Metal oxide electrodes

• US 5,009,766 A
• Filed: 10/30/1990
• Issued: 04/23/1991
• Est. Priority Date: 02/08/1988
• Status: Expired due to Term

• Current Assignee: i STAT Corporation (Abbott Laboratories Incorporated)
• Original Assignee: i STAT Corporation (Abbott Laboratories Incorporated)
• Inventors: Lauks, Imants R.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Phasge, Arun S.
• Application Number:
  US07/608,601
• Time in Patent Office: 175 Days
• Field of Search: 204/419, 204/433, 204/291, 204/400, 204/403, 204/153.21, 204/153.12, 435/817, 435/291
• US Class Current: 204/403.14
• CPC Class Codes: G01N 27/333 Ion-selective electrodes or membranes glass electrodes G01N27/36
• CPC Class Codes: Y10S 435/817 Enzyme or microbe electrode

Abstract

An electrode for measuring the activity of ionic species. The electrode comprises a material which is chemically sensitive to at least one ionic species. The material comprises an insulating component and a conductive component of lower resistivity than the insulating component. The insulating component has a density of proton binding sites sufficiently large to be sensitive to the ionic species. The conductive component comprises particles, the size of which are sufficiently small to modify the bulk conductive properties such that the susceptibility of the particles to redox interference in the operation of the electrode is decreased, while maintaining sufficient conductivity to operate in Faradaic electrode configurations. Illustratively, the insulating component is tantalum oxide, zirconium oxide or aluminum oxide and the conductive component is iridium, platinum, ruthenium, palladium, rhodium or osmium oxide.

Claims

1. A metal oxide electrode sensitive to hydrogen ions comprising:

a mixture of at least one insulating material having a density of binding sites sufficiently large to be sensitive to hydrogen ions, and at least one conductive metal oxide selected from the Group VIIIB metal oxides,

wherein the size of the particles of conductive metal oxide in said mixture is sufficiently small as to not exhibit bulk conductive properties, thereby reducing the susceptibility of said mixture to redox interference, while the molar ratio of said conductive metal oxide to said insulating material is sufficiently large than the resistivity of said mixture is in the range of 10¹⁰ to 10¹⁴ ohm-cm, whereby the electrode, as a whole, has sufficient conductivity to operate in a Faradaic configuration.

2. The electrode of claim 1 wherein said insulating material is an insulating metal oxide with a resistivity of at least 10¹⁴ ohm-cm.

3. The electrode of claim 2 wherein said mixture is deposited on a surface of a substrate by sputter coating.

4. The electrodes of claim 3 wherein said metal oxide mixture has no metal atoms in common with said substrate.

5. The electrode of claim 1 further comprising:

at least one layer of material placed over said mixture, said layer of material being reactive with an analyte to be measured,

wherein reaction with said analyte to be measured produces a change in concentration of hydrogen ions which is sensed by said mixture.

6. The electrode of claim 1 wherein the size of conductive metal oxide particles is in the range of less than 100 angstroms.

7. The electrode of claim 1 wherein particle size is controlled in a manner such that the insulating material and conductive metal oxide form an amorphous alloy.

8. The electrode of claim 1 wherein said conductive metal oxide is selected from the group consisting of iridium, platinum, ruthenium, palladium, rhodium, and osmium oxides.

9. The electrode of claim 1 wherein said insulating material is selected from the group consisting of aluminum oxide, zirconium oxide and tantalum oxide.

10. The electrode of claim 1 wherein the insulating material has density of hydrogen ion binding sites greater than 10¹³ /cm².

11. An electrode for measuring pH comprising:

a mixture of a first component which is conductive in bulk form, and a second component having a substantially greater resistivity in bulk form than that of said first component, said second component having a redox-interference-free surface response to hydrogen ions, said first component being present in said mixture in sufficiently small particle size so as to modify its bulk conductive properties enough that it does not affect the redox-interference-free surface response of said second component to hydrogen ions,

wherein the molar ratio of said first component to said second component is sufficiently large that the resistivity of said mixture is in the range of 10¹⁰ to 10¹⁴ ohm-cm, whereby the electrode, as a whole, has sufficient conductivity to operate as a pH sensing electrode.

12. The electrode of claim 11 wherein said first component is a conductive metal oxide and said second component is an insulating metal oxide.

13. The electrode of claim 11 wherein said first component is iridium oxide.

14. The electrode of claim 11 wherein said second component is selected from the group consisting of aluminum oxide, zirconium oxide, and tantalum oxide.

15. The electrode of claim 13 wherein said second component is tantalum oxide.

16. The electrode of claim 11 wherein the size of the particles of the first component are in the range of less than 100 angstroms.

17. The electrode of claim 11 wherein particle size is controlled in a manner such that the insulating material and conductive metal oxide form an amorphous alloy.

18. The electrodes of claim 11 wherein said mixture is deposited on a substrate by sputter coating.

19. The electrode of claim 18 wherein said mixture has no metal atoms in common with said substrate.

20. The electrode of claim 11 further comprising:

at least one layer of material placed over said mixture, said layer of material being reactive with an analyte to be measured,

wherein reaction with said analyte to be measured produces a change in concentration of hydrogen ions which is sensed by said mixture.