EP0418359A1 - Ensemble de plusieurs microelectrodes - Google Patents

Ensemble de plusieurs microelectrodes

Info

Publication number
EP0418359A1
EP0418359A1 EP19900905379 EP90905379A EP0418359A1 EP 0418359 A1 EP0418359 A1 EP 0418359A1 EP 19900905379 EP19900905379 EP 19900905379 EP 90905379 A EP90905379 A EP 90905379A EP 0418359 A1 EP0418359 A1 EP 0418359A1
Authority
EP
European Patent Office
Prior art keywords
electrode
electrodes
arrangement according
electrode arrangement
insulating layer
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Withdrawn
Application number
EP19900905379
Other languages
German (de)
English (en)
Inventor
Gerald Dr. Urban
Gerhard Mag. Nauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0418359A1 publication Critical patent/EP0418359A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies

Definitions

  • the invention relates to a micro-multi-electrode arrangement for electrochemical measurement and generation of electroactive species, in which the electrodes are arranged on a carrier.
  • Miniaturized electrodes for the intended purposes must have a certain material quality of the surface for surfaces in the square micrometer range. For measurements in the biological field, it must be ensured that the electrochemical system is not disturbed by a correspondingly low conversion of substances, which means that extremely low currents must flow through the electrodes. In the case of potentiodynamic measurements, such a microelectrode arrangement at rates of increase in the potential of up to 100 mV / s must still enable diffusion-controlled currents, the level of which, similar to the processes in polarography, directly is proportional to the concentration of the electroactive species in the electrolyte solution under investigation.
  • micro-multi-electrode arrangements are primarily intended to make it possible to carry out electrochemical investigations in areas which were previously not accessible to an investigation.
  • examinations in biological tissues examinations in electrochemical reactors, in battery systems and in corrosion examinations, in which measurements were previously not possible with conventional macroelectrodes, are of particular importance.
  • the aim of the invention is to create a micro-multi-electrode arrangement which is distinguished by defined geometry and reproducible measured values in electrochemical measurements and at the same time reduces susceptibility to interference and enables largely noise-free measurements.
  • the micro multi-electrode arrangement according to the invention essentially consists in that an inner Electrode and at least two further electrodes are provided, the inner electrode being connected as a reference electrode and the further electrodes at least partially surrounding the inner electrode in the projection onto the carrier. Because an inner electrode is connected as a reference electrode and the further electrodes, which can optionally be used as measuring electrodes or counter electrodes, at least partially surround this inner electrode, the inner electrode is largely shielded, which enables substantially noise-free measurements.
  • micro-multi-electrode arrangement creates the possibility of defining a defined geometry in which the electrodes can be kept at considerably shorter distances from one another.
  • the much smaller distance is clearly defined by the geometry of the micro-multi-electrode arrangement and the influence of poorly conductive electrolyte solutions, such as physiological solutions, can be largely reduced due to such a small distance between the electrodes.
  • micro-multi-electrode arrangements not only succeed in noise-free measurements, but also in measurements for the first time in systems that were previously not accessible at all or only using complex correction methods, without that excessive instructive effort is required.
  • micro-multi-electrode arrangement it has been possible for the first time to quantitatively determine different neurotransmitters side by side using a simple three-electrode structure with gold as the electrode material.
  • platinum as the electrode material and an enzyme immobilized on the electrode material, it has been possible, for example, to implement a miniaturized, reliable glucose sensor.
  • platinum as the electrode material and a tracking membrane covering the electrodes, it is possible to measure oxygen concentrations in different electrolytes.
  • the micro-multi-electrode arrangement according to the invention can also be used in a simple manner for structures in which, in addition to a reference electrode and at least two further electrodes, additional electrodes are accommodated in a very small space, a plurality of different electrochemically active species being detectable at the same time.
  • the lateral resolution of the concentration of the substance to be measured is also possible.
  • a geometrically particularly favorable electrode arrangement with a particularly homogeneous current density distribution can be achieved in the context of the invention if the design is such that the electrodes are arranged concentrically.
  • the individual electrodes can be applied to the carrier material, and contact can be made, for example, by conductor tracks on the carrier material.
  • the design can advantageously be such that the layers forming the electrodes are separated by at least one insulating layer.
  • a concentric arrangement of electrodes can in principle enable different geometrical designs of the electrodes arranged concentrically to a center.
  • the design is advantageously made such that the electrodes are formed from at least partially circular segments and that the area of the non-active separating areas is small compared to the area of the active electrode segments, with the Measure to keep the area of the inactive separation areas small compared to the area of the active electrode segments ensures that capacitive effects can be largely excluded.
  • a particularly preferred embodiment of the micro-multi-electrode arrangement according to the invention essentially consists in that the electrodes are arranged in a common plane.
  • the contacting of the electrodes can advantageously be made in such a design that the individual electrodes are connected to contacts via openings in the carrier on the side of the carrier facing away from the electrodes.
  • the inner electrode can take on the function of a counter electrode in addition to its function as a reference electrode.
  • the inner electrode it is particularly advantageous to design it in such a way that an electrode of the second type is used as the inner electrode.
  • Such electrodes of the second type in particular require a certain minimum volume, and particularly effective shielding of such inner electrodes is achieved if the design is such that the inner electrode is arranged on the carrier material and at least one further electrode with the interposition of at least one insulating layer is arranged at a distance from the surface of the carrier carrying the inner electrode. In this way, the spatial expansion of the inner electrode can be taken into account and better shielding and thus noise-free measurement can be guaranteed.
  • a counter electrode can also be arranged, the design advantageously being such that at least two working electrodes and one counter electrode are arranged at a radial distance from the reference electrode and preferably the counter electrode is larger than the working electrode (s) and is located at a greater central distance from the inner reference electrode than the working electrodes. In this way, the working electrodes are also effectively shielded ensured so that a further noise reduction of the measurements can be ensured.
  • the design can advantageously be such that the inner electrode is formed by a needle-shaped electrode, that at least one further electrode at least partially encloses the inner electrode with the interposition of at least one insulating layer and that the inner electrode is over an opening in the insulating layer is connected to the respective electrolyte.
  • the electrolyte required in each case for an electrode of the second type can be accommodated in the cavity of the inner electrode, the inner electrode being connected to the respective electrolyte in which the measurement is carried out, and in this way also can be used as a counter electrode.
  • the design is such that the inner electrode is arranged in a cavity formed by insulating layers and that at least one further electrode is embedded in the insulating layer and opens into the cavity and / or is arranged on the surface of the insulating layer, with such a design, a reusable inner electrode can be realized with good long-term durability.
  • the selective detection of certain electroactive species is achieved by using appropriately permeable membranes, the design according to the invention advantageously being such that at least one membrane is arranged above the electrodes.
  • metals in particular gold, platinum, palladium, iridium, Rhodium, molybdenum and tungsten, or carbon-containing, conductive substances, in particular glass-like carbon, polythiophene or polypyrrole, are used, the dimensions of the electrodes advantageously being between fractions of micrometers and millimeters for the desired miniaturization.
  • the design can advantageously be such that biologically active molecules and substances, in particular enzymes and antibodies, are immobilized on the electrode arrangement, the handling of the micro-multi-electrode arrangement according to the invention thereby being made particularly simple can that the electrode arrangement is applied to a carrier designed as a puncture sensor.
  • the design is advantageously made such that the electrode arrangement is built into a carrier designed as a catheter.
  • FIG. 1 shows a section through a first embodiment of a micro multi-electrode arrangement according to the invention
  • FIG. 2 shows a plan view in the direction of arrow II of the embodiment according to FIG. 1 on a reduced scale, FIG. 1 showing a section along line II of FIG. 2
  • 3 shows a modified embodiment in a view similar to that shown in FIG. 2
  • Fig. 4 shows a section through another modified Embodiment of a micro multi-electrode arrangement according to the invention
  • 5 shows a view in the direction of arrow V on the design according to FIG. 4 on a reduced scale, FIG. 4 showing a section along the line IV-IV of FIG. 5
  • 6 shows a modified embodiment with a multilayer structure in a representation analogous to FIGS.
  • FIG. 7 shows a plan view in the direction of arrow VII on the design according to FIG. 6 on a reduced scale, FIG. 6 showing a section along the line VI-VI of FIG. 7; 8 shows a section through a needle-shaped electrode arrangement according to the invention;
  • FIG. 9 shows a plan view of a further embodiment in a representation similar to FIG. 2, 3, 5 or 7; 10 to 13 show further modified embodiments in section, the electrodes being at least partially embedded in an insulating layer and opening into a cavity formed in the insulating layer or layers;
  • 14 and 15 are top views of different designs of carriers for micro-multi-electrode arrangements according to the invention, several systems of micro-electrodes being arranged on a common carrier; 16 and 17 show further possible uses of the micro-multi-electrode arrangement according to the invention, the electrode arrangement according to the invention being installed in a catheter in the embodiment according to FIG. 16 and being used in a flow measuring system in the embodiment according to FIG. 17.
  • the electrodes 1, 2 and 3 are arranged on an inert carrier 5 and are each electrically separated from one another by an insulating layer 4.
  • Essential for the function is the fact that the inner electrode 1, used as a reference electrode, is at least partially surrounded by the next outer electrode 2, an interrupted electrode structure consisting of at least partially circular segments 2a, 2b, 3a, 3b, as shown in Fig. 2, can be used, the non-active separation areas are smaller than the active electrode areas.
  • the inner electrode 1 is surrounded by two, almost semicircular electrodes 2 lying on the same radius, the inner electrode 1 in addition to the function of the reference electrode also as a counter electrode to the measuring or working electrodes can be switched.
  • the individual electrodes 1 to 3 are again located on an inert carrier material 5, again the reference electrode 1 being concentrically surrounded by the measuring electrode or working electrode 2.
  • the counterelectrode 3 again encloses the measuring electrode 2.
  • the derivation and contacting takes place through the inert carrier 5 with the aid of lead-through contacts 6. This arrangement enables a closed electrode structure.
  • the reference electrode 1 is applied to an inert support 5 in the middle of the structure.
  • the reference electrode 1 is then enclosed by an insulating layer 4, which at the same time isolates the electrically contacting conductor track, which is denoted schematically by 15, to form an external connection (not shown in more detail).
  • at least one measuring electrode 2 is applied to this insulating layer 4, and this and the contact conductor track are in turn surrounded by an insulating layer 4.
  • the counter electrode 3 is arranged concentrically on this insulating layer 4. When projected onto the carrier 5, the inner electrode 1 is thus surrounded by the further electrodes 2 and 3. This arrangement, shown in FIG. 6, in turn enables an uninterrupted electrode structure.
  • the respective electrodes are electrically insulated from one another and electrically conductively connected to a plug contact with a lead.
  • the inner electrode is quasi shielded from the outer one, which means that in many measuring methods even the smallest measurement variables can be determined with little noise.
  • the outer electrode can be made slightly larger than the next inner electrode, which means that the requirement for an inert counterelectrode, which should be larger than the respective measuring electrode, can be met.
  • a major advantage of the arrangement of the electrodes according to the invention is the feasibility of the smallest, optimal, geometric, flat design of a multi-electrode structure. This enables miniaturization down to the submicrometer range.
  • FIG. 8 A further possible three-dimensional arrangement is shown in section in FIG. 8.
  • a conductive needle-shaped carrier 1 which is designed as a glass or metal microelectrode, an insulation 4 is applied, which has an opening 7 to the measurement environment.
  • the or a measuring electrode 2 is arranged concentrically to this and separated from the counter electrode 3 by an insulating layer 4. The entire structure is then surrounded on the outside by an insulating layer 4.
  • This arrangement could advantageously be used as a puncture sensor.
  • FIG. 9 A further multi-electrode arrangement is shown in FIG. 9.
  • the electrode 1, used as a reference electrode, is surrounded concentrically by two measuring electrodes 2a and 2b.
  • the counter electrode 3 encloses the overall structure.
  • this arrangement has the advantage that two different electrochemically active species can be detected and on the other hand, a product formed on the electrode 2a can be reacted on the electrode 2b again, which enables characterization of the species.
  • the arrangement according to FIG. 9 has the advantage of a favorable diffusion geometry compared to the arrangement according to FIG. 2.
  • Suitable constructive measures and special processing techniques also make it possible to keep the insulating layers applied to the respective electrodes as thin as possible, so that the electroactive species and the resulting products can be optimally transported in and out. With these arrangements there is no accumulation of reaction products in the area of corners and edges at the transition zone between the insulating layer and the electrode material.
  • a defined amount of these substances can be applied in front of the metal electrode and with regard to the by producing thick insulating layers or by three-dimensional structures according to FIGS Concentration of this substance can be kept constant over a long period.
  • such three-dimensional structures can be used to keep protective and diffusion membranes in a defined location in a defined quantity for a long period of time.
  • FIG. 10 shows one of the possible constructions where the electrode 1 is seated directly on an inert carrier 5.
  • the electrode 1 is surrounded by the insulating layer 4.
  • An electrode 2 is applied to this insulating layer 4.
  • An insulating layer 4 follows again and the electrode 3 is applied thereon.
  • the electrode 3 is advantageously used as a counter electrode.
  • the arrangement of the electrode 3 can take place in different variants, a further variant being shown in FIG. 11.
  • the electrode 3 follows an insulating layer 4 directly on the electrode 2. A three-dimensional structure in a quasi cylindrical pore is thereby achieved.
  • special insulating layers such as polyimide, heights and thus pore lengths of up to several 100 micrometers can be achieved.
  • the 12 in turn shows a quasi-closed variant of an electrode arrangement.
  • the electrode 1 is concentrically surrounded by an insulating layer 4 on an inert carrier 5.
  • the electrode 2 used as the measuring electrode is located on the insulating layer 4, an insulating layer 4 'on top of it and the electrode 3 above it.
  • the insulating layer 4' can be formed as micromachined silicon.
  • a variant according to FIG. 13 can also be implemented here with a different arrangement of the electrode 3.
  • Electrode materials in particular metals, conductive polymers and vitreous carbon, can be used as electrode materials, noble metals such as gold, platinum, palladium and silver which can be processed by thin-layer lithography being preferred. Other metals can also be used as electrode material for special applications.
  • electrodes 1 to 3 can be constructed from different electrode materials.
  • FIGS. 1 to 7 or 10 to 13 show examples. At least two of the electrode structures according to FIGS. 1 to 7 or 10 to 13 are arranged on an inert carrier 5.
  • these microelectrode structures can be used as a three-electrode arrangement for all electrochemical measurement processes in all those systems which are not accessible to a macroscopic examination.
  • the structure can also be used as a miniaturized reference electrode, pH sensor or conductometric sensor.
  • such structures can be used as electrochemical actuators, e.g. for oxygen or hydrogen production or as stimulation electrodes.
  • Such structures can also be used as microsensors for impedance spectroscopy.
  • the use as a biosensor was also proven.
  • enzymes are immobilized on one of the electrodes.
  • Several electrodes for example according to FIGS. 2, 3 or 9, can also be coated with different enzymes.
  • the electrode structure according to FIG. 14 can also be used to carry out a difference measurement in the smallest space between active and denatured enzymes in the respective measuring medium. The interference suppression achieved in this way results in a significant improvement in the accuracy and reproducibility of the measurements.
  • a further advantage of the electrode arrangement consists in the possibility of applying protective membranes to one or other electrodes, whereby three-dimensional electrode arrangements and structures according to FIGS. 10 to 13 can advantageously be used, for example in the embodiment according to FIGS. 11 and 13 the top layer instead of an insulating layer 4 or 4 1 can be formed by a protective membrane.
  • a puncture sensor (Fig. 15) can be implemented as a handling option, as can the variant as a sensor, e.g. Glucose sensor 9, on a catheter 10 (FIG. 16) with feed lines 11, whereby investigations of substance concentrations e.g. directly possible in body caves.
  • micro multi-electrode arrangements can be integrated on a measuring chip 12 in a channel 13 as a flow sensor, e.g. be installed in a medical analyzer (FIG. 17), the measuring chip 12 being accommodated in a casting compound 14.
  • the microelectrode structures can be arranged as sensors in a two-dimensional array for the investigation of cell cultures as well as for the determination of gases, e.g. Oxygen in the blood can be used directly.

Abstract

Un ensemble de plusieurs microélectrodes pour effectuer des mesures électrochimiques et produire des espèces électroactives, dont les électrodes (1, 2, 3) sont agencées sur un support (5), comporte une électrode interne (1) et au moins deux autres électrodes (2, 3), l'électrode interne (1) servant d'électrode de référence et les autres électrodes (2, 3) entourant au moins en partie l'électrode interne (1), vue en projection sur le support (5).
EP19900905379 1989-04-04 1990-04-04 Ensemble de plusieurs microelectrodes Withdrawn EP0418359A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT783/89 1989-04-04
AT0078389A AT403528B (de) 1989-04-04 1989-04-04 Mikro-mehrelektrodenstruktur für elektrochemische anwendungen und verfahren zu ihrer herstellung

Publications (1)

Publication Number Publication Date
EP0418359A1 true EP0418359A1 (fr) 1991-03-27

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EP19900905379 Withdrawn EP0418359A1 (fr) 1989-04-04 1990-04-04 Ensemble de plusieurs microelectrodes

Country Status (6)

Country Link
EP (1) EP0418359A1 (fr)
JP (1) JPH03505785A (fr)
AT (1) AT403528B (fr)
AU (1) AU5348790A (fr)
DD (1) DD301930A9 (fr)
WO (1) WO1990012314A1 (fr)

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Also Published As

Publication number Publication date
ATA78389A (de) 1997-07-15
AU5348790A (en) 1990-11-05
JPH03505785A (ja) 1991-12-12
WO1990012314A1 (fr) 1990-10-18
AT403528B (de) 1998-03-25
DD301930A9 (de) 1994-07-21

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