EP0830590A1 - Ph-sensitive microsensor and a method of manufacturing it - Google Patents

Ph-sensitive microsensor and a method of manufacturing it

Info

Publication number
EP0830590A1
EP0830590A1 EP96915992A EP96915992A EP0830590A1 EP 0830590 A1 EP0830590 A1 EP 0830590A1 EP 96915992 A EP96915992 A EP 96915992A EP 96915992 A EP96915992 A EP 96915992A EP 0830590 A1 EP0830590 A1 EP 0830590A1
Authority
EP
European Patent Office
Prior art keywords
sensor
sensitive
microsensor
sensor membrane
membrane
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Withdrawn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
EP96915992A
Other languages
German (de)
French (fr)
Inventor
Michael Josef SCHÖNING
Willi Zander
Jürgen Schubert
Lutz Beckers
Axel Michael Schaub
Peter Kordos
Hans LÜTH
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
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
Priority claimed from DE1995120059 external-priority patent/DE19520059C1/en
Application filed by Forschungszentrum Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Publication of EP0830590A1 publication Critical patent/EP0830590A1/en
Withdrawn legal-status Critical Current

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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
    • G01N27/333—Ion-selective electrodes or membranes
    • 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
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood

Definitions

  • pH-sensitive microsensor pH-sensitive microsensor and method for its production
  • the invention relates to a pH-sensitive microsensor based on silicon according to the preamble of claim 1. Furthermore, the invention relates to a method for its production according to the preamble of claim 4.
  • ISFET ion-sensitive field effect transistors
  • the basic structure of which corresponds to a conventional MOSFET instead of the metallic gate electrode, such a component has a combination of a sensitive layer (sensor membrane), electrolyte and reference electrode.
  • a sensitive layer sensor membrane
  • electrolyte electrolyte
  • reference electrode for example, C. Cui et al. , An experimental study of inorganic gate ISFETS, Sensors and Actuators B, 1 (1990), p. 421, instead of a complete ISFET also using capacitive field effect structures which correspond in structure to the gate area of an ISFET as pH sensors.
  • this sensor membrane consists, for example, of Si 3 N 4 , Ta 2 0 5 or also Al 2 0 3 .
  • the sensor membrane is formed, in particular when Al 2 0 3 is selected, by means of sputtering technology or chemical vapor deposition (CVD).
  • a disadvantage of the known microsensors containing such sensor membranes is the relatively high drift rates.
  • the object is achieved by a microsensor according to the entirety of the features according to claim 1.
  • the object is further achieved by a method according to the The entirety of the features according to claim 4. Further expedient or advantageous embodiments or variants can be found in the subclaims which refer back to one of these claims.
  • the characteristics with regard to the sensor properties for the sensor according to the invention are comparable or even better with the known sensors.
  • the drift rate of the sensor according to the invention is considerably reduced in comparison with the known sensors. While the sensors manufactured with sputter technology or CVD have a drift rate of at least 5 to 10 mV per day, as for example from IEEE Trans, on Electron Dev., Vol. Ed-26, No. 12, December 1979, p. 1939 ff., The sensor according to the invention shows a drift rate of, for example, only 1.0 mVolt per day or better.
  • the microsensor according to the invention can be used as a chemical pH sensor.
  • a biochemical sensor can also be formed on the basis thereof.
  • a biosensitive layer can be formed on the sensor membrane, for example from an enzyme.
  • the biosensitive sensor has the advantages mentioned above for the microsensor, in particular with regard to the lower drift rate.
  • the micro- or biosensor can optionally be re-annealed in an oxygen atmosphere during production after formation of the membrane.
  • Fig. 1 Micro or biosensor according to the invention
  • the micro or biosensor according to the invention is shown in FIG.
  • an insulating SiO 2 layer 2 (with a thickness in the range of 30-100 nm, for example) was successively placed on a substrate 1 made of p-doped silicon (with a concentration of, for example, 5 * 10 p / cm and a substrate thickness of 400 ⁇ m) ) and the sensor membrane 3 made of Al 2 0 3 and formed in this way.
  • layer 3 shown in FIG. 1 is to be understood as a sensor membrane with a biosensitive layer formed thereon from, for example, an enzyme.
  • An Ag-AgCl reference electrode 7 protruding into the electrolyte is connected via the voltage U bias and an alternating voltage U_ to an aluminum contact electrode 8 (with a layer thickness of 200 nm) located on the back of the substrate 1.
  • the thickness of the sensor membrane was selected in the range from 5 nm to 1000 nm, in particular in the range from 30 nm to 100 nm.
  • the insulating layer 2 for forming the sensor membrane can be coated by means of laser-induced evaporation of an Al 2 O 3 target by means of a KrF laser, for example.
  • the growth rate of the target material to form the membrane is in the range from 0.01 nm / s to 10 nm / s, in particular 1.0 nm / s.
  • the set oxygen partial pressure was selected in the range from 1 * 10 "4 mbar to 1 * 10 " 2 mbar.
  • the temperature on the substrate surface during the ablation was up to 1500 ° C., in particular in the range from 600 ° C. to 900 ° C., preferably 800 ° C.
  • the invention is not limited to the materials or dimensions mentioned here. Rather, other materials or dimensions are also conceivable and usable, depending on the required boundary conditions. Also it is conceivable to provide multiple systems with several sensitive layers 3, in particular sensor membranes and / or biosensitive layers.

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)
  • Physical Vapour Deposition (AREA)

Abstract

The invention concerns a pH-sensitive microsensor with sensor diaphragm. The latter is formed by laser ablation and can be produced by ablation from aluminium oxide or another material. This results in a sensor with very low drift.

Description

B e s c h r e i b u n gDescription
pH-sensitiver Mikrosensor, sowie Verfahren zu seiner HerstellungpH-sensitive microsensor and method for its production
Die Erfindung betrifft einen pH-sensitiven Mikrosensor auf Siliziumbasis gemäß dem Oberbegriff des Anspruchs 1. Desweiteren betrifft die Erfindung ein Verfahren zu seiner Herstellung gemäß dem Oberbegriff des Anspruchs 4.The invention relates to a pH-sensitive microsensor based on silicon according to the preamble of claim 1. Furthermore, the invention relates to a method for its production according to the preamble of claim 4.
Als Stand der Technik sind aus T. Matsuo et al. , Me- thods of ISFET fabrication, Sensors and Actuators 1 (1981) , S. 77, H. Abe et al . , ISFETs using inorganic gate thin fil s, IEEE Trans. Electron. Dev. Ed. 26, 12 (1979) , S.1939 oder L. Bousse et al. , Hysteresis in Al203-gate ISFETS, Sensors and Actuators B, 2 (1990) , S. 103, pH-sensitive Mikrosensoren auf Siliziumbasis bekannt.As prior art, T. Matsuo et al. , Methods of ISFET fabrication, Sensors and Actuators 1 (1981), p. 77, H. Abe et al. , ISFETs using inorganic gate thin fil s, IEEE Trans. Electron. Dev. Ed. 26, 12 (1979), p.1939 or L. Bousse et al. , Hysteresis in Al 2 0 3 -gate ISFETS, Sensors and Actuators B, 2 (1990), p. 103, pH-sensitive microsensors based on silicon are known.
Dabei handelt es sich um sog. Ionensensitive Feldef¬ fekttransistoren (ISFET) , die in ihrem Grundaufbau ei¬ nem herkömmlichen MOSFET entsprechen. Anstelle der me- tallischen Gateelektrode weist ein solches Bauelement eine Kombination aus sensitiver Schicht (Sensormembran) , Elektrolyt und Referenzelektrode auf. Weiterhin ist aus z.B. C. Cui et al. , An experimental study of inorganic gate ISFETS, Sensors and Actuators B, 1 (1990), S. 421 bekannt, anstelle eines kompletten ISFETs auch kapazitive Feldeffektstrukturen, die in ih¬ rem Aufbau dem Gatebereichs eines ISFETs entsprechen, als pH Sensoren einzusetzen.These are so-called ion-sensitive field effect transistors (ISFET), the basic structure of which corresponds to a conventional MOSFET. Instead of the metallic gate electrode, such a component has a combination of a sensitive layer (sensor membrane), electrolyte and reference electrode. Furthermore, for example, C. Cui et al. , An experimental study of inorganic gate ISFETS, Sensors and Actuators B, 1 (1990), p. 421, instead of a complete ISFET also using capacitive field effect structures which correspond in structure to the gate area of an ISFET as pH sensors.
Bei einem pH-sensitiven ISFET besteht diese Sensormem- bran z.B. aus Si3N4, Ta205 oder auch Al203. Die bestenIn the case of a pH-sensitive ISFET, this sensor membrane consists, for example, of Si 3 N 4 , Ta 2 0 5 or also Al 2 0 3 . The best
Resultate bezüglich Sensitivität, Stabilität und Selek¬ tivität wurden für Ta205 und A1203 erzielt.Results regarding sensitivity, stability and selectivity were achieved for Ta 2 0 5 and A1 2 0 3 .
Die Sensormembran wird, insbesondere bei Wahl des Al203 mittels Sputtertechnologie oder Chemical Vapor Deposi¬ tion (CVD) gebildet.The sensor membrane is formed, in particular when Al 2 0 3 is selected, by means of sputtering technology or chemical vapor deposition (CVD).
Nachteilig bei den bekannten, solche Sensormembrane enthaltenden Mikrosensoren sind die relativ großen Driftraten.A disadvantage of the known microsensors containing such sensor membranes is the relatively high drift rates.
Es ist deshalb Aufgabe der Erfindung einen Sensor zu schaffen, sowie ein Verfahren zur Herstellung eines solchen bereitzustellen, bei dem eine verbesserte, ver- ringerte Driftrate des Sensors erreicht wird.It is therefore an object of the invention to provide a sensor and to provide a method for producing one in which an improved, reduced drift rate of the sensor is achieved.
Die Aufgabe wird gelöst durch einen Mikrosensor gemäß der Gesamtheit der Merkmale nach Anspruch 1. Die Aufga¬ be wird ferner gelöst durch ein Verfahren gemäß der Ge- samtheit der Merkmale nach Anspruch 4. Weitere zweckmä¬ ßige oder vorteilhafte Ausfuhrungsformen oder Varianten finden sich in den auf jeweils einen dieser Ansprüche rückbezogenen Unteransprüchen.The object is achieved by a microsensor according to the entirety of the features according to claim 1. The object is further achieved by a method according to the The entirety of the features according to claim 4. Further expedient or advantageous embodiments or variants can be found in the subclaims which refer back to one of these claims.
Es wurde erkannt, die Abscheidung von Al203 als pH- sensitive Schicht mittels Laserablation für kapazitive Feldeffektsensoren auf Halbleiterbasis einzusetzen. Der Vorteil der Laserablation liegt dabei sowohl in der einfachen Prozeßführung als auch in der gezielt stöchiometrischen Abscheidung von Mehrkomponentensyste¬ men. Dabei kann vorteilhafterweise gemäß Anspruch 2 bzw. 5 als Material Al203 Einsatz finden. Es sind je¬ doch auch andere Materialien zur Bildung der Membran vorstellbar.It was recognized that the deposition of Al 2 0 3 as a pH-sensitive layer by means of laser ablation was used for capacitive field effect sensors based on semiconductors. The advantage of laser ablation lies both in the simple process control and in the targeted stoichiometric deposition of multicomponent systems. 5 can advantageously be used as material Al 2 0 3 . However, other materials for forming the membrane are also conceivable.
Außerdem ist bei Verwendung der Laserablation gemäß An¬ spruch 1 bzw. 4 vorteilhaft, daß weder eine aufwendige UHV-Technologie wie beim Sputterprozeß, insbesondere lange Pumpzeiten und zudem nur geringe Aufwachsraten, noch die Zufuhr von speziellen Prozeßgasen (AlCl3, AlBr3, NO) und eine aufwendige Prozeßgasführung und - entsorgung wie bei der CVD-Abscheidung, erforderlich sind.In addition, when using laser ablation according to claim 1 or 4, it is advantageous that neither complex UHV technology as in the sputtering process, in particular long pumping times and also only low growth rates, nor the supply of special process gases (AlCl 3 , AlBr 3 , NO ) and complex process gas routing and disposal as in CVD separation are required.
Der erfindungsgemäße Mikrosensor besitzt vorteilhafter- weise eine hohe Empfindlichkeit im Bereich von bei¬ spielsweise 56 mV/pH für Konzentrationsbereiche von pH=3 bis zu pH=10. Besonders vorteilhaft erweist sich der Mikrosensor hinsichtlich der Langzeitstabilität un¬ ter ständiger Elektrolytexposition. Sie beträgt bei¬ spielsweise mehr als sechs Monate. Dabei sind die Cha- rakteristika bzgl. der Sensoreigenschaften für den er- findungsgemäßen Sensor mit den bekannten Sensoren ver¬ gleichbar oder sogar besser.The microsensor according to the invention advantageously has a high sensitivity in the range of, for example, 56 mV / pH for concentration ranges from pH = 3 to pH = 10. It has proven to be particularly advantageous the microsensor with regard to long-term stability under constant electrolyte exposure. For example, it is more than six months. The characteristics with regard to the sensor properties for the sensor according to the invention are comparable or even better with the known sensors.
Schließlich ist beim Einsatz von mit Hilfe der La¬ serablation gebildeten Sensormembranen beim erfindungs- gemäßen Mikrosensor in besonders vorteilhafter Weise die Driftrate des erfindungsgemäßen Sensors gegenüber den bekannten Sensoren erheblich reduziert. Während die mit Sputtertechnologie oder CVD hergestellten Sensoren einen Driftrate von wenigstens 5 bis 10 mV pro Tag auf- weisen, wie beispielsweise aus IEEE Trans, on Electron Dev., Vol. Ed-26, No. 12, December 1979, S. 1939 ff. bekannt, zeigt der erfindungsgemäße Sensor eine Drif¬ trate von beispielsweise nur 1,0 mVolt pro Tag oder besser.Finally, when sensor membranes formed with the aid of laser ablation are used in the microsensor according to the invention, the drift rate of the sensor according to the invention is considerably reduced in comparison with the known sensors. While the sensors manufactured with sputter technology or CVD have a drift rate of at least 5 to 10 mV per day, as for example from IEEE Trans, on Electron Dev., Vol. Ed-26, No. 12, December 1979, p. 1939 ff., The sensor according to the invention shows a drift rate of, for example, only 1.0 mVolt per day or better.
Der erfindungsgemäße Mikrosensor kann als chemischer pH-Sensor eingesetzt werden. Auf seiner Basis kann aber auch ein biochemischer Sensor gemäß Anspruch 3 bzw. 6 gebildet werden. Dazu kann auf der Sensormembran eine biosensitive Schicht z.B. aus einem Enzym gebildet sein. Der biosensitive Sensor weist insofern die oben für den Mikrosensor genannten Vorteile, insbesondere hinsichtlich der niedrigeren Driftrate, auf. Zur weiteren Annährung an die ideale Stöchiometrie kann der Mikro- bzw. Biosensor bei der Herstellung nach Bil¬ dung der Membran in einer Sauerstoffatmosphäre gegebe¬ nenfalls nachgetempert werden.The microsensor according to the invention can be used as a chemical pH sensor. However, a biochemical sensor can also be formed on the basis thereof. For this purpose, a biosensitive layer can be formed on the sensor membrane, for example from an enzyme. In this respect, the biosensitive sensor has the advantages mentioned above for the microsensor, in particular with regard to the lower drift rate. To further approximate the ideal stoichiometry, the micro- or biosensor can optionally be re-annealed in an oxygen atmosphere during production after formation of the membrane.
Die Erfindung ist im weiteren an Hand von Figur und Ausführungsbeispiel näher erläutert. Es zeigt:The invention is explained in more detail with reference to the figure and embodiment. It shows:
Fig. 1: Erfindungsgemäßer Mikro- bzw. BiosensorFig. 1: Micro or biosensor according to the invention
AusführungsbeispielEmbodiment
In der Figur 1 ist der erfindungsgemäße Mikro- bzw. Biosensor dargestellt. Dazu wurde auf einem Substrat 1 aus p-dotiertem Silicium (mit einer Konzentration von beispielsweise 5*10 p/cm und einer Substratdicke von 400 μm) nacheinander eine isolierende Si02-Schicht 2 (mit einer Dicke beispielsweise im Bereich von 30-100 nm) und die Sensormembran 3 aus Al203 aufgebracht und auf diese Weise gebildet . Zur Ausbildung als Biosensor ist die in Figur 1 dargestellte Schicht 3 als eine Sen- sormembran mit darauf gebildeter, biosensitiver Schicht aus z.B. einem Enzym, zu verstehen.The micro or biosensor according to the invention is shown in FIG. For this purpose, an insulating SiO 2 layer 2 (with a thickness in the range of 30-100 nm, for example) was successively placed on a substrate 1 made of p-doped silicon (with a concentration of, for example, 5 * 10 p / cm and a substrate thickness of 400 μm) ) and the sensor membrane 3 made of Al 2 0 3 and formed in this way. To form a biosensor, layer 3 shown in FIG. 1 is to be understood as a sensor membrane with a biosensitive layer formed thereon from, for example, an enzyme.
Über der sensitiven Schicht 3 ist ein flüssiger Elek¬ trolyt (in Abhängigkeit der gewählten Pufferlösung im Bereich von beispielsweise pH=2 bis zu pH=ll gewählt) von einer Wandung 5 über O-Ringe zur Schicht flüssig¬ dicht abgedichtet angeordnet. Eine in den Elektrolyten hineinragende Ag-AgCl-Referenzelektrode 7 ist über die Spannung UBias und eine Wechselspannung U_ mit einer an der Rückseite des Substrats 1 befindlichen Aluminium- Kontaktelektrode 8 (mit einer Schichtdicke von 200 nm) verbunden.A liquid electrolyte (depending on the selected buffer solution in the Range selected from, for example, pH = 2 to pH = 11) from a wall 5 via O-rings to the layer in a liquid-tight manner. An Ag-AgCl reference electrode 7 protruding into the electrolyte is connected via the voltage U bias and an alternating voltage U_ to an aluminum contact electrode 8 (with a layer thickness of 200 nm) located on the back of the substrate 1.
Die Dicke der Sensormembran wurde im Bereich von 5 nm bis 1000 nm, insbesondere im Bereich von 30 nm bis zu 100 nm, gewählt.The thickness of the sensor membrane was selected in the range from 5 nm to 1000 nm, in particular in the range from 30 nm to 100 nm.
Die Beschichtung der isolierenden Schicht 2 zur Bilde- ung der Sensormembran kann mittels laserinduzierten Verdampfens eines Al203-Targets durch beispielsweise einen KrF-Laser erfolgen. Die Aufwachsrate des Target- material zur Bildung der Membran liegt im Bereich von 0,01 nm/s bis zu 10 nm/s, insbesondere 1,0 nm/s . Der eingestellte Sauerstoffpartialdruck wurde im Bereich von 1*10"4 mBar bis zu 1*10"2 mBar gewählt. Die Tempera¬ tur an der Substratoberfläche während der Ablation be¬ trug bis zu 1500 °C, insbesondere im Bereich von 600 °C bis zu 900 °C, vorzugsweise 800 °C.The insulating layer 2 for forming the sensor membrane can be coated by means of laser-induced evaporation of an Al 2 O 3 target by means of a KrF laser, for example. The growth rate of the target material to form the membrane is in the range from 0.01 nm / s to 10 nm / s, in particular 1.0 nm / s. The set oxygen partial pressure was selected in the range from 1 * 10 "4 mbar to 1 * 10 " 2 mbar. The temperature on the substrate surface during the ablation was up to 1500 ° C., in particular in the range from 600 ° C. to 900 ° C., preferably 800 ° C.
Die Erfindung beschränkt sich nicht auf die hier ge¬ nannten Materialien oder Abmessungen. Vielmehr sind auch andere Materialien oder Abmessungen denkbar und brauchbar, je nach geforderten Randbedingungen. Auch ist es vorstellbar, mehrfache Systeme mit mehreren sen¬ sitiven Schichten 3, insbesondere Sensormembranen und / oder biosensitive Schichten, vorzusehen. The invention is not limited to the materials or dimensions mentioned here. Rather, other materials or dimensions are also conceivable and usable, depending on the required boundary conditions. Also it is conceivable to provide multiple systems with several sensitive layers 3, in particular sensor membranes and / or biosensitive layers.

Claims

Patentansprüche claims
1. pH-sensitiver Mikrosensor mit Sensormembran, gekennzeichnet durch eine mit Hilfe der Laserablation gebildete Sensormembran.1. pH-sensitive microsensor with sensor membrane, characterized by a sensor membrane formed with the aid of laser ablation.
2. pH-sensitiver Mikrosensor nach Anspruch 1, gekennzeichnet durch Al203 als Material für die Sensormembran.2. pH-sensitive microsensor according to claim 1, characterized by Al 2 0 3 as material for the sensor membrane.
3. Biosensitiver Sensor mit einem Mikrosensor nach Anspruch 1 oder 2 mit einer auf der Sensormembran gebildeten, biosensitiven, insbesondere aus einem Enzym bestehenden Schicht.3. Biosensitive sensor with a microsensor according to claim 1 or 2 with a biosensitive layer formed on the sensor membrane, in particular consisting of an enzyme.
4. Verfahren zur Herstellung eines pH-sensitiven Mikrosensors mit Sensormembran, dadurch gekennzeichnet , daß mit Hilfe eines Lasers Material aus einem Target herausgelöst und zur Bildung der Sensormembran auf einer Oberfläche abgeschieden wird. 4. A method for producing a pH-sensitive microsensor with a sensor membrane, characterized in that material is removed from a target with the aid of a laser and is deposited on a surface to form the sensor membrane.
5. Verfahren zur Herstellung eines pH-sensitiven Mikrosensors nach Anspruch 4, dadurch gekennzeichnet , daß als Material zur Bildung der Sensormembran Al203 gewählt wird.5. A method for producing a pH-sensitive microsensor according to claim 4, characterized in that Al 2 0 3 is selected as the material for forming the sensor membrane.
6. Verfahren zur Herstellung eines biosensitiven Sensors mit einem pH-sensitiven Mikrosensor nach6. Process for the production of a biosensitive sensor with a pH-sensitive microsensor
Anspruch 4 oder 5, dadurch gekennzeichnet , daß auf der Sensormembran eine biosensitive Schicht gebildet wird.Claim 4 or 5, characterized in that a biosensitive layer is formed on the sensor membrane.
7. Verfahren zur Herstellung eines pH-sensitiven Mikrosensors nach einem der Ansprüche 4 bis 6, dadurch gekennzeichnet , daß nach Bildung der Sensormembran diese in einer Sauerstoff- atmosphäre getempert wird. 7. A method for producing a pH-sensitive microsensor according to one of claims 4 to 6, characterized in that after formation of the sensor membrane, this is annealed in an oxygen atmosphere.
EP96915992A 1995-06-06 1996-06-04 Ph-sensitive microsensor and a method of manufacturing it Withdrawn EP0830590A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1995120059 DE19520059C1 (en) 1995-06-06 1995-06-06 Acidity micro-sensor with diaphragm vapour-deposited by laser ablation
DE19520059 1995-06-06
DE29512999U DE29512999U1 (en) 1995-06-06 1995-08-12 pH-sensitive microsensor
DE29512999U 1995-08-12
PCT/DE1996/001021 WO1996039624A1 (en) 1995-06-06 1996-06-04 Ph-sensitive microsensor and a method of manufacturing it

Publications (1)

Publication Number Publication Date
EP0830590A1 true EP0830590A1 (en) 1998-03-25

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EP96915992A Withdrawn EP0830590A1 (en) 1995-06-06 1996-06-04 Ph-sensitive microsensor and a method of manufacturing it

Country Status (2)

Country Link
EP (1) EP0830590A1 (en)
WO (1) WO1996039624A1 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2391467A1 (en) * 1977-05-20 1978-12-15 Anvar MEASUREMENT CELL FOR MICRODOSAGES, INCLUDING ELECTRODES WITH ENZYMATIC MEMBRANES
DK133280A (en) * 1980-03-27 1981-09-28 Radiometer As Electrode arrangement
US5348776A (en) * 1991-04-23 1994-09-20 Osaka Gas Company Limited Method of producing interconnectors for solid oxide electrolyte fuel cells

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9639624A1 *

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