Planar oxygen sensor

• US 5,102,525 A
• Filed: 12/10/1990
• Issued: 04/07/1992
• Est. Priority Date: 12/14/1989
• Status: Expired due to Fees

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi, Ltd.
• Inventors: Miyahara, Yuji, Tsukada, Keiji, Shibata, Yasuhisa, Miyagi, Hiroyuki
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): BELL, BRUCE F
• Application Number:
  US07/625,014
• Time in Patent Office: 484 Days
• Field of Search: 204/128, 204/412, 204/426, 204/415, 204/414
• US Class Current: 204/415
• CPC Class Codes: G01N 27/404 Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid , e.g. Clark-type oxygen sensors

Abstract

A planar oxygen sensor has an insulating substrate, a cathode formed on the insulating substrate generally at the center thereof; another electrode formed on the insulating substrate in a region other than the region of the cathode, a gas permeable membrane stretched to cover these electrodes and having its peripheral portion supported on the insulating substrate, and an electrolytic solution charged between the gas permeable membrane and the insulating substrate. A surface of the cathode is substantially in contact with the gas permeable membrane and is formed at a position higher than the gas permeable membrane support portion of the insulating substrate. A portion of the insulating substrate surface other than the region where the cathode is formed is recessed. Because the layer of electrolytic solution on the cathode is thin, oxygen molecules passing through the gas permeable membrane can immediately serve for the reduction at the cathode, thereby increasing the response speed of the planar oxygen sensor. Also, the amount of electrolytic solution is increased by the recess to extend the life of the sensor.

Claims

1. A planar oxygen sensor comprising:

an insulating substrate;

a frame formed so as to surround at least a part of a major surface of said insulating substrate;

a cathode formed on said insulating substrate generally at the center of the part of the major surface surrounded by said frame;

an anode formed on said insulating substrate between said frame and said cathode;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said cathode and said anode within the electrolyte chamber and having a peripheral portion supported on said frame; and

an electrolytic solution in said electrolyte chamber defined between said gas permeable membrane, said frame and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said frame at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said cathode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral portion of said stretched gas permeable membrane.

2. A planar oxygen sensor according to claim 1, wherein a portion of the insulating substrate surface inside the electrolyte chamber, other than the region where said cathode is formed, is formed as a recessed bottom surface with respect to the portion of the insulating substrate on which said cathode is formed.

3. A planar oxygen sensor according to claim 1, wherein said cathode is formed of platinum.

4. A planar oxygen sensor according to claim 1, wherein said insulating substrate comprises a silicon dioxide film.

20. A planar oxygen sensor as claimed in claim 1, wherein the stretched gas permeable membrane and said cathode surface are separated only by a layer of said electrolytic solution.

21. A planar oxygen sensor as claimed in claim 1, wherein the stretched gas permeable membrane substantially contacts said cathode surface.

22. A planar oxygen sensor as claimed in claim 4, further comprising a silicon substrate supporting said silicon dioxide film.

5. A planar oxygen sensor comprising:

an insulating substrate;

a cathode formed on said insulating substrate generally at the center thereof;

an anode formed in a region of said insulating substrate other than the region where said cathode is formed;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said cathode and said anode within the electrolyte chamber and having a peripheral portion supported on said insulating substrate; and

an electrolytic solution in said electrolyte chamber defined between said gas permeable membrane and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said insulating substrate at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said cathode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral point of said stretched gas permeable membrane.

6. A planar oxygen sensor according to claim 5, wherein a portion of the insulating substrate surface inside the electrolyte chamber, other than the region where said cathode is formed, is formed as a recessed bottom surface with respect to the portion of the insulating substrate on which said cathode is formed.

7. A planar oxygen sensor according to claim 5, wherein said cathode is formed of platinum.

8. A planar oxygen sensor according to claim 5, wherein said insulating substrate comprises a silicon dioxide film.

23. A planar oxygen sensor as claimed in claim 5, wherein the stretched gas permeable membrane and said cathode surface are separated only by a layer of said electrolytic solution.

24. A planar oxygen sensor as claimed in claim 5, wherein the stretched gas permeable membrane substantially contacts said cathode surface.

25. A planar oxygen sensor as claimed in claim 8, further comprising a silicon substrate supporting said silicon dioxide film.

9. A planar oxygen sensor comprising:

an insulating substrate;

a frame formed so as to surround at least a part of a major surface of said insulating substrate;

a working electrode formed on said insulating substrate generally at the center of the part of the major surface surrounded by said frame;

a counter electrode and a reference electrode formed on said insulating substrate between said frame and said working electrode;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said working electrode, said counter electrode and said reference electrode within the electrolyte chamber and having a peripheral portion supported on said frame; and

an electrolytic solution in said electrolyte chamber defined between said gas permeable membrane, said frame and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said frame at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said working electrode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral portion of said stretched gas permeable membrane.

10. A planar oxygen sensor according to claim 9, wherein a portion of the insulating substrate surface inside the electrolyte chamber, other than the region where said working electrode is formed, is formed as a recessed bottom surface with respect to the portion of the insulating substrate on which said working electrode is formed.

11. A planar oxygen sensor according to claim 9, wherein said reference electrode serves to apply a constant voltage to said working electrode.

12. A planar oxygen sensor according to claim 9, wherein each of said working electrode and said counter electrode is formed of platinum.

13. A planar oxygen sensor according to claim 9, wherein said insulating substrate comprises a silicon dioxide film.

18. A planar oxygen sensor according to claim 9, wherein said insulating substrate comprises a silicon dioxide film.

26. A planar oxygen sensor as claimed in claim 9, wherein the stretched gas permeable membrane and said working electrode surface are separated only by a layer of said electrolytic solution.

27. A planar oxygen sensor as claimed in claim 9, wherein the stretched gas permeable membrane substantially contacts said working electrode surface.

28. A planar oxygen sensor as claimed in claim 13, further comprising a silicon substrate supporting said silicon dioxide film.

31. A planar oxygen sensor as claimed in claim 18, further comprising a silicon substrate supporting said silicon dioxide film.

14. A planar oxygen sensor comprising:

an insulating substrate;

a working electrode formed on said insulating substrate generally at the center thereof;

a counter electrode and a reference electrode formed in a region of said insulating substrate other than the region where said working electrode is formed;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said working electrode, said counter electrode and said reference electrode within the electrolyte chamber and having a peripheral portion supported on said insulating substrate;

an electrolytic solution in said electrolyte chamber defined between said gas permeable membrane and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said insulating substrate at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said working electrode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral portion of said stretched gas permeable membrane.

15. A planar oxygen sensor according to claim 14, wherein a portion of the insulating substrate surface inside the electrolyte chamber, other than the region where said working electrode is formed, is formed as a recessed bottom surface with respect to the portion of the insulating substrate on which said working electrode is formed.

16. A planar oxygen sensor according to claim 14, wherein said reference electrode serves to apply a constant voltage to said working electrode.

17. A planar oxygen sensor according to claim 14, wherein each of said working electrode and said counter electrode is formed of platinum.

29. A planar oxygen sensor as claimed in claim 14, wherein the stretched gas permeable membrane and said working electrode surface are separated only by a layer of said electrolytic solution.

30. A planar oxygen sensor as claimed in claim 14, wherein the stretched gas permeable membrane substantially contacts said working electrode surface.

19. A planar oxygen sensor comprising:

an insulating substrate including a silicon substrate and a silicon dioxide film formed on said silicon substrate;

a frame formed so as to surround a part of said insulating substrate, said frame being formed of polyimide;

a working electrode formed on an upper surface of a support pad formed on said insulating substrate generally at the center of the part of the insulating substrate surrounded by said frame, said support pad being formed of polyimide;

a counter electrode and a reference electrode formed in a region of said insulating substrate inside said frame other than the region of said support pad;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said working electrode, said counter electrode and said reference electrode within the electrolyte chamber and having a peripheral portion fixed to and supported on said frame, said gas permeable membrane being formed of Teflon; and

an electrolytic gel in said electrolyte chamber defined between said gas permeable membrane, said frame and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said frame at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said working electrode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral portion of said stretched gas permeable membrane, the thickness of said silicon dioxide film being about 300 nm, the thickness of said support pad being about 50 μ

m, said working electrode and said counter electrode formed as a Ti--Pt two-layer film by photolithography, said reference electrode being formed as a Ti-Ag-AgCl three-layer film by photolithography, and the peripheral portion of said gas permeable membrane being bonded to said frame by an adhesive formed of an epoxy resin.

32. In a flow cell including a printed circuit board, a planar oxygen sensor supported by said printed circuit board, and a cap fixedly attached to said printed circuit board over said planar oxygen sensor, said cap including a flow passage for admitting a specimen to be tested to flow to said planar oxygen sensor, the improvement wherein said planar oxygen sensor comprises:

an insulating substrate including a silicon substrate and a silicon dioxide film formed on said silicon substrate;

a frame formed so as to surround a part of said insulating substrate, said frame being formed of polyimide;

a working electrode formed on an upper surface of a support pad formed on said insulating substrate generally at the center of the part of the insulating substrate surrounded by said frame, said support pad being formed of polyimide;

a counter electrode and a reference electrode formed in a region of said insulating substrate inside said frame other than the region of said support pad;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said working electrode, said counter electrode and said reference electrode within the electrolyte chamber and having a peripheral portion fixed to and supported on said frame, said gas permeable membrane being formed of Teflon; and

an electrolytic gel in said electrolyte chamber defined between said gas permeable membrane, said frame and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said frame at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said working electrode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral portion of said stretched gas permeable membrane, the thickness of said silicon dioxide film being about 300 nm, the thickness of said support pad being about 50 μ

m, said working electrode and said counter electrode formed as a Ti-Pt two-layer film by photolithography, said reference electrode being formed as a Ti-Ag-AgCl three-layer film by photolithography, and the peripheral portion of said gas permeable membrane being bonded to said frame by an adhesive formed of an epoxy resin.

33. In a measuring system for measuring the oxygen content of a specimen flowing in a flow cell, the measuring system including a flow cell having a printed circuit board, a planar oxygen sensor supported by said printed circuit board, and a cap fixedly attached to said printed circuit board over said planar oxygen sensor, said cap including a flow passage for admitting a specimen to be tested to flow to said planar oxygen sensor;

a first source of substantially pure oxygen gas;

a second source of substantially pure nitrogen gas;

first and second mixers each for mixing gas obtained from both the first and second sources, and for outputting respective first and second gas outputs of predetermined percentages;

first and second gas bubblers each containing a buffer solution for dissolving said first and second gas outputs therein, respectively, and for outputting first and second specimens to said flow cell for measurement therein;

the improvement wherein the planar oxygen sensor comprises;

an insulting substrate including a silicon substrate and a silicon dioxide film formed on said silicon substrate;

a frame formed so as to surround a part of said insulating substrate, said frame being formed of polyimide;

a working electrode formed on an upper surface of a support pad formed on said insulating substrate generally at the center of the part of the insulating substrate surrounded by said frame, said support pad being formed of polyimide;

a counter electrode and a reference electrode formed in a region of said insulating substrate inside said frame other than the region of said support pad;

a gas permeable membrane stretched over a portion of said insulating substrate to define an electrolyte chamber therebetween, said gas permeable membrane thereby covering said working electrode, said counter electrode and said reference electrode within the electrolyte chamber and having a peripheral portion fixed to and supported on said frame, said gas permeable membrane being formed of Teflon; and

an electrolytic gel in said electrolyte chamber defined between said gas permeable membrane, said frame and said insulating substrate;

wherein the peripheral portion of the gas permeable membrane is supported on said frame at a locus of support points, one said support point being displaced a minimum distance from said insulating substrate greater than or equal to the minimum such displacement of all other said support points, and wherein said working electrode has a surface that is displaced from said insulating substrate a distance greater than that of said one support point in the same direction as said one support point displacement, said direction being toward a non-peripheral portion of said stretched gas permeable membrane, the thickness of said silicon dioxide film being about 300 nm, the thickness of said support pad being about 50 μ

m, said working electrode and said counter electrode formed as a Ti-Pt two-layer film by photolithography, said reference electrode being formed as a Ti-Ag-AgCl three-layer film by photolithography, and the peripheral portion of said gas permeable membrane being bonded to said frame by an adhesive formed of an epoxy resin.