Microband electrode arrays

• US 6,110,354 A
• Filed: 10/31/1997
• Issued: 08/29/2000
• Est. Priority Date: 11/01/1996
• Status: Expired due to Term

• Current Assignee: University of Washington
• Original Assignee: University of Washington
• Inventors: Yager, Paul, Darling, Robert B., Saban, Steven
• Primary Examiner(s): Warden, Sr., Robert J.
• Assistant Examiner(s): MCNEIL, JENNIFER C
• Application Number:
  US08/963,678
• Time in Patent Office: 1,033 Days
• Field of Search: 204/412, 204/413, 204/434, 205/775
• US Class Current: 205/775
• CPC Class Codes: G01N 27/27 Association of two or more measuring systems or cells, each measuring a different parameter, where the measurement results may be either used independently, the systems or cells being physically associated, or combined to produce a value for a further parameter
• CPC Class Codes: G01N 27/42 Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
• CPC Class Codes: G01N 33/1813 specific cations in water, e.g. heavy metals electrochemical analysis G01N27/26; detection of ions by colorimetry G01N31/22

Abstract

The present invention provides microband electrode array sensors for detecting the presence and measuring the concentration of analytes in a sample. The microband electrodes of the invention have both a width and a thickness of microscopic dimensions. Preferably the width and thickness of the microband electrodes are less than the diffusion length of the analyte(s) of interest. In general, both the thickness and width of the electrodes are less than about 25 micrometers. The electrodes are separated by a gap insulating material that is large enough that the diffusion layers of the electrodes do not overlap such that there is no interference and the currents at the electrodes are additive. Microband electrode arrays of this invention exhibit true steady-state amperometric behavior.

Claims

1. A microband electrode array sensor for detecting the presence or measuring the concentration of analytes in a sample, said sensor comprising:

a substrate having a first edge;

a layer of insulating material having a first edge aligned with said first edge of said substrate; and

a plurality of microband electrodes between said substrate and layer of insulating material;

said microband electrodes having a surface exposed at said first edges of said substrate and said insulating layer; and

said insulating material forming a plurality of gaps, wherein there is one gap between each two adjacent electrodes, wherein the exposed surface of each of said microband electrodes has a width less than or equal to about 25 micrometers; and

said electrode array sensor being constructed and arranged such that the width of each said electrode and the size of each said gap is selected such that in operation, the signals produced by said microelectrodes are additive.

2. The sensor of claim 1 wherein said substrate is planar.

3. The sensor of claim 2 wherein each of said microband electrodes has a thickness of about 0.1 micrometers and a width of about 10 micrometers and said gaps are about 400 micrometers in length.

4. The sensor of claim 1 wherein said substrate is annular.

5. The sensor of claim 4 wherein said aligned first edges of said substrate and said insulating layer form an inner edge of an annulus and wherein said microband electrodes are exposed at said inner edge.

6. The sensor of claim 1 wherein said microband electrodes are platinide metals.

7. The sensor of claim 6 wherein said microband electrodes are platinum.

8. The sensor of claim 6 wherein said microband electrodes are gold.

9. The sensor of claim 1 wherein said microband electrodes are carbon.

10. The sensor of claim 1 wherein said microband electrodes are mercury plated electrodes.

11. A multi-layer microband electrode sensor for detecting the presence or measuring the concentration of analytes in a sample, said sensor comprising:

a plurality of sensors of claim 1 separated from each other by insulating material.

12. The multi-layer microband electrode sensor of claim 11 wherein each of said substrates is planar.

13. The multi-layer microband electrode sensor of claim 11 wherein each of said substrates is annular.

14. The multi-layer microband electrode sensor of claim 11 wherein said insulating material is epoxy.

15. The multi-layer microband electrode sensor of claim 11 wherein said insulating material is deposited as a thin film.

16. A method for performing electrochemical measurements on a sample wherein the sensor of claim 1 is integrated into a channel.

17. The sensor of claim 1 wherein the exposed surface of each of said microband electrodes has a width between about 2 and about 10 micrometers.

18. The sensor of claim 17 wherein the exposed surface of each of said microband electrodes has a thickness of about 0.03 micrometers to about 5 micrometers.

19. The sensor of claim 17 wherein the exposed surface of each of said microband electrodes has a thickness of about 0.1 micrometers to about 0.2 micrometers.

20. The sensor of claim 17 wherein the gap between the electrodes is greater than 50 micrometers.

21. The sensor of claim 1 which exhibits steady-state behavior.

22. The sensor of claim 1 wherein the gap between the electrodes is greater than 50 micrometers.

23. The sensor of claim 22 wherein the exposed surface of each of said microband electrode has a width between about 2 and about 10 micrometers and a thickness of about 0.1 micrometers to about 0.2 micrometers.

24. The sensor of claim 23 wherein said substrate is annular and the exposed surfaces of said electrodes are formed at an inner edge of the annulus.

25. The sensor of claim 22 wherein said substrate is glass, said insulating material is silicon nitride and said electrodes are platinum.

26. The sensor of claim 1 wherein one or more of the electrodes is a reference electrode.

27. The sensor of claim 1 made by the etch-back technique.

28. The sensor of claim 1 made by the lift-off technique.

29. A method of performing anodic stripping voltammetry to detect analytes in a sample, the method comprising the steps of:

(a) contacting the sample with the microband electrodes of the sensor of claim 1,

(b) applying a negative voltage for a sufficient time to allow for an analyte to be reduced onto the microband electrode; and

(c) scanning the voltage in a positive direction to oxidize the plated analyte off the microband electrode.

30. A method of performing cathodic stripping voltammetry to detect analytes in a sample, the method comprising the steps of:

(a) contacting the sample with the microband electrodes of the sensor of claim 1;

(b) applying a positive voltage for a sufficient time to allow for an analyte to be oxidized from the microband electrode; and

(c) scanning the voltage in a negative direction to reduce the plated analyte off the microband electrode.

31. A method of detecting the presence and measuring the concentration of analytes in a sample, the method comprising the steps of:

(a) contacting the sensor of claim 1 with a sample suspected of containing an analyte; and

(b) performing cyclic voltammetry.

32. A method of detecting the presence and measuring the concentration of analytes in a sample, the method comprising the steps of:

(a) contacting the sensor of claim 1 with a sample suspected of containing an analyte; and

(b) performing stripping voltammetry.

33. A method for detecting the presence of or measuring the concentration of at least one analyte in a sample, said method comprising the steps of:

(a) contacting a sample containing at least one analyte with the sensor of claim 1;

(b) applying an electrical potential to the sensor; and

(c) measuring the electrical current flowing through the sensor.

34. A method for detecting the presence of or measuring the concentration of a plurality of analytes in a sample, said method comprising the steps of:

(a) contacting a sample containing a plurality of analytes with the multi-layer sensor of claim 11;

(b) applying an electrical potential to the sensor; and

(c) measuring the electrical current flowing through the sensors.

37. The sensor of claim 26 wherein the width and thickness of each deposited electrode are both about 25 micrometers or less along the length of the electrode.

35. A microband electrode array sensor for detecting the presence and measuring the concentration of analytes in a sample, said sensor comprising:

a plurality of electrodes embedded between a substrate and a layer of insulating material, each of said electrodes having a tip exposed along the edge of said substrate and said insulating layer, and each adjacent tip having positioned therebetween a gap consisting of insulating material and wherein each exposed electrode tip has a width less than or equal to about 25 micrometers said electrode array sensor being constructed and arranged such that the width of each said electrode and the size of each said gap is selected such that in operation, the signals produced by said microelectrodes are additive.

36. A microband electrode array sensor for detecting the presence and measuring the concentration of analytes in a sample, said sensor comprising:

a plurality of electrodes deposited on a substrate and covered with a layer of insulating material, each of said electrodes having a tip exposed along the edge of said substrate and said insulating layer, and each adjacent tip having positioned therebetween a gap and wherein each exposed electrode tip has a width less than or equal to about 25 micrometers said electrode array sensor being constructed and arranged such that the width of each said electrode and the size of each said gap is selected such that in operation, the signals produced by said microelectrodes are additive.