Ion-sensitive FET sensor

• US 4,816,118 A
• Filed: 06/02/1988
• Issued: 03/28/1989
• Est. Priority Date: 01/24/1986
• Status: Expired due to Term

• Current Assignee: Terumo Corporation
• Original Assignee: Terumo Corporation
• Inventors: Yamaguchi, Shuichiro, Shimomura, Takeshi, Oyama, Noboru
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US07/203,504
• Time in Patent Office: 299 Days
• Field of Search: 204/416, 204/418, 204/419, 357/25, 128/635
• US Class Current: 204/418
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS

Abstract

An ion-sensitive FET sensor has a MOSFET gate isolating membrane whose surface is covered by an ion-sensitive layer. A redox layer having a redox function is provided between the isolating membrane and the ion-sensitive layer to improve operating stability and speed of response. An electrically conductive layer or a combination of a thin metal film and an electrically conductive layer is provided between the isolating membrane and the redox layer to further improve operating stability, the adhesion of the layers and the durability of the sensor. Also disclosed are optimum materials for use as an ion carrier employed in the ion-sensitive layer.

Claims

1. An ion-sensitive FET sensor comprising:

a MOSFET having a gate portion;

a redox layer containing at least one material capable of undergoing a quinone-hydroquinone type redox reaction covering a surface of an isolating membrane of the gate portion; and

an ion-sensitive layer exhibiting ion selectivity covering a surface of said redox layer, wherein said ion-sensitive layer generates a potential corresponding to a concentration of an ion of interest and said redox layer generates an electric field on the gate portion of the MOSFET corresponding to the potential generated by the ion-sensitive layer.

2. The ion-sensitive FET sensor according to claim 1, further comprising an electrically conductive layer exhibiting electrical conductivity between said surface of said isolating membrane of said gate portion and said redox layer.

3. The ion-sensitive FET sensor according to claim 2, wherein said electrically conductive layer is comprised of multiple conductive layers.

4. The ion-sensitive FET sensor according to claim 1, wherein said redox layer has a thickness of from 0.01 μ

m to 1.0 mm.

5. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer has a thickness of from 1 μ

m to 10 mm.

6. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is a compound expressed by the formula ##STR14## where R¹, R², R³ represent the same or different alkyl groups, among which at least two alkyl groups have a carbon number of 8-18, and is selective to hydrogen ion.

7. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is a compound expressed by the formula ##STR15## where R⁴ represents an alkyl group having a carbon number of 8-18, and is selective to hydrogen ion.

8. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of valinomycin, nonactin, monactin, crown ether compounds comprising dicyclohexyl-18-crown-6, naphtho-15-crown-5, bis(15-crown-5), and is selective to potassium ion.

9. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of aromatic amides or diamides, aliphatic amides or diamides, and crown compounds, and is selective to sodium ion.

10. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of the quaternary ammonium salts expressed by the formula ##STR16## and is selective to chlorine ion wherein R₇, R₈ and R₉ represent the same or different alkyl groups C₈ -C₁₈ and R₁₀ represents hydrogen or a C₁ to C₈ alkyl group.

11. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, triphenyl tin chloride expressed by the formula ##STR17## is selective to chlorine ion.

12. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of bis(di-(octylphenyl)phosphate), (-)-(R,R)-N,N'"'"'-bis(11-ethoxy carbonyl)undecyl)-N,N'"'"',4,5-tetramethyl-3,6-dioxaoctane-diamide and calcium bis(di(n-decyl)phosphate), and is selective to calcium ion.

13. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of quaternary ammonium salts expressed by the formula ##STR18## and is selective to hydrogencarbonate ion wherein R₁₁, R₁₂ and R₁₃ represent the same or different C₈ to C₁₈ alkyl groups and R₁₄ represents a hydrogen or a C₁ to C₄ alkyl group and X represents Cl, Br or OH.

14. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of tertiary amine compounds expressed by the formula ##STR19## and is selective to hydrogencarbonate ion wherein R₁₅ represents a phenyl group, hydrogen or a methyl group, R₁₆ represents hydrogen, or methyl and R₁₇ represents methyl or octadecyl.

15. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of tertiary amine compounds expressed by the formula ##STR20## selects hydrogencarbonate ion.

16. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing a ion carrier material nonactin or monactin containing nonalkene, and is selective to ammonium ion.

17. The ion-sensitive FET sensor according to claim 1, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, N,N'"'"'-diheptyl-N,N'"'"'-dimethyl-1,4-butane diamide, and is selective to magnesium ion.

18. An ion-sensitive FET sensor comprising:

a MOSFET having a gate portion;

a redox layer containing at least one material capable of undergoing an amine-quinoid type redox reaction covering a surface of an isolating membrane of the gate portion; and

an ion-sensitive layer exhibiting ion selectivity covering the surface of said redox layer, wherein said ion-sensitive layer generates a potential corresponding to a concentration of an ion of interest and said redox layer generates an electric field on the gate portion of the MOSFET corresponding to the potential generated by the ion-sensitive layer.

19. The ion-sensitive FET sensor according to claim 18, further comprising an electrically conductive layer exhibiting electrical conductivity between said surface of said isolating membrane of said gate portion and said redox layer.

20. The ion-sensitive FET sensor according to claim 19, wherein said electrically conductive layer is comprised of multiple conductive layers.

21. The ion-sensitive FET sensor according to claim 18, wherein said redox layer has a thickness of from 0.01 μ

m to 1.0 mm.

22. The ion-sensitive FET sensor according to claim 18, wherein said electrically conductive layer is selected from the group consisting of carbon, metals and metallic oxides.

23. The ion-sensitive FET sensor according to claim 22, wherein said electrically conductive layer comprises multiple layers.

24. The ion-sensitive FET sensor according to claim 22, wherein said electrically conductive layer has a thickness of from 0.01 μ

m to 1 μ

m.

25. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer has a thickness of from 1 μ

m to 10 mm.

26. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is a compound expressed by the formula ##STR21## where R¹, R², R³ represent the same or different alkyl groups, among which at least two alkyl groups have a carbon number of 8-18, and is selective to hydrogen ion.

27. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is a compound expressed by the formula ##STR22## where R⁴ represents an alkyl group having a carbon number of 8-18, and is selective to hydrogen ion.

28. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of aromatic amides or diamides, aliphatic amides or diamides, and crown compounds, and is selective to sodium ion.

29. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of quaternary ammonium salts expressed by the formula ##STR23## and is selected to chlorine ion wherein R₇, R₈ and R₉ represent the same or different C₈ to C₁₈ alkyl groups and R₁₀ represents a hydrogen or a C₁ to C₈ alkyl group.

30. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material triphenyl tin chloride expressed by the formula ##STR24## and is selective to chlorine ion.

31. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of bis(di-(octylphenyl)phosphate), (-)-(R,R)-N,N'"'"'-bis(11-ethoxy carbonyl)undecyl)-N,N'"'"',4,5-tetramethyl-3,6-dioxaoctane-diamide and calcium bis(di(n-decyl)phosphate), and is selective to calcium ion.

32. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of quaternary ammonium salts expressed by the formula ##STR25## and is selective to hydrogencarbonate ion wherein R₁₁, R₁₂ and R₁₃ represent the same or different C₈ to C₁₈ alkyl groups and R₁₄ represents a hydrogen or a C₁ to C₄ alkyl group and X represents Cl, Br or OH.

33. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group or tertiary amine compounds expressed by the formula ##STR26## and is selective to hydrogencarbonate ion wherein R₁₅ represents a phenyl group, hydrogen or a methyl group, R₁₆ represents hydrogen, or methyl and R₁₇ represents methyl or octadecyl.

34. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of tertiary amine compounds expressed by the formula ##STR27## and is selective to hydrogencarbonate ion.

35. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, nonactin or monactin containing nonactin, and is selective to ammonium ion.

36. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, N,N'"'"'-diheptyl-N,N'"'"'-dimethyl-1,4-butane diamide, and is selective to magnesium ion.

37. The ion-sensitive FET sensor according to claim 18, wherein said ion-sensitive layer is selective to potassium ion, and comprises an organic polymeric membrane containing an ion carrier material selected from the group consisting of valinomycin, nonactin, monactin and crown ether compounds.

38. The ion-sensitive FET sensor according to Claim 37, wherein crown ether compounds are dicyclohexyl-18-crown-6 , naphtho-15-crown-5 and bis(15-crown-5).

39. An ion-sensitive FET sensor comprising:

a MOSFET having a gate portion;

a redox layer containing at least one member selected from the group consisting of poly(pyrrole) and poly(thionylene) covering a surface of an isolating membrane of the gate portion; and

an ion-sensitive layer exhibiting ion selectivity covering a surface of said redox layer, wherein said ion-sensitive layer generates a potential corresponding to a concentration of an ion of interest and said redox layer generates an electric field on the gate portion of the MOSFET corresponding to the potential generated by the ion-sensitive layer.

40. The ion-sensitive FET sensor according to claim 39, further comprising an electrically conductive layer exhibiting electrical conductivity between said surface of said isolating membrane of said gate portion and said redox layer.

41. The ion-sensitive FET sensor according to claim 40, wherein said electrically conductive layer is comprised of multiple conductive layers.

42. The ion-sensitive FET sensor according to claim 39, wherein said redox layer has a thickness of from 0.01 μ

m to 1.0 mm.

43. The ion-sensitive FET sensor according to claim 39, wherein said electrically conductive layer is selected from the group consisting of carbon, metals and metallic oxides.

44. The ion-sensitive FET sensor according to claim 39, wherein said electrically conductive layer has a thickness of from 0.01 μ

m to 1 μ

m.

45. The ion-sensitive FET sensor according to claim 39, wherein one of said multiple layers is selected from the group consisting of nickel, chromium and gold, wherein said one layer covers the insulating membrane.

46. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer has a thickness of from 1 μ

m to 10 mm.

47. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is a compound expressed by the formula ##STR28## where R¹, R², R³ represent the same or different alkyl groups, among which at least two alkyl groups have a carbon number of 8-18, and is selective to hydrogen ion.

48. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is a compound expressed by the formula ##STR29## where R⁴ represents an alkyl group having a carbon number of 8-18, and is selective to hydrogen ion.

49. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of aromatic amides or diamides, aliphatic amides or diamides, and crown compounds, and is selective to sodium ion.

50. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of quaternary ammonium salts expressed by the formula ##STR30## and is selective to chlorine ion wherein R₇, R₈ and R₉ represent the same or different C₈ to C₁₈ alkyl groups and R₁₀ represents a hydrogen or a C₁ to C₈ alkyl group.

51. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, triphenyl tin chloride expressed by the formula ##STR31## and is selective to chlorine ion.

52. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group consisting of bis(di-(octylphenyl)phosphate, (31 )-(R,R)-N,N'"'"'-bis(11-ethoxy carbonyl) undecyl(-N,N'"'"',4,5-tetramethyl-3,6-dioxaoctane-diamide and calcium bis(di(n-decyl) phosphate), and is selective to calcium ion.

53. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of quanternary ammonium salts expressed by the formula ##STR32## and is selective to hydrogencarbonate ion wherein R₁₁, R₁₂ and R₁₃ represent the same or different C₈ to C₁₈ alkyl groups and R₁₄ represents a hydrogen or a C₁ to C₄ alkyl group and X represents Cl, Br or OH.

54. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of tertiary amine compounds expressed by the formula ##STR33## and is selective to hydrogencarbonate ion wherein R₁₅ represents a phenyl group, hydrogen or a methyl group, R₁₆ represents hydrogen, or methyl and R₁₇ represents methyl or octadecyl.

55. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, which is selected from the group of tertiary amine compounds expressed by the formula ##STR34## and is selective to hydrogencarbonate ion.

56. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, nonactin or monactin containing nonactin, and is, selective to ammonium ion.

57. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer, comprising an organic polymeric membrane containing an ion carrier material, N,N'"'"'-diheptyl-N,N'"'"'-dimethyl-1,4-butane diamide, and is selective to magnesium ion.

58. The ion-sensitive FET sensor according to claim 39, wherein said ion-sensitive layer is selective to potassium ion, and comprises an organic polymeric membrane containing an ion carrier material selected from the group consisting of valinomycin, nonactin, monactin and crown ether compounds.

59. The ion-sensitive FET sensor according to claim 58, wherein crown ether compounds are dicyclohexyl-18-crown-6, naphtho-15-crown-5 and bis(15-crown-5).