CN1641346A - Method for preparing electrochemical micro-flor controlled chip of sunk copper electrode - Google Patents
Method for preparing electrochemical micro-flor controlled chip of sunk copper electrode Download PDFInfo
- Publication number
- CN1641346A CN1641346A CN 200410082842 CN200410082842A CN1641346A CN 1641346 A CN1641346 A CN 1641346A CN 200410082842 CN200410082842 CN 200410082842 CN 200410082842 A CN200410082842 A CN 200410082842A CN 1641346 A CN1641346 A CN 1641346A
- Authority
- CN
- China
- Prior art keywords
- microelectrode
- chip
- sunk
- electrode
- pmma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 19
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 19
- 238000005530 etching Methods 0.000 claims abstract description 10
- 238000007731 hot pressing Methods 0.000 claims description 13
- 229920002120 photoresistant polymer Polymers 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 238000001039 wet etching Methods 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000012742 biochemical analysis Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000013016 damping Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001499 laser induced fluorescence spectroscopy Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Automatic Analysis And Handling Materials Therefor (AREA)
- Micromachines (AREA)
Abstract
The invention is a method for preparing electrochemical microflow control chip with sunk copper electrode, used in preparing electrochemical microflow control chips. The method: using microchannel mould to thermally press PMMA (polymethyl methacrylate) substrate to obtain microchannel; using microelectrode mould to thermally press another PMMA substrate to obtaining microelectrode sinkage ans spattering Cu on this PMMA and using etching and wet-corroding processes to make sunk Cu microelectrode; adopting thermal interlinking mode to sealing the two PMMA substrates to obtain electrochemical microflow control chip with sunk Cu electrode. Its effects and benefits: adopting thermal pressing, spattering, etching and wet-corroding methods to obtain sunk Cu electrode, integrating the sunk Cu electrode on the microflow control chip so as to raise the yield of manufacturing chips and simultaneously adopting Cu as the material of working electrode for electrochemical detecting, largely reducing the cost of chip. This chip can be widely applied to sugar detection in biochemical analysis.
Description
Technical field
The invention belongs to polymer chip manufacture technology field and technical field of analysis and detection, relate to a kind of preparation method of depression Cu electrode electro Chemical micro-fluidic chip, be used for the making of galvanochemistry micro-fluidic chip.
Background technology
Micro-fluidic chip be present micro-total analysis system (one of research emphasis of μ-TAS), it makes the microstructure based on the microchannel network by means of Micrometer-Nanometer Processing Technology, by the control of convection cell, realization is to integrated processing of biological sample and analysis.The detection method of micro-fluidic chip mainly contain three kinds of laser-induced fluorescence (LIF), mass spectrum and Electrochemical Detection (R.Scott Martin, et al, Anal.Chem., 2000,72,3196-3204).Owing to microelectrode can be integrated on the chip, therefore this type of chip is further integrated and microminiaturizedly provide a brand-new thinking for micro-total analysis system, the miniaturization of equipment and the traceization of refuse make it comply with development trend (the Joseph Wang of " green analytical chemistry ", et al, Analytica Chimica Acta, 2000,416,9-14).The core technology of this method is the preparation of galvanochemistry micro-fluidic chip.The material of making this type of chip mainly contains several classes of silicon, glass, organic polymer and silicon rubber, organic polymer material, for example PMMA and silicon and glassy phase ratio, material price is cheap, and is wide in variety, and chip fabrication technique is simple, produce cost low (Holger Becker, et al, Talanta in batches, 2002,56,267-287), compare with silicon rubber, its electroosmotic flow characteristic is outstanding, and therefore the micro-fluidic chip of this type of material has caused concern in fields such as analytical chemistry in recent years.
Galvanochemistry micro-fluidic chip microelectrode material is Pt normally, noble metals such as Au (B.Gra β, et al, Sensorsand Actuators B, 2001,72,249-258, Nicole E.Hebert, et al, Anal.Chem.2003,75,2969-2975), in order to improve the adhesion of noble metal and glass or polymeric substrates, need between them, increase the middle layer, need the two kinds of materials in corroding electrode and middle layer to obtain microelectrode during for example Cr, so wet etching, complex technical process, and the noble metal electrode cost is higher, can not satisfy disposable request for utilization, need clean microchannel and microelectrode during repeated use, as deal with improperly, easily detected sample is polluted.
Because the deflection of polymkeric substance thermal bonding is bigger, reaches 10-20 μ m, when therefore adopting the method sealing-in galvanochemistry chip of thermal bonding, plane microelectrode distortion fracture causes the chip manufacturing failure.Usually the bonding of microelectrode polymer electrochemical chip adopt gluing process (B.Gra β, et al, Sensors andActuators B, 2001,72,249-258), because the microchannel is stopped up by glue easily, the method success ratio is very low.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Cu of making electrode electro Chemical micro-fluidic chip, adopt Cu to substitute the noble metal microelectrode and can reduce chip cost, the adhesion of Cu and base material PMMA is good simultaneously, has avoided the use in middle layer, has simplified processing step; Adopt thermal bonding mode sealing-in chip, can prevent the microchannel obstruction, make the depression microelectrode and substitute plane microelectrode, the breakage problem when having solved the microelectrode sealing-in.
Technical scheme of the present invention is as follows:
1. utilize corrosion of photoetching, silicon or UV-LIGA technology that microchannel and microelectrode figure and alignment mark point are transferred on silicon chip and the sheet metal, obtain hot pressing die;
2. adopt the method for hot pressing the microchannel to be copied on the PMMA substrate 100 ℃ of hot pressing temperatures, pressure 0.7Mpa, retention time 6min;
3. sputter after the employing hot pressing, alignment and wet etching obtain the depression microelectrode on PMMA.100 ℃ of hot pressing temperatures, pressure 1.4Mpa, retention time 6min; Utilize the thick Cu of radio-frequency sputtering platform sputter 200nm; The spin coating photoresist utilizes the gauge point on PMMA and the mask to realize aiming at alignment; Etching Cu in 5% (wt) salpeter solution; Adopt the method for re-expose, development to remove the photoresist on Cu microelectrode surface, obtain the Cu microelectrode of depression;
4. utilize micro-vision to aim to have the gauge point on two PMMA of microchannel and microelectrode, thereby effectively ensure the distance between microchannel outlet and the microelectrode, adopt the mode of thermal bonding will have two PMMA sealing-ins of microchannel and microelectrode, obtain chip.100 ℃ of bonding temperatures, pressure 0.7Mpa, retention time 10min.
Effect of the present invention and benefit are: adopt Cu to substitute the noble metal microelectrode and be integrated on the micro-fluidic chip, simplified processing step, reduce chip cost; The breakage problem of electrode had improved the chip manufacturing yield rate when making depression microelectrode had solved the chip thermal bonding.The carbohydrate that this type of chip can be applicable in the biochemical analysis detects.
Description of drawings
Fig. 1 is the structural representation of depression Cu electrode electro Chemical micro-fluidic chip.
1. damping fluid sample inlet pools among the figure; 2. sample feeding pond; 3. sample waste liquid pool; 4. microchannel; 5. damping fluid waste liquid pool.
Fig. 2 is a depression Cu electrode electro Chemical micro-fluidic chip damping fluid waste liquid pool partial enlarged drawing.
5. damping fluid waste liquid pools among the figure; 6. microchannel outlet; 7. microelectrode.
Fig. 3 is a depression Cu electrode synoptic diagram.
Embodiment
Be described in detail embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
The preparation of step 1. hot pressing die
Silicon chip is put into H
2O
2: H
2SO
4=1: 3 solution boil deionized water rinsing 15min to the 10min that smolders, and the oven dry back obtains hydrophobic surface; Silicon chip after the processing places the two-tube diffusion furnace of ZKLS-2A, and heating-up temperature to 1180 ℃ kept 3.5 hours, and obtaining thickness at silicon face is the silicon dioxide masking film of 1 μ m.On silicon chip, apply the BP212 photoresist equably, pre-spin coating time 5s, the spin coating time is 30s, pre-spin coating speed 500rpm, spin speed is 3000rpm; Preceding baking BP212 photoresist carries out in 80 ℃ baking oven, and the time is 20min; Exposing on BGJ-3 type litho machine in cooling back, is 0.97mw/cm in the light intensity of I line
2Situation under, the time shutter is 35s; Develop in 0.5% (wt) NaOH solution, developer temperatur is 25 ℃, and development time is 15s, and mask patterns has so far just accurately copied on the silicon chip.
What next carry out is the wet etching of silicon chip.Remove the silicon dioxide masking film earlier, etching condition is HNO
3: HF: H
2O=40: 20: 40 (volume ratio), the normal temperature corrosion, etching time is 5min.The etching condition of silicon anisotropic corrosion is 73 ℃, and corrosive liquid is KOH: IPA: H
2O=40g: 30ml: 100ml, corrosion speed is 0.4 μ m/min.The figure height of microchannel hot pressing die is 60 μ m, and the figure height of microelectrode hot pressing die is 10 μ m.
Microchannel and microelectrode are duplicated in step 2. hot pressing
PMMA substrate after the washed with de-ionized water (20 * 50mm) and the silicon micro-channel mould place on the hot press, 100 ℃ of hot pressing temperatures, pressure 0.7Mpa, retention time 6min duplicates the microchannel; PMMA substrate after another sheet cleans (50 * 50mm) and the microelectrode mould place on the hot press 100 ℃ of hot pressing temperatures, pressure 1.4Mpa, retention time 6min.
The preparation of step 3. depression Cu microelectrode
With the thick Cu of radio-frequency sputtering platform sputter 200nm; Spin coating photoresist BP212 utilizes the gauge point on PMMA and the mask to realize aiming at alignment, and etching condition is with silicon mould figure etching condition; Etching Cu in 5% (wt) salpeter solution; In order to remove the photoresist on Cu surface, (light intensity at the I line is 0.97mw/cm to re-expose
2Situation under, the time shutter is 50s) in the NaOH solution of 0.5% (wt), develop to remove the photoresist on Cu microelectrode surface afterwards, obtain the Cu microelectrode of depression.
Step 4. thermal bonding chip
Utilize the microscope vision alignment to have gauge point on two PMMA of microchannel and microelectrode, thereby effectively ensure the distance between microchannel outlet and the microelectrode, after aiming at, two PMMA that will have microchannel and a microelectrode are positioned on the hot press, 100 ℃ of bonding temperatures, pressure 0.7Mpa, retention time 10min.Obtain the galvanochemistry micro-fluidic chip of depression Cu electrode.
Claims (1)
1. the preparation method of an electrochemical micro-flor controlled chip of sunk copper electrode is characterized in that comprising the steps:
A) adopt Cu to make little working electrode material, be integrated on the micro-fluidic chip;
B) adopt hot pressing, sputter, alignment and wet etching on the polymethyl methacrylate base sheet, to obtain depression Cu microelectrode: 100 ℃ of hot pressing temperatures, pressure 1.4Mpa, retention time 6min; Utilize the thick Cu of radio-frequency sputtering platform sputter 200nm; The spin coating photoresist utilizes the gauge point on polymethyl methacrylate base sheet and the mask to realize aiming at alignment; Etching Cu in 5% (wt) salpeter solution; Adopt the method for re-expose, development to remove the photoresist on Cu microelectrode surface, obtain the Cu microelectrode of depression.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100828422A CN100344964C (en) | 2004-12-01 | 2004-12-01 | Method for preparing electrochemical micro-flor controlled chip of sunk copper electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100828422A CN100344964C (en) | 2004-12-01 | 2004-12-01 | Method for preparing electrochemical micro-flor controlled chip of sunk copper electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1641346A true CN1641346A (en) | 2005-07-20 |
| CN100344964C CN100344964C (en) | 2007-10-24 |
Family
ID=34869203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100828422A Expired - Fee Related CN100344964C (en) | 2004-12-01 | 2004-12-01 | Method for preparing electrochemical micro-flor controlled chip of sunk copper electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100344964C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431487C (en) * | 2007-01-25 | 2008-11-12 | 中国科学院上海微系统与信息技术研究所 | Processing method of three-dimensional implantable microelectrode array |
| CN100465621C (en) * | 2006-02-10 | 2009-03-04 | 厦门大学 | Micro-fluid control chip with surface enhanced Raman spectral active substrate and producing method thereof |
| CN103808776A (en) * | 2014-03-12 | 2014-05-21 | 杭州霆科生物科技有限公司 | Preparation method of electrochemical sensor |
| CN103934049A (en) * | 2014-04-14 | 2014-07-23 | 西安交通大学 | Scale type micro-fluidic chip for quantitative immediate diagnosis and preparation method of scale type micro-fluidic chip |
| CN105548315A (en) * | 2016-02-02 | 2016-05-04 | 苏州甫一电子科技有限公司 | Polymer micro-fluidic chip and preparation method thereof |
| CN109701674A (en) * | 2019-01-28 | 2019-05-03 | 广东工业大学 | Micro-fluidic chip microelectrode technique |
| CN112346308A (en) * | 2020-11-10 | 2021-02-09 | 南通大学 | Alignment operation flow of alignment process in PDMS micro-fluidic chip processing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1305615B1 (en) * | 2000-07-21 | 2004-09-29 | Aclara BioSciences, Inc. | Method and devices for capillary electrophoresis with a norbornene based surface coating |
| CN1228631C (en) * | 2002-06-20 | 2005-11-23 | 中国科学院理化技术研究所 | Preparation method of high polymer micro-fluidic chip |
-
2004
- 2004-12-01 CN CNB2004100828422A patent/CN100344964C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465621C (en) * | 2006-02-10 | 2009-03-04 | 厦门大学 | Micro-fluid control chip with surface enhanced Raman spectral active substrate and producing method thereof |
| CN100431487C (en) * | 2007-01-25 | 2008-11-12 | 中国科学院上海微系统与信息技术研究所 | Processing method of three-dimensional implantable microelectrode array |
| CN103808776A (en) * | 2014-03-12 | 2014-05-21 | 杭州霆科生物科技有限公司 | Preparation method of electrochemical sensor |
| CN103934049A (en) * | 2014-04-14 | 2014-07-23 | 西安交通大学 | Scale type micro-fluidic chip for quantitative immediate diagnosis and preparation method of scale type micro-fluidic chip |
| CN103934049B (en) * | 2014-04-14 | 2016-06-08 | 西安交通大学 | A kind of quantitative care diagnostic micro-fluidic chip of scale-type and preparation method thereof |
| CN105548315A (en) * | 2016-02-02 | 2016-05-04 | 苏州甫一电子科技有限公司 | Polymer micro-fluidic chip and preparation method thereof |
| CN109701674A (en) * | 2019-01-28 | 2019-05-03 | 广东工业大学 | Micro-fluidic chip microelectrode technique |
| CN112346308A (en) * | 2020-11-10 | 2021-02-09 | 南通大学 | Alignment operation flow of alignment process in PDMS micro-fluidic chip processing |
| CN112346308B (en) * | 2020-11-10 | 2022-04-05 | 南通大学 | Alignment operation flow of alignment process in PDMS micro-fluidic chip processing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100344964C (en) | 2007-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106391151B (en) | It is suitable for the multilayer micro-fluid chip production method of mass production | |
| Lei | Materials and fabrication techniques for nano-and microfluidic devices | |
| Kim et al. | Rapid prototyping of microfluidic systems using a PDMS/polymer tape composite | |
| Grosse et al. | Deep wet etching of fused silica glass for hollow capillary optical leaky waveguides in microfluidic devices | |
| Chen et al. | UV-nanoimprint lithography as a tool to develop flexible microfluidic devices for electrochemical detection | |
| CN105548315A (en) | Polymer micro-fluidic chip and preparation method thereof | |
| Chen et al. | A rapid and low-cost procedure for fabrication of glass microfluidic devices | |
| JP5583972B2 (en) | Microfabricated device having non-wettable or non-absorbable polymer coating surface or apparatus which is a part thereof | |
| CN100387980C (en) | Preparation method of polymer microflow control chip having metal microelectrode | |
| CN100503222C (en) | Solvent assistant hot-pressed packing method for polymethylmethacrylate microflow controlled chip | |
| CN101598717A (en) | Mould the method that legal system is equipped with polydimethylsiloxanechip chip based on the liquid of hydrogel planar micro-patterning | |
| CN1212515C (en) | Electrochemical detection-micro fluid control chip,and manufacturing method and regeneratnig method thereof | |
| CN100344964C (en) | Method for preparing electrochemical micro-flor controlled chip of sunk copper electrode | |
| CN109317228A (en) | One kind being based on the micro-machined micro-flow control chip preparation method of body laser inner carving | |
| WO2019134547A1 (en) | Gene sequencing substrate and preparation method therefor, gene sequencing device, and gene sequencing method | |
| CN103723676A (en) | Manufacturing method of micro-fluid channel | |
| CN103808776B (en) | The preparation method of electrochemical sensor | |
| Nag et al. | Performance enhancement of electronic sensor through mask-less lithography | |
| KR20040100646A (en) | Micor/nano fluidic 3 dimensional electrode system | |
| Liu et al. | Plasma assisted thermal bonding for PMMA microfluidic chips with integrated metal microelectrodes | |
| CN1928534A (en) | Method for preparing micro-flowing injection type chemical luminous chip | |
| CN104190482B (en) | Take photosensitive dry film as the method that etching mask makes glass microfluidic devices | |
| US20030232450A1 (en) | Microfluidic device and method for producing the same | |
| CN103460336A (en) | Micro-device on glass | |
| CN110560185B (en) | Self-sealing micro-nano fluidic chip processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071024 Termination date: 20101201 |