Surface type microelectronic gas and vapor sensor

• US 4,900,405 A
• Filed: 07/15/1987
• Issued: 02/13/1990
• Est. Priority Date: 07/15/1987
• Status: Expired due to Fees

• Current Assignee: Comtech International Company Limited
• Original Assignee: SRI International, Inc.
• Inventors: Madou, Marc J., Otagawa, Takaaki
• Primary Examiner(s): Walton, Donald L.
• Application Number:
  US07/073,712
• Time in Patent Office: 944 Days
• Field of Search: 204/1 T, 204/412, 204/415, 204/421, 204/424, 204/426, 204/430, 204/280
• US Class Current: 205/781
• CPC Class Codes: G01N 27/4045 for gases other than oxygen

Abstract

The present invention is concerned with electrode structures and microsensors having fast response times and high sensitivity and to methods using such structures and/or microsensors. This is accomplished in any one of several ways. In one, the sensing and counter electrodes are positioned close enough together on an active area so that ion migration therebetween is fast. The thickness of the electrolytic medium on the active area is restricted to be no more than about 10 microns so that diffusion therethrough between the electrodes is at least as fast as the ion migration. In another, the sensing electrode may have outwardly extending portions extending beyond the electrolytic medium and not being covered thereby. Or, conductive particles can be distributed in the electrolytic medium. Or the medium can be very thin. Or, the electrodes can be interdigited. Combinations of the above structural features are also set forth.

Claims

1. A voltammetric microsensor structure, comprising:

a substrate having an active area on a surface thereof;

a sensing electrode having a portion thereof on said active area;

a counter electrode having a portion thereof on said active area;

a reference electrode having a portion thereof on said active area;

said sensing electrode, said counter electrode and said reference electrode defining respectively therebetween a sensing-counter gap, a sensing-reference gap and a counter-reference gap;

a solid polymer electrolyte bridging said gaps;

a barrier covering said solid polymer electrolyte electrolyric medium, said barrier being permeable to an analyte gas; and

an aqueous reservoir internal of said substrate in flow contact with said electrolyte.

2. A microsensor structure as set forth in claim 1, wherein said barrier is water impermeable.

3. A microsensor structure as set forth in claim 1, further including:

a dielectric wall extending outwardly from said substrate surface about said active area and said solid polymer electrolyte.

4. A microsensor structure as set forth in claim 1, wherein said substrate is of a dielectric material.

5. A microsensor structure as set forth in claim 1, wherein said substrate is of a semiconductor material and further including:

an insulator between said substrate and said electrodes.

6. A microsensor as set forth in claim 1, wherein said sensing-counter electrode gap is no more than about 50 microns.

7. A microsensor structure as set forth in claim 1, wherein said barrier is water impermeable.

8. A microsensor structure as set forth in claim 1, further including:

a plurality of sets of said sensing, counter and reference electrodes, each of said sets being on said substrate, each of said sets being in contact with a respective one of a corresponding plurality of solid polymer electrolytes, said polymer electrolytes being electrically isolated from one another.

9. A method of voltammetrically determining the concentration of a gaseous species, comprising:

contacting a microsensor structure with the gaseous species in a gas phase and voltammetrically measuring the electrochemical effect of the species between sensing and counter electrode, the microsensor structure comprising a substrate having a sensing electrode, a counter electrode and a reference electrode, the electrodes defining respective sensing-counter, sensing-reference and counter-reference gaps between portions thereof mounted on an active area on the surface of the substrate, the gaps being bridged by a solid polymer electrolyte, a barrier covering said electrolyte, said barrier being permeable to an analyte gas and an aqueous reservoir internal of said substrate in flow contact with said electrolyte.

10. A method as set forth in claim 9, further including:

positioning said sensing and counter electrodes sufficiently closely adjacent one another whereby said sensing-counter electrode gap is no more than about 50 microns.

11. A method as set forth in claim 10, wherein said solid polymer electrolyte is of a thickness upon said sensing electrode of no more than about 10 microns.

12. In a microsensor structure comprising a substrate having a surface having an active area, first and second adjacent electrodes having, respectively, sensing and counter portions on the active area;

and an electrolytic medium covering the active area, the improvement comprising;

positioning the first and second electrodes sufficiently close together on said active area so that the time of migration of an ionic moiety from one to the other of the electrodes is no more than about 1 minute;

restricting the thickness of the electrolytic medium to be no more than about 10 microns so that the time of diffusion of the gaseous species through the electrolytic medium to the first electrode is no more than about equal to the time of migration of the ionic moiety from one to the other of the electrodes;

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas; and

an aqueous reservoir internal of said substrate in flow communication with said electrolytic medium.

13. In a microsensor structure comprising a substrate having a surface having an active area, first and second adjacent electrodes having, respectively, sensing and counter portions on the active area;

and an electrolytic medium covering the active area, the improvement comprising;

positioning the first and second electrodes sufficiently close together on said active area so that the time of migration of an ionic moiety from one to the other of the electrodes is no more than about 1 minute;

restricting the thickness of the electrolytic medium to be no more than about 10 microns so that the time of diffusion of the gaseous species through the electrolytic medium to the first electrode is no more than about equal to the time of migration of the ionic moiety from one to the other of the electrodes;

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas;

a third electrode having a reference portion in contact with said electrolytic medium and free from contact with said first and second electrodes; and

an aqueous reservoir internal of said substrate in flow contact with said electrolytic medium.

14. A microsensor structure for sensing an analyte in a gas phase, comprising:

a substrate having a surface having an active area;

a sensing electrode having a sensing portion on said active area, said sensing portion comprising a plurality of sensing fingers and having an outfacing surface facing away from said substrate;

a counter electrode having a counter portion on said active area, said counter portion comprising a plurality of counter fingers, said counter fingers being positioned between and aligned generally along said sensing fingers to define sensing finger-counter finger gaps of no more than about 50 microns;

a reference electrode having a reference portion on said active area and being free from contact with said sensing and counter electrodes;

an electrolytic medium on said active area bridging said sensing finger-counter finger gaps and communicating said reference portion with said sensing portion, said electrolytic medium covering the active area by not covering the outfacing surface of said sensing electrode, the electrolytic medium, the sensing electrode and the gas phase forming a 3-phase sensing boundary;

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas; and

an aqueous reservoir internal of said substrate in flow contact with said electrolytic medium.

15. A microsensor structure for sensing an analyte in a gas phase, comprising:

a substrate having a substrate surface having an active area;

a sensing electrode on the substrate surface having a sensing portion upon the active area, the sensing portion having an outfacing surface facing away from the substrate;

a solid electrolytic medium covering the active area but not covering the outfacing surface, the electrolytic medium, the first electrode and the gas phase forming a 3-phase sensing boundary;

a counter electrode in contact with the electrolytic medium and free from contact with the sensing electrode; and

a reference electrode in contact with the electrolytic medium and free from contact with the sensing and counter electrodes;

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas; and

an aqueous reservoir internal of said substrate in flow contact with said electrolytic medium.

16. A microsensor structure as set forth in claim 15, wherein said barrier is water impermeable.

17. A microsensor structure as set forth in claim 15, further including:

a dielectric wall extending outwardly from said substrate surface about said active area and said electrolytic medium.

18. A microsensor structure as set forth in claim 15, wherein said substrate is of a dielectric material.

19. A microsensor structure as set forth in claim 15, wherein said substrate is of a semiconductor material and further including:

an insulator between said substrate and said first and second electrodes.

20. A microsensor as set forth in claim 15, wherein said sensing and counter electrodes are adjacent one another and are separated by a sensing-counter electrode gap of no more than about 50 microns.

21. A microsensor as set forth in claim 20, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

22. A microsensor as set forth in claim 21, wherein said member is water impermeable.

23. A microsensor as set forth in claim 20, wherein said solid electrolytic medium is of a thickness upon said outfacing surface of no more than about 10 microns.

24. A microsensor as set forth in claim 23, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

25. A microsensor structure as set forth in claim 15, further including:

a plurality of sets of said sensing and counter electrodes, each of said sets being on said substrate, said sets each being in contact with a respective one of a corresponding plurality of solid electrolytic mediums, said electrolytic mediums being electrically isolated from one another.

26. An electrode structure, comprising:

a first electrode having a sensing portion having an outfacing surface having uneven configuration including a plurality of outwardly extending portions; and

an electrolytic medium covering said outfacing surface with said outwardly extending portions extending outwardly beyond said electrolytic medium and not being covered thereby.

27. An electrode structure as set forth in claim 26, wherein said outfacing extending portions extend outwardly from said outfacing surface from about 0.01 micron to about 5 microns.

28. An electrode structure as set forth in claim 27, wherein said electrolytic medium is of a thickness upon said outfacing surface of no more than about 10 microns.

29. A microsensor structure, comprising:

a substrate having a substrate having an active area;

a first electrode on with said substrate surface, said first electrode having a sensing portion on said active area, said sensing portion having an infacing surface facing said substrate surface and an outfacing surface facing away from said substrate surface, said outfacing surface having an uneven configuration including a plurality of outwardly extending portions;

an electrolytic medium covering said outfacing surface with said outwardly extending portions extending outwardly beyond said electrolytic medium and not being covered thereby; and

a second electrode on said electrolytic medium and free from contact with said first electrode.

30. A microsensor as set forth in claim 29, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

31. A microsensor structure as set forth in claim 30, wherein said barrier is water impermeable.

32. A microsensor as set forth in claim 30, further including:

an aqueous reservoir in flow contact with said electrolytic medium.

33. A microsensor structure as set forth in claim 29, further including:

a dielectric wall extending outwardly from said substrate surface about said active area and said electrolytic medium.

34. A microsensor structure as set forth in claim 29, wherein said substrate is of a dielectric material.

35. A microsensor structure as set forth in claim 29, wherein said substrate is of a semiconductor material and further including:

an insulator between said substrate and said first and second electrodes.

36. A microsensor as set forth in claim 29, wherein said outfacing extending portions extend outwardly from said outfacing surface from about 0.01 micron to about 5 microns.

37. A microsensor as set forth in claim 29, wherein said second electrode is on said substrate surface and wherein said first and second electrodes are adjacent one another and are separated by a first-second electrode gap of no more than about 50 microns.

38. A microsensor as set forth in claim 37, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

39. A microsensor as set forth in claim 38, wherein said member is water impermeable.

40. A microsensor as set forth in claim 29, further including:

a third electrode in contact with said electrolytic medium and free from contact with said first and second electrodes.

41. A microsensor as set forth in claim 40, wherein said first electrode is a sensing electrode, said second electrode is a counter electrode and said third electrode is a reference electrode.

42. A microsensor as set forth in claim 41, wherein said second and third electrodes are on said substrate surface, wherein said first and second electrodes are adjacent one another and are separated by a first-second electrode gap of no more than about 50 microns.

43. A microsensor structure as set forth in claim 29, wherein said outwardly extending portions extend upwardly from said outfacing surface from about 0.01 micron to about 5 microns.

44. A microsensor as set forth in claim 43, wherein said solid electrolytic medium is of a thickness upon said outfacing surface of no more than about 10 microns.

45. A microsensor as set forth in claim 44, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

46. A microsensor structure as set forth in claim 45, further including:

an aqueous reservoir in flow contact with said electrolytic medium.

47. A microsensor structure as set forth in claim 46, wherein said outfacing extending portions extend outwardly from said outfacing surface from about 0.01 micron to about 5 microns.

48. A microsensor structure as set forth in claim 47, wherein said second electrode is on said substrate surface and wherein said first and second electrodes are adjacent one another and are separated by first-second electrode gap of no more than about 50 microns.

49. A microsensor as set forth in claim 47, further including:

a third electrode in contact with said electrolytic medium and free from contact with said first and second electrodes.

50. A microsensor structure as set forth in claim 49, wherein said first electrode is a sensing electrode, said second electrode is a counter electrode and said third electrode is a reference electrode.

51. A microsensor structure as set forth in claim 50, wherein said second and third electrodes are on said substrate surface, wherein said first and second electrodes are adjacent one another and are separated by first-second electrode gap of no more than about 50 microns.

52. A microsensor structure as set forth in claim 51, further including:

an aqueous reservoir in flow contact with said electrolytic medium.

53. A microsensor structure as set forth in claim 51, wherein said member is water impermeable.

54. A microsensor structure as set forth in claim 29, further including:

a plurality of said first electrodes and a plurality of said second electrodes, each of said first electrodes being on said substrate, said first electrodes each being in contact with a respective one of a corresponding plurality of solid electrolytic mediums, said electrolytic mediums being electrically isolated from one another.

55. In a method of determining the concentration of a particular gaseous species which comprises contacting the species with a sensor having a substrate having a sensing electrode and a counter electrode on a surface thereof, the electrodes being covered by an electrolytic medium, and measuring the electrochemical effect of said species on said sensing electrode, the improvement comprising:

utilizing as said sensing electrode a first electrode having an outfacing surface having an uneven configuration including a plurality of outwardly extending portions which extend outwardly beyond said electrolytic medium and are not covered thereby.

56. A method as set forth in claim 55, wherein said method further includes:

providing a reference electrode as a third electrode on said surface and utilizing said reference electrode along with said sensing and counter electrode when measuring said effect.

57. A method as set forth in claim 56, wherein said outfacing extending portions extend outwardly from said outfacing surface from about 0.01 micron to about 5 microns.

58. A method as set forth in claim 55, further including:

positioning said sensing and counter electrodes adjacent one another and separated by sensing-counter electrode gap of no more than about 50 microns.

59. A method as set forth in claim 58, wherein said solid electrolytic medium is of a thickness upon said outfacing surface of no more than about 10 microns.

60. A method as set forth in claim 59, wherein said solid electrolytic medium comprises a solid polymer electrolyte.

61. A method as set forth in claim 55, wherein said outwardly extending portions extend outwardly from said outfacing surface from about 0.01 micron to about 5 microns.

62. A microsensor structure, comprising:

a substrate having a substrate surface having an active area;

a first electrode in contact with said substrate surface, said first electrode having a sensing portion on said active area, said sensing portion having infacing surface facing said substrate surface and an outfacing surface facing away from said substrate surface;

a solid electrolytic medium covering said outfacing surface, said solid electrolytic medium having a plurality of conductive microparticles dispersed therein; and

a second electrode in contact with said electrolytic medium and free from contact with said first electrode.

63. A microsensor as set forth in claim 62, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

64. A microsensor as set forth in claim 63, wherein said barrier is water impermeable.

65. A microsensor as set forth in claim 63, further including:

an aqueous reservoir in flow contact with said electrolytic medium.

66. A microsensor structure as set forth in claim 62, wherein said substrate is of a dielectric material.

67. A microsensor structure as set forth in claim 62, wherein said substrate is of a semiconductor material and further including:

an insulator between said substrate and said first and second electrodes.

68. A microsensor as set forth in claim 62, wherein said second electrode is on said substrate surface and wherein said first and second electrodes are adjacent one another and are separated by a first-second electrode gap of no more than about 50 microns.

69. A microsensor as set forth in claim 68, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

70. A microsensor as set forth in claim 69, wherein said member is water impermeable.

71. A microsensor as set forth in claim 62, further including:

a third electrode in contact with said electrolytic medium and free from contact with said first and second electrodes.

72. A microsensor as set forth in claim 71, wherein said first electrode is a sensing electrode, said second electrode is a counter electrode and said third electrode is a reference electrode.

73. A microsensor as set forth in claim 72, wherein said second and third electrodes are on said substrate surface and wherein said first and second electrodes are adjacent one another and are separated by a first-second electrode gap of no more than about 50 microns.

74. A microsensor as set forth in claim 62, wherein said solid electrolytic medium is of a thickness upon said outfacing surface of no more than about 10 microns.

75. A microsensor as set forth in claim 74, further including:

a barrier covering said electrolytic medium, said barrier being permeable to an analyte gas.

76. A microsensor structure as set forth in claim 75, further including:

an aqueous reservoir in flow contact with said electrolytic medium.

77. A microsensor structure as set forth in claim 76, wherein said second electrode is on said substrate surface and wherein said first and second electrodes are adjacent one another and are separated by first-second electrode gap of no more than about 50 microns.

78. A microsensor as set forth in claim 77, further including:

a third electrode in contact with said electrolytic medium and free from contact with said first and second electrodes.

79. A microsensor structure as set forth in claim 78, wherein said first electrode is a sensing electrode, said second electrode is a counter electrode and said third electrode is a reference electrode.

80. A microsensor structure as set forth in claim 79, wherein said second and third electrodes are on said substrate surface, wherein said first and second electrodes are adjacent one another and are separated by first-second electrode gap of no more than about 50 microns.

81. A microsensor structure as set forth in claim 80, further including:

an aqueous reservoir in flow contact with said electrolytic medium.

82. A microsensor structure as set forth in claim 80, wherein said member is water impermeable.

83. A microsensor structure as set forth in claim 62, further including:

a plurality of sets of said first and second electrodes, each of said sets being on said substrate, said sets each being in contact with a respective one of a corresponding plurality of solid electrolytic mediums, said electrolytic mediums being electrically isolated from one another.

84. In a method of determining the concentration of a particular gaseous species which comprises contacting the species with a sensor having a substrate having a sensing electrode and a counter electrode on a surface thereof, the electrode being covered by a solid electrolytic medium, and measuring the effect of said species on the sensing electrode, the improvement comprising:

including a plurality of conductive microparticles dispersed in said solid electrolytic medium.

85. A method as set forth in claim 84, wherein said method further includes:

providing a reference electrode as a third electrode on said surface and utilizing said reference electrode along with said sensing and counter electrode when measuring said effect.

86. A method as set forth in claim 85, further including:

positioning said sensing and counter electrodes adjacent one another and separated by sensing-counter electrode gap of no more than about 50 microns.

87. A method as set forth in claim 84, wherein said solid electrolytic medium is of a thickness upon said outfacing surface of no more than about 10 microns.

88. A method as set forth in claim 87, wherein said solid electrolytic medium comprises a solid polymer electrolyte.