Electrochemical microsensors and method of making such sensors

• US 4,874,499 A
• Filed: 05/23/1988
• Issued: 10/17/1989
• Est. Priority Date: 05/23/1988
• Status: Expired due to Term

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Smith, Rosemary L., Collins, Scott D.
• Primary Examiner(s): Kaplan, G. L.
• Application Number:
  US07/197,561
• Time in Patent Office: 512 Days
• Field of Search: 204/403, 204/416, 204/417, 204/418, 204/419, 204/420, 204/1 T, 357/25, 156/60
• US Class Current: 204/403.03
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
• CPC Class Codes: Y10T 156/10 Methods of surface bonding and/or assembly therefor

Abstract

Electrochemical microsensors formed of a substrate containing means for sensing potential or current, including active and passive electronic devices and electronic circuits, and a micromachined structure containing at least one cavity overlying the sensing means, wherein the structure and substrate are bonded together at a temperature less than about 400° C., in the absence of high voltage fields, using means not requiring highly planarized surfaces. A wide variety of materials can be utilized for both the substrate and overlying structure.

Diverse embodiments are possible, having in common a cavity containing a chemically sensitive material and means for sensing potential or current.

The resulting structural organization of materials transduces a chemical signal, such as concentration, to an electrical signal, which is then "processed" by the underlying FET or metallic connections. The present invention resolves the problems of the prior art in combining sensing devices with chemically sensitive material(s) to form a functional microsensor in a conveniently manufacturable fashion.

Claims

1. An electrochemical microsensor comprising:

a substrate containing microelectronic means for sensing potential or current;

a micromachined structure having openings extending into a cavity therein from opposite sides of the structure, wherein said structure has been produced by photolithographic transfer of a two dimensional pattern onto a material to form a three dimensional structure following selective removal of the material; and

wherein the structure containing the cavity has been positioned over the substrate so that an opening into the cavity extends over the sensing means and the cavity containing structure has been adhered to the substrate using a process which simultaneously adheres multiple structures to substrates as a single unit, with an adhesive forming a seal between the substrate and structure at a temperature less than approximately 400°

C.

2. The device of claim 1 wherein the material for the machined structure is selected from the group consisting of silicon, glass, and micromachinable organic materials.

3. The device of claim 1 further comprising a material having a specific chemical reactivity in the cavity of the structure.

4. The device of claim 3 wherein the material is selected from the group consisting of solid state materials, biological materials, and combinations thereof.

5. The device of claim 4 wherein the material is selected from the group consisting of valinomycin, liquid polyether ester tetraphenyl borate, silver chloride, LaF₃, Si₃ N₄, pH sensitive glass, aluminum oxide, lipid bilayers, lipid bilayers doped with antibiotics, and combinations of proteins and lipid bilayers.

6. The device of claim 3 wherein the chemically sensitive material is cast into the cavity of the machined structure to form a second cavity between the material and the substrate.

7. The device of claim 1 wherein the sensing means is a electronically active device.

8. The device of claim 7 wherein the sensing means is a transistor.

9. The device of claim 1 wherein the sensing means is a passive electronic device.

10. The device of claim 9 wherein the sensing means is a conductive film.

11. The device of claim 1 wherein the sensing means is a circuit.

12. The device of claim 1 further comprising a reference electrode.

13. The device of claim 1 further comprising an electrolyte.

14. The device of claim 1 wherein the cavity containing structure is adhered to the substrate with an adhesive selected from the group of organic adhesives, and spin on glass.

15. The device of claim 14 wherein the adhesive is selected from the group consisting of a photocurable epoxy or silicon.

16. The device of claim 1 further comprising means for connecting the microsensor to an external electrical circuit.

17. The device of claim 1 for sensing a molecule in a solution wherein the sensor is encapsulated with a coating impermeable to the solution.

18. The device of claim 17 wherein the coating is selected from the group consisting of silicon nitride, aluminum oxide, tantalum oxide, silicon dioxide, polyimide, silicones, and epoxy resins.

19. The device of claim 1 further comprising at least one cavity containing structure adhered to the upper surface of the cavity containing structures overlying the substrate.

20. The device of claim 19 further comprising electrolyte wherein the chemically sensitive material and electrolyte are in separate cavities.

22. The device of claim 1 encapsulated for measuring the concentration of chemical species in a solution or gas.

21. A multi-sensor device comprising electrochemical microsensors having

a substrate containing microelectronic means for sensing potential or current;

a micromachined structure having opening extending into a cavity therein from opposite sides of the structure, wherein said structure has been produces by photolithographic transfer of a two dimensional pattern onto a material to form a three dimensional structure following selective removal of the material, and;

wherein the cavity containing-structure has been positioned over the substrate so that an opening into the cavity extends over the sensing means and the cavity containing structure has been adhered to the substrate using a process which simultaneously adheres multiple structures to substrates as a single unit, with an adhesive forming a seal between the substrate and structure at a temperature less than approximately 400°

C.; and

a chemically sensitive material within the cavity;

wherein the electrochemical microsensors contain materials having chemical sensitivities to different chemical species.

23. A method for manufacturing a chemical microsensor comprising:

(i) providing a substrate containing microelectronic means for sensing potential or current;

(ii) providing a micromachined structure having openings extending into a cavity therein from opposite sides of the structure, wherein said structure has been produced by photolithographic transfer of a two dimensional pattern onto a material to form a three dimensional structure following selective removal of the material, and;

(iii) positioning the structure containing the cavity over the substrate wherein an opening into the cavity extends over the sensing means; and

(iv) using a process to adhere the cavity containing structure to the substrate which simultaneously adheres multiple structures to substrates as a single unit, at a temperature less than approximately 400°

C.

24. The method of claim 23 further comprising selecting the material for the machined structure from the group consisting of silicon, glass, and photoreactive organics.

25. The method of claim 23 further comprising providing a material having a specific chemical reactivity in the cavity of the structure.

26. The method of claim 25 further comprising selecting the material from the group consisting of valinomycin, liquid polyether ester tetraphenyl borate, silver chloride, LaF₃, Si₃ N₄, pH sensitive glass, aluminum oxide, lipid bilayers, lipid bilayers doped with antibiotics, and combinations of proteins and lipid bilayers.

27. The method of claim 25 wherein the material is cast into the cavity of the machined structure to form a second cavity between the material and the substrate.

28. The method of claim 23 wherein the sensing means is an electronically active device.

29. The method of claim 28 wherein the sensing means is a transistor.

30. The method of claim 23 wherein the sensing means is a passive electronic device.

31. The method of claim 30 wherein the sensing means is a conductive film.

32. The method of claim 23 wherein the sensing means is a circuit.

33. The method of claim 23 further comprising providing a reference electrode.

34. The method of claim 23 further comprising providing an electrolyte.

35. The method of claim 23 wherein the cavity containing structure is adhered to the substrate with an adhesive selected from the group of organic adhesives, and spin on glass.

36. The method of claim 23 further comprising encapsulating the sensor with a coating impermeable to the external environment.

37. The method of claim 36 wherein the coating is selected from the group consisting of silicon nitride, aluminum oxide, tantalum oxide, silicon dioxide, polyimide, silicones, and epoxy resins.

38. The method of claim 23 further comprising adhering additional cavity containing structures to the cavity containing structures overlying the device containing substrate.

39. The method of claim 38 further comprising providing material sensitive to different chemical species and electrolyte in separate cavities.

40. The method of claim 39 further comprising placing the devices on a single chip.