Microelectrochemical devices based on inorganic redox active material and method for sensing

• US 4,936,956 A
• Filed: 10/29/1987
• Issued: 06/26/1990
• Est. Priority Date: 11/23/1984
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Wrighton, Mark S.
• Primary Examiner(s): Nguyen, Nam X.
• Application Number:
  US07/114,566
• Time in Patent Office: 971 Days
• Field of Search: 204/1 T, 204/403, 204/412, 204/415, 204/416, 204/418, 204/419, 204/433, 204/435, 204/420, 357/25, 324/71.5, 435/817
• US Class Current: 205/777.5
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: G01N 27/12 of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid , for detecting components in the fluid
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: G02F 2001/1557 Side by side arrangements of working and counter electrodes
• CPC Class Codes: G11C 13/0009 RRAM elements whose operation depends upon chemical change
• CPC Class Codes: G11C 2213/34 Material includes an oxide or a nitride
• CPC Class Codes: H01G 7/00 Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
• CPC Class Codes: H10K 10/26 Diodes comprising organic-organic junctions
• CPC Class Codes: H10K 10/46 Field-effect transistors, e.g. organic thin-film transistors [OTFT] H10K10/43 takes precedence
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 71/125 using electrolytic deposition e.g. in-situ electropolymerisation
• CPC Class Codes: H10K 71/233 by photolithographic etching
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/30 Coordination compounds

Abstract

Novel microelectrochemical devices are provided which consist of closely spaced microelectrodes coated with metal ion based inorganic redox active material such as oxides or mixed oxides of any of the following transition metals: W, Ni, Ru, Co, Rh, Ir, Nb, Mo, V, or any other metal that undergoes a change in electrical conductivity upon electrochemical oxidation or reduction, in contact with an electrolyte. Additionally, other metal based redox materials whose conductivity changes as a function of the movement of ions into or out of the material can be used in the construction of microelectronic devices, for example, Prussian Blue, Fe₄ [Fe(CH)₆ ]₃.

"Metal ion-based microelectrochemical devices" encompasses all devices based on an inorganic redox active material which incorporate an active "gate" region or "channel", or exhibit rectification. Included in this classification are devices analogous to diodes, field effect transistors, p-n-p transistors, and n-p-n transistors, and pH sensors, among others. A number of specific examples of transistors and sensors are described in detail.

Claims

1. A microelectrochemical device comprising at least two electrically conductive electrodes, separated by less than two microns, on an insulating substrate overlaid with a metal ion-based redox active material.

2. The device of claim 1 wherein said redox active material is selected from the group consisting of oxides and mixed oxides of W, Ni, Co, Rh, Ir, Nb, Mo, and V and Prussian Blue.

4. The device of claim 1 further comprising at least one electroactive polymer, wherein said device is responsive to a signal that changes the state of charge of the electroactive polymer which results in a net change in the concentration of ionic species in said polymer.

5. The device of claim 4 wherein said polymer is polymerized from monomers selected from the group consisting of N-methylpyrrole, aniline, thiophene, 3-methylthiophene, 3,4-dimethylthiophene, vinylferrocene, styrene, nitrostyrene, viologens, vinyl-pyridine, vinyl-2,2'"'"'-bipyridine, vinylrubrene, quinone-based compounds, and derivatives thereof.

6. The device of claim 1 wherein said redox active material is derivatized with a material selected from the group consisting of metals, enzymes, and ionophores.

7. The device of claim 1 Wherein said device responds to an electrical signal.

8. The device of claim 1 wherein said device responds to a chemical signal.

11. The device of claim 1 wherein said device exhibits rectification.

12. The device of claim 1 wherein said device functions analogously to a diode.

13. The device of claim 12 wherein said device is a pH sensitive transition metal oxide/electroactive redox polymer diode.

3. The device of claim I further comprising an electrolyte solution.

9. The device of claim wherein said device functions analogously to a transistor.

10. The device of claim 9 wherein said device is a pH-sensitive p-n-p transistor prepared by derivatizing adjacent microelectrodes with poly(3-methylthiophene), a transition metal oxide, and poly(3-methylthiophene).

14. A method for sensing a chemical signal comprising

providing a device constructed from at least two microelectrodes, separated by less than two microns, on an insulating substrate, overlaid with a metal ion-based redox active material whose conductivity changes as a function of the movement of ions into or out of the material, and

detecting signals by measuring changes in conductivity of said metal ion based redox active material.

15. The method of claim 14 for monitoring pH further comprising selecting the redox active material for stability within the pH range to be monitored.

16. The method of claim 15 further comprising maintaining a set V_D and V_G across the microelectrodes and determining the pH from variations in I_D.

17. The method of claim 14 further comprising selecting said redox material from the group consisting of transition metal oxides and mixed oxides and Prussian Blue.

18. The method of claim 14 further comprising derivatizing the material with an enzyme reacting with a chemical substance to be measured wherein the reaction of the enzyme and chemical substance causes a change in the oxidation/reduction state of the metal oxide.

19. The method of claim 18 further comprising measuring the current passing between adjacent microelectrodes as a function of the reaction of the enzyme with the substance to be measured, taking the derivative of the measured current to the rate of reduction of the metal oxide, and determining the concentration of the substance to be measured by calculating the enzyme kinetics.

20. The method of claim 14 wherein the signal is determined by a change in the measured current through the metal oxide as a function of the oxidation/reduction of the oxide.

21. The method of claim 14 further comprising increasing the sensitivity of the device by decreasing the distance between the microelectrodes.

22. The method of claim 14 further comprising decreasing the response time of the device by decreasing the thickness of the metal oxide on the microelectrodes.