions: oxygen pressure 40Pa, irradiation power 100W; 3 minutes processing times; Immediately two treated sides are pasted together after the taking-up, and placed under 80 ℃ the temperature insulation 3 hours, just can obtain the passage of complete closed., lay contrast electrode and, be connected respectively to the import and export pond to the microtubule of teflon in the punching of the relevant position of cover plate with card punch, use the encapsulation of transparent epoxy resin glue, obtain can be used for the micro-fluidic chip that Optical Electro-Chemistry detects electrode.
Embodiment 3
The PDMS matrix and the hardening agent of liquid state is even with 10: 1 mixed of mass ratio.To be of a size of 25mm * 75mm, thickness is that the glass sheet of 3mm is adsorbed on the sol evenning machine rotating disk, is poured over PDMS on the glass sheet, with 500 rev/mins rotating speed rotations 60 seconds.Then, place the glass sheet that is loaded with PDMS 150 ℃ environment insulation that PDMS is solidified.Figure according to Drawing Design is as shown in Figure 2, uses CO 2Laser carves passage on PDMS.At first carve part as shown in Figure 3, employed laser power is 20W, and carving speed is 70cm/s, and the gained channel depth is 0.4mm, and width is 1mm.Carve remainder then, employed laser power is 20W, and carving speed is 50cm/s, and the gained figure degree of depth is 0.5mm, and size is as shown in Figure 2.Engraving is placed in the electrode that is covered with the nano titanium oxide active layer in the working electrode pond as working electrode, and connects with lead after accomplishing; Do not have the PDMS (as cover plate) of etching to put into oxygen plasma together with other a slice then and handle treatment conditions: oxygen pressure 60Pa, irradiation power 200W; 1 minute processing time; Immediately two treated sides are pasted together after the taking-up, and placed under 120 ℃ the temperature insulation 2 hours, just can obtain the passage of complete closed., lay contrast electrode and, be connected respectively to the import and export pond to the microtubule of teflon in the punching of the relevant position of cover plate with card punch, use the encapsulation of transparent epoxy resin glue, obtain can be used for the micro-fluidic chip that Optical Electro-Chemistry detects electrode.

Claims (9)

1. the method for making of the micro-fluidic detection chip of three-electrode system Optical Electro-Chemistry comprises:
(1) liquid dimethyl silicone polymer PDMS and the supporting hardening agent mass ratio with 10:1 is mixed, the method that adopts rotation to apply then is coated on PDMS on the glass sheet equably, makes it solidify to form substrate;
(2) use the laser engraving method, through the pattern of software design, on PDMS, form microchannel and corresponding work electrode cell, contrast electrode pond, to electrode cell with import and export the pond in advance;
(3) in the working electrode pond of above-mentioned substrate, lay working electrode, and connect with lead;
(4) PDMS that does not have etching to above-mentioned substrate and another sheet use oxygen plasma treatment as cover plate, then the treated side of two PDMS is pasted together, and is incubated 1 ~ 3 hour in 80 ~ 150 ℃, forms permanent sealing-in;
(5) the cooling back, is laid contrast electrode and to electrode, is connected import pond and outlet pond respectively with microtubule in the punching of the relevant position of cover plate with card punch, with the encapsulation of transparent epoxy resin glue, accomplishes the making of micro-fluidic detection chip.
2. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1, it is characterized in that: the glass sheet thickness described in the step (1) is 1 ~ 3mm.
3. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1 is characterized in that: the rotating speed that the rotation described in the step (1) applies is 500 ~ 1000 rev/mins; Rotational time is 30 ~ 60 seconds.
4. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1 is characterized in that: the curing described in the step (1), its condition are 100 ~ 150 ℃ of solidification temperatures; 3 ~ 10 minutes set times.
5. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1; It is characterized in that: what the laser engraving method described in the step (2) adopted is carbon dioxide laser; Used laser power is 12 ~ 20W, and carving speed is 40 ~ 70cm/s.
6. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1, it is characterized in that: the degree of depth in microchannel described in the step (2) and pond is 0.2~0.5mm, width is 0.2~5mm.
7. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1, it is characterized in that: the working electrode described in the step (3) is the electrode that is covered with the nano titanium oxide active layer.
8. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1; It is characterized in that: the oxygen plasma treatment condition described in the step (4): oxygen pressure 40 ~ 60Pa; Irradiation power 100 ~ 200W, 1 ~ 3 minute processing time.
9. the method for making of the micro-fluidic detection chip of a kind of three-electrode system Optical Electro-Chemistry according to claim 1, it is characterized in that: the contrast electrode described in the step (5) is the Ag/AgCl contrast electrode, is platinum filament to electrode; The microtubule material therefor is a teflon.
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