Microelectrochemical devices

• US 4,717,673 A
• Filed: 11/19/1985
• Issued: 01/05/1988
• Est. Priority Date: 11/23/1984
• Status: Expired due to Term

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Thackeray, James W., White, Henry S. Jr., Wrighton, Mark S.
• Primary Examiner(s): Marcus, Michael S.
• Application Number:
  US06/798,263
• Time in Patent Office: 777 Days
• Field of Search: 350/357, 422/90, 422/98, 422/97, 422/68, 436/151, 436/806, 436/138, 436/163, 324/438, 204/78, 204/433, 204/435, 204/290 F, 204/291, 435/291
• US Class Current: 436/68
• 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 27/4145 specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: G11C 13/0009 RRAM elements whose operation depends upon chemical change
• CPC Class Codes: G11C 13/0014 comprising cells based on organic memory material
• CPC Class Codes: G11C 13/0016 comprising polymers
• 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 30/00 Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation integrated devices or assemblies of multiple devices H10K39/00, H10K65/00; electrolytic light-sensitive devices H01G9/20
• CPC Class Codes: H10K 71/125 using electrolytic deposition e.g. in-situ electropolymerisation
• 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
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y10S 436/806 Electrical property or magnetic property
• CPC Class Codes: Y10T 436/209163 Dissolved or trace oxygen or oxygen content of a sealed environment

Abstract

Very stable, polymer-based electrochemical devices, formed by polymerization of thiophene or a derivative such as 3-methylthiophene which is durable in an aqueous electrolyte over a wide pH range, which respond rapidly to chemical or electrical signals, are disclosed. In one embodiment, the device functions as an extremely sensitive sensor which measures changes in chemical concentration or pH. For example, a poly-3-methylthiophene-based device is sensitive to as little as 8×10^-16 moles of an oxidant which reversibly interacts with the polymer, including gas phase oxidants such as I₂. In a variation of the polymer-based device, a catalyst such as a noble metal or an enzyme, is dispersed on or within the conducting polymer matrix so that the device is responsive to chemicals such as H₂ and O₂ which the polymer would otherwise respond very slowly to. In a second embodiment, a polymer-based electrochromic device consists of polymer-coated microelectrodes which are individually addressed. Very high resolution is achieved by separating the microelectrodes by distances on the order of 10,000 Angstroms. In still another embodiment, the polymer-based device functions as a capacitor with an energy density as high as 200-300 J/cm³ which can operate at frequencies as high as 100 Hz. Large polymer-based capacitors are useful for storage of solar energy or as automobile batteries. Microcapacitors may be incorporated into conventional integrated circuit designs.

Claims

1. A microelectrochemical device comprising at least two electrically conductive electrodes, separated by less than two microns, on an inert insulating substrate overlaid with a conducting polymer polymerized from thiophene or derivatives of thiophene.

2. The device of claim 1 wherein said conducting polymer is selected from the group consisting of polythiophene, poly-3-methylthiophene and poly-3,4-dimethylthiphene.

3. The device of claim 2 comprising two electrodes formed of a metal and overlaid with the minimum thickness of poly-3-methylthiophene to connect two electrodes.

4. The device of claim 1 wherein the polymer further comprises a catalyst.

5. The device of claim 4 wherein the catalyst is selected from the group consisting of noble metals and enzymes.

6. The device of claim 5 wherein the noble metal is in the form of particles electrically insulated from each other when the polymer is not conducting.

7. An electrochromic device comprising one or more individually addressable, electrically conductive electrodes on an inert insulating substrate overlaid with a conducting polymer polymerized from thiophene or a derivative of thiophene, an electrolyte solution, a counter-electrode and an optically transparent material covering the electrolyte and polymer-overlaid electrodes, wherein said polymer-overlaid electrodes are separated by an approximate distance of up to one micron.

8. A polymer-based electrochemical device for storing electrical energy comprising two electrically conductive electrodes separated by less than two microns on an inert insulating substrate and an ionic conductor wherein said electrodes are coated with a polymer formed from thiophene or a thiophene derivative and separated by the ionic conductor.

9. The device of claim 8 wherein the polymer is highly conductive, exhibits a linear relationship between charge and potential within a desired range of potentials, has a high capacity for electrical charge per unit area of polymer, and can store and discharge energy at high frequencies.

10. The device of claim 9 wherein the polymer is durable in an aqueous solution.

11. The device of claim 9 wherein the polymer is selected from the group consisting of polythiophene, poly-3-methylthiophene, and poly-3,4-dimethylthiophene.

12. The device of claim 11 further comprising

an electrolyte solution, and

a housing which seals the electrolyte solution in the device adjacent the polymer and ionic conductor, wherein the polymer overlaying the electrodes is physically separated by the ionic conductor.

13. The device of claim 12 wherein the polymer layer is greater than 5 microns thick.

14. A method for sensing low magnitude chemical or electrical signals comprising:

providing a device including at least two electrically conductive electrodes separated by less than two microns on an inert insulating substrate, wherein said electrodes are overlaid with a polymer of thiophene or derivatives of thiophene, and

detecting signals by measuring changes in conductivity of said polymer that are a result of a change in the state of charge of said polymer which results in a net change in the concentration of ionic species in said polymer.

15. The method of claim 14 further comprising applying a potential of between 0.0 V and +1.4 V to said device and measuring changes in conductivity as changes in potential.

16. The method of claim 14 further comprising increasing the sensitivity of said device by decreasing the distance between said electrodes.

17. The method of claim 14 further comprising equilibrating said device with a reactant selected from the group of O₂, H₂, I₂ and other redox reagents and measuring changes in concentration of said reactants as changes in conductivity of said polymer.

18. The method of claim 14 further comprising contacting said device with a biological solution and measuring changes in blood components as a function of changes in conductivity of said polymer.

19. The method of claim 18 wherein the blood component is selected from the group consisting of O₂ and H+(aq).