EP2193363A1 - Electrode pour systeme microfluidique - Google Patents
Electrode pour systeme microfluidiqueInfo
- Publication number
- EP2193363A1 EP2193363A1 EP08835770A EP08835770A EP2193363A1 EP 2193363 A1 EP2193363 A1 EP 2193363A1 EP 08835770 A EP08835770 A EP 08835770A EP 08835770 A EP08835770 A EP 08835770A EP 2193363 A1 EP2193363 A1 EP 2193363A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detection electrode
- layer
- microfluidic system
- metal
- electrode
- 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.)
- Withdrawn
Links
- 238000001514 detection method Methods 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 230000004888 barrier function Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000010931 gold Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910010380 TiNi Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000013060 biological fluid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000708 deep reactive-ion etching Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006037 cell lysis Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/307—Disposable laminated or multilayered electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
Definitions
- the present invention relates to an electrode for a microfluidic system.
- Microfluidic systems are known structures used in chemistry, physico-chemistry & biology, particularly in the following areas:
- microreaction which aims to produce all kinds of compounds (molecules, particles, emulsions, etc.) from starting reagents introduced into a microfluidic system which acts as a synthesis reactor,
- microfluidic systems performs the function of detector.
- the role of microfluidic systems is not however limited to the aforementioned functions; in particular, microfluidic systems may be designed to function as heat exchangers, filters, mixers, extractors, separators (for example operating by electrophoresis), devices for generating droplets of given size or solid particles, or as devices allowing to carry out particular operations (cell lysis, amplification of DNA, ).
- miniaturization of chemical or biological analysis systems is a marked trend in chemistry and analytical biochemistry. This makes it possible, on the one hand, to reduce the analysis times and, on the other hand, to reduce the quantity of reagents required. Miniaturization also makes it possible to integrate in the same system several steps of a detection protocol, which increases automation and therefore reduces handling costs. Miniaturization implies ever weaker detection volumes, hence the development of detection techniques and the development of increasingly sensitive detection components. Under these components, detection electrodes, in particular electrochemical electrodes, which are generally based on gold or platinum, are known to guarantee electrochemical stability and biological and chemical compatibility.
- these noble materials are deposited on rigid substrates or substrates based on inorganic material (silico-soda-lime glass) or organic material, in particular thermoplastics (polycarbonate, polymethylmethacrylate, polyimide, etc.).
- inorganic material silicon-soda-lime glass
- thermoplastics polycarbonate, polymethylmethacrylate, polyimide, etc.
- the present invention proposes to overcome the drawbacks of the electrochemical detection electrodes of the prior art by proposing a biologically compatible and electrochemically stable metallic layer electrode configuration (stability in operation and stability during eventual storage).
- the detection electrode for a microfluidic system is characterized in that it comprises a substrate of which at least one surface portion is coated by a stack of thin layers comprising a metal layer with intrinsic properties of electrical conductivity, said metal layer being associated with a so-called electrochemical barrier layer, said electrochemical barrier layer being associated with a terminal layer ensuring the biological compatibility and the electrochemical functionality (exchange of electric charges with molecules of the sample). This last layer also ensures the chemical and biological inertness of the electrode.
- this particular stacking structure it is possible to obtain, at lower cost, a detection electrode having an electrochemical resistance and a chemical and biological compatibility which makes its use possible within microfluidic analysis systems.
- the end layer further allows an exchange of electrical charges with molecules of the biological sample. This last layer also ensures the chemical and biological inertness of the electrode.
- the single figure shows the oxidation of the electrode as a function of the applied voltage.
- the metal layer is based on a pure material chosen from silver, or copper, zinc, or aluminum
- the electrochemical barrier layer is based on a metal or on the basis of a nitride of this metal, this metal possibly being, for example, titanium, or an electron-conduction oxide of the aluminum doped zinc oxide type (ZnO: A1); , mixed indium tin oxide (ITO), mixed indium zinc oxide (IZO) -
- the chemical and biological compatibility layer is based on a noble metal material selected for example from gold or platinum or any other metal compatible with the products to be tested.
- the thickness of the metal layer is between 50 to 1000 nm preferably between 150 to 500 nm, and even more preferably substantially close to 200 nm.
- the thickness of the electrochemical barrier layer is between 10 and 100 nm, preferably between 15 and 50 nm, and even more preferably substantially close to 20 nm.
- the thickness of the chemical and biological compatibility layer is between 10 to 100 nm, preferably between 15 to 50 nm, and even more preferably substantially close to 20 nm.
- the thickness of the layer of hooking between 2 and 10 nm it comprises a stack of layers of the Cu / TiNi / Au or TiN / Ag / Ti / Au type.
- the detection electrode for a microfluidic system has an electrical resistivity of between 0.1 and 10 ohm. square, which makes its use as a perfectly satisfactory electrode.
- it has a total thickness of between 200 and 500 nm.
- the electrode according to the invention is deposited, for example, by vacuum deposition techniques (for example by magnetic field assisted sputtering) or by electroplating on a substrate, which will thus constitute with the electrode a microfluidic system.
- the substrate of the microfluidic system can be made of materials of different kinds.
- polymer silicon or metal.
- these materials are unsatisfactory in many ways: the polymers are most often sensitive to certain organic solvents, are difficult to withstand prolonged treatments at temperatures above 200-300 ° C., deform under the effect of pressure, and are not entirely chemically inert (they can adsorb compounds present in the fluids, possibly salting them out later).
- the surface condition of the polymers is difficult to control, in particular because it can change over time.
- some polymers are not adapted to detection techniques operating by spectroscopy, in particular Raman, because of the disturbances they may cause.
- metals are likely to corrode, are not transparent or compatible with certain biological fluids, and are not compatible with the use of electrical function.
- support substrate for the electrode according to the invention glass, glass-ceramic or ceramic.
- a metal layer with intrinsic properties of electrical conductivity which is based on a pure material chosen from silver, or copper, zinc, aluminum and whose thickness is between 50 and 1000 nm, preferably between between 150 to 500 nm, and even more preferably substantially close to 200 nm.
- an electrochemical barrier layer which is based on a metal or on the basis of a nitride of this metal, this metal possibly being, for example, titanium or an electronically conductive oxide of the ZnO: Al, ITO, IZO type;
- a chemical and biological compatibility layer which is based on a noble metallic material chosen from gold and platinum.
- a hooked layer of a few nanometers, for example 1 and 10 nm, is deposited between the substrate and the metal layer. This layer of hooked can be based on titanium, chromium, nickel
- CVD Chemical Vapor Deposition
- electroplating electroplating
- spraying etc.
- an exemplary embodiment of an electrode for a microfluidic system according to the invention is given below.
- the glass is 0.7 mm sodocalcic and coated with a stack of Cu / TiNi / Au type magnetron deposited thin films.
- This electrode has a resistivity of 1 Ohm. square and a biological compatibility allowing the electrochemical interaction of the electrode with proteins in solution, without degrading them.
- the electrochemical detection electrode then undergoes surface treatments which, after removal of material forming the stack, form a plurality of detection cells.
- the array of detection cells can be obtained by physical etching, in particular by sand blasting or by irradiation using a CO 2 laser (JP-A-2000-298109), or by chemical etching of stacking.
- the detection cell array in several steps (depositAg / etchAg - depositTi / etchTi depositAu / etchAu), which makes it possible to modulate the lateral dimensions of each of the deposits, in particular to overcome any contamination by the edges.
- a deposition method based on electrodeposition is also well suited.
- the glass-function substrate advantageously has large dimensions so that several patterns can be made simultaneously, and therefore a large number of detection cells can be obtained in a single operation.
- substrates having a surface area of up to several square meters which makes it possible to make several thousand detection cells on a single substrate that can be subsequently cut into complete unit elements.
- the detection cells obtained in accordance with the invention have microstructures having a substantially square or rectangular cross section, which may be slightly rounded at the level of the substrate, having a depth that may range from several tens of microns to a few ⁇ m, or even less than micron.
- Systems entirely made of glass are interesting in that the substrate or substrates which constitute them have a small thickness and are transparent, which allows their use in complementary techniques of optical detection.
- the pure Ag electrode is oxidized as early as 0.4 V with an oxidation peak centered around 0.5-0.6 (dashed curve).
- An overlay of 20 nm Au slightly limits the oxidation of Ag (square dot curve).
- the most effective protection is obtained with the Ti electrochemical barrier layer (12 nm) where the Ag starts to be oxidized only from 1.5 V (DC line curve).
- the electrode undergoes an oxidation cycle using a so-called 'three-electrode' assembly with a working electrode (studied electrode), a reference electrode (saturated calomel electrode). ) and a counter-electrode (glass + 500 nm ITO) immersed in a liquid electrolyte H3PO4 (orthophosphoric acid).
- a working electrode studied electrode
- a reference electrode saturated calomel electrode
- a counter-electrode glass + 500 nm ITO immersed in a liquid electrolyte H3PO4 (orthophosphoric acid).
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0757646A FR2921157A1 (fr) | 2007-09-18 | 2007-09-18 | Electrode pour systeme microfluidique |
| PCT/FR2008/051598 WO2009044063A1 (fr) | 2007-09-18 | 2008-09-08 | Electrode pour systeme microfluidique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2193363A1 true EP2193363A1 (fr) | 2010-06-09 |
Family
ID=39301095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08835770A Withdrawn EP2193363A1 (fr) | 2007-09-18 | 2008-09-08 | Electrode pour systeme microfluidique |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2193363A1 (fr) |
| FR (1) | FR2921157A1 (fr) |
| WO (1) | WO2009044063A1 (fr) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324761A (en) * | 1981-04-01 | 1982-04-13 | General Electric Company | Hydrogen detector |
| US5119441A (en) * | 1989-03-28 | 1992-06-02 | Ricoh Company, Ltd. | Optical character recognition apparatus and method using masks operation |
| US5110441A (en) * | 1989-12-14 | 1992-05-05 | Monsanto Company | Solid state ph sensor |
| US5989402A (en) * | 1997-08-29 | 1999-11-23 | Caliper Technologies Corp. | Controller/detector interfaces for microfluidic systems |
| US20050103624A1 (en) * | 1999-10-04 | 2005-05-19 | Bhullar Raghbir S. | Biosensor and method of making |
| US6662439B1 (en) * | 1999-10-04 | 2003-12-16 | Roche Diagnostics Corporation | Laser defined features for patterned laminates and electrodes |
| US6783647B2 (en) * | 2001-10-19 | 2004-08-31 | Ut-Battelle, Llc | Microfluidic systems and methods of transport and lysis of cells and analysis of cell lysate |
| WO2003076052A1 (fr) * | 2002-03-05 | 2003-09-18 | Caliper Life Sciences, Inc. | Systemes microfluidiques en mode mixte |
| US20060022130A1 (en) * | 2004-07-29 | 2006-02-02 | Predicant Biosciences, Inc., A Delaware Corporation | Microfluidic devices and methods with integrated electrical contact |
-
2007
- 2007-09-18 FR FR0757646A patent/FR2921157A1/fr not_active Withdrawn
-
2008
- 2008-09-08 EP EP08835770A patent/EP2193363A1/fr not_active Withdrawn
- 2008-09-08 WO PCT/FR2008/051598 patent/WO2009044063A1/fr not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2009044063A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2921157A1 (fr) | 2009-03-20 |
| WO2009044063A1 (fr) | 2009-04-09 |
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| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: GASCON, HELENE Inventor name: DUISIT, GERALDINE Inventor name: VALENTIN, EMMANUEL Inventor name: BRUNET, EDOUARD |
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| DAX | Request for extension of the european patent (deleted) | ||
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| 18D | Application deemed to be withdrawn |
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