Micro-machined thin film sensor arrays for the detection of H2, NH3, and sulfur containing gases, and method of making and using the same

• US 20020017126A1
• Filed: 04/06/2001
• Published: 02/14/2002
• Est. Priority Date: 01/15/1999
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Baum, Thomas H., DiMeo, Frank Jr.
• Granted Patent: US 6,596,236 B2
• Time in Patent Office: Days
• US Class Current: 73/31.05
• CPC Class Codes: G01N 21/59 Transmissivity G01N21/25 takes precedence
• CPC Class Codes: G01N 21/783 for analysing gases
• CPC Class Codes: G01N 2291/02863 Electric or magnetic parameters
• CPC Class Codes: G01N 27/124 varying the temperature, e.g. in a cyclic manner
• CPC Class Codes: G01N 27/128 Microapparatus
• CPC Class Codes: G01N 33/0014 by eliminating a gas G01N33/0013 and G01N33/0024 take precedence
• CPC Class Codes: G01N 33/005 for H2
• CPC Class Codes: Y10T 436/175383 Ammonia
• CPC Class Codes: Y10T 436/22 Hydrogen, per se

Abstract

The present invention provides a hydrogen sensor including a thin film sensor element formed by metal organic chemical vapor deposition (MOCVD) or physical vapor deposition (PVD), on a micro-hotplate structure. The thin film sensor element includes a film of a hydrogen-interactive metal film that reversibly interacts with hydrogen to provide a correspondingly altered response characteristic, such as optical transmissivity, electrical conductance, electrical resistance, electrical capacitance, magneto resistance, photoconductivity, etc., relative to the response characteristic of the film in the absence of hydrogen. The hydrogen-interactive metal film may be overcoated with a thin film hydrogen-permeable barrier layer to protect the hydrogen-interactive film from deleterious interaction with non-hydrogen species. The hydrogen permeable barrier may comprise species to scavenge oxygen and other like species. The hydrogen sensor of the invention may be usefully employed for the detection of hydrogen in an environment susceptible to the incursion or generation of hydrogen and may be conveniently configured as a hand-held apparatus.

Claims

1. A hydrogen sensor, comprising:

at least one hydrogen-interactive thin film sensor element comprising a rare earth metal or a rare metal dihydride;

at least one micro-hotplate structure coupled to said hydrogen-interactive sensor element for selective heating of the sensor element; and

a hydrogen-permeable material overlaying each hydrogen-interactive element for selective permeation of hydrogen, wherein said hydrogen-permeable material comprises an alloy to suppress a phase change in said rare earth metal or rare metal dihydride.

2. The hydrogen sensor of claim 1, wherein said alloy to suppress a phase change in said rare earth metal or rare metal dihydride comprises at least one element selected from the group of silver, titanium, nickel, chromium, aluminum.

3. The hydrogen sensor of claim 1, wherein said alloy to suppress a phase change in said rare earth metal or rare metal dihydride comprises a rare metal oxide.

4. The hydrogen sensor of claim 1, wherein the rare earth metal or rare earth metal dihydride of the hydrogen-interactive sensor element, arranged for exposure to an environment susceptible to the incursion or generation of hydrogen exhibits a detectable change of physical property, is exposed to hydrogen.

5. The hydrogen sensor of claim 4, wherein said detectable change of physical property is selected from the group consisting of optical transmissivity, electrical resistivity, electrical conductivity, electrical capacitance, magneto-resistance and photoconductivity.

6. The hydrogen sensor of claim 4, further comprising a detector constructed and arranged to convert said detectable change of physical property to a perceivable output selected from the group consisting of visual outputs, auditory outputs, tactile outputs, and auditory outputs.

7. The hydrogen sensor of claim 1, wherein the rare earth metal or rare earth metal dihydride of the hydrogen-interactive sensor element comprises at least one rare earth metal component selected from the group consisting of trivalent rare earth metals that react with hydrogen to form both metal dihydride and metal trihydride reaction products, wherein the metal dihydride and metal trihydride reaction products have differing physical properties.

8. The hydrogen sensor of claim 1, wherein the hydrogen-interactive thin film sensor element comprises at least one thin film layer comprising one or more metals, present in elemental metal form and/or in a dihydride thereof, wherein the metal is selected from the group consisting of:

magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, and alloys thereof.

9. The hydrogen sensor of claim 4, wherein said detectable change of physical property comprises a change of electrical property when the hydrogen-interactive thin film sensor element is contacted with hydrogen gas.

10. The hydrogen sensor of claim 1, further including a monitor operatively arranged in monitoring relationship to the hydrogen-interactive thin film sensor element to provide an output indicative of the presence of hydrogen.

11. The hydrogen sensor of claim 4, wherein said detectable change of physical property comprises a change from a metallic state to a semiconducting state.

12. The hydrogen sensor of claim 1, further including an electrical resistance monitor operatively arranged in monitoring relationship to the hydrogen-interactive thin film sensor element to provide an output indicative of the presence of hydrogen in an environment in contact with the hydrogen-interactive thin film sensor element.

13. The hydrogen sensor of claim 1, wherein the hydrogen-interactive thin film sensor element is formed of a material consisting essentially of rare earth metal dihydride of one or more trivalent rare earth metals, wherein said rare earth metal dihydride is reversibly reactive with hydrogen to form corresponding metal trihydride exhibiting a detectable change of physical properties.

14. The hydrogen sensor of claim 4, wherein the hydrogen-interactive thin film sensor element comprises yttrium, and the physical property change comprises a change of electrical conductivity or resistivity when the hydrogen-interactive thin film sensor element is contacted with hydrogen gas.

15. The hydrogen sensor of claim 1, wherein the hydrogen-permeable material is selected from the group consisting of palladium, platinum, iridium, silver, gold, cobalt, and alloys thereof.

16. The hydrogen sensor of claim 1, wherein the hydrogen-interactive thin film sensor element comprises a rare earth metal thin film that is doped with a dopant.

17. The hydrogen sensor of claim 14, wherein said dopant is selected from the group consisting of magnesium, calcium, strontium, barium, and any combination thereof.

18. The hydrogen sensor of claim 17, wherein said dopant is deposited on the hydrogen-interactive thin film.

19. The hydrogen sensor of claim 1, wherein the micro-hotplate structure is controlled by a predetermined time-temperature program for cyclic heating of the hydrogen-interactive thin film gas sensor element by the micro-hotplate structure.

20. The hydrogen sensor of claim 1, wherein said hydrogen-interactive thin film has a thickness of from about 50 to about 2000 nm.

21. The hydrogen sensor of claim 1, wherein the hydrogen-permeable material is in the form of a thin film.

22. The hydrogen sensor according to claim 1, wherein the hydrogen-permeable thin film has a thickness of from about 2 to about 1000 nm.

23. The hydrogen sensor according to claim 1, comprising a plurality of hydrogen-I interactive thin films.

24. The hydrogen sensor according to claim 21, wherein at least two hydrogen-interactive thin film sensor elements are covered by hydrogen-permeable material of different thickness.

25. The hydrogen sensor according to claim 21, wherein at least two hydrogen-interactive films are differing materials.

27. The hydrogen sensor of claim 26, wherein said alloy to suppress a phase change in said rare earth metal or rare metal dihydride comprises at least one element selected from the group of silver, titanium, nickel, chromium, aluminum.

28. The hydrogen sensor of claim 26, wherein said alloy to suppress a phase change in said rare earth metal or rare metal dihydride comprises a rare metal oxide.

29. The hydrogen sensor device according to claim 26, further comprising a power supply for the device.

30. The hydrogen sensor device according to claim 29, wherein the power supply is constructed and arranged for actuating the micro-hotplate structure during and/or subsequent to sensing the detectable change of physical property of the hydrogen-interactive thin film gas sensor element in exposure to hydrogen.

31. The hydrogen sensor device according to claim 29, wherein the power supply is constructed and arranged for energizing the detector.

32. The hydrogen sensor device of claim 26, wherein said detectable change of physical property is selected from the group consisting of optical transmissivity, electrical resistivity, electrical conductivity, electrical capacitance, magneto-resistance and photoconductivity.

33. The hydrogen sensor device of claim 26, wherein the detector is constructed and arranged to convert said detectable change of physical property to a perceivable output selected from the group consisting of visual outputs, auditory outputs, tactile outputs, and auditory outputs.

34. The hydrogen sensor device of claim 29, wherein the rare earth metal or rare earth metal dihydride of the hydrogen-interactive sensor element comprises at least one rare earth metal component, in an elemental metal form and/or in a metal dihydride thereof, selected from the group consisting of trivalent rare earth metals that react with hydrogen to form both metal dihydride and metal trihydride reaction products, wherein the metal dihydride and metal trihydride reaction products have differing physical properties.

35. The hydrogen sensor device of claim 29, wherein the rare earth metal and/or rate earth metal dihydride of the hydrogen-interactive sensor element comprises one or more metals, in elemental metal form and/or in a corresponding metal dihydride, selected from the group consisting of:

magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, and alloys containing one or more of such metals.

37. The method of claim 36, wherein said alloy to suppress a phase change in said rare earth metal or rare metal dihydride comprises at least one element selected from the group of silver, titanium, nickel, chromium, aluminum.

38. The method of claim 36, wherein said alloy to suppress a phase change in said rare earth metal or rare metal dihydride comprises a rare metal oxide.

39. The method of claim 36, further comprising coupling the hydrogen-interactive thin film with a detector for outputting the detectable change of physical property of the hydrogen-interactive thin film when the hydrogen-interactive thin film is exposed to hydrogen.

40. The method of claim 36, wherein the hydrogen-interactive thin film comprises a rare earth metal component, in elemental metal form and/or in a corresponding metal dihydride, selected from the group consisting of trivalent rare earth metals that react with hydrogen to form both metal dihydride and metal trihydride reaction products, wherein the metal dihydride and metal trihydride reaction products have differing physical properties.

41. The method of claim 36, wherein the hydrogen-interactive thin film comprises one or more metal components, in elemental metal form and/or in a corresponding metal dihydride selected from the group consisting of:

magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, and alloys containing one or more of such metals.

42. The method of claim 36, further comprising coupling the hydrogen-interactive thin film with an electrical resistance monitor to provide an output indicative of the presence of hydrogen in an environment in contact with the rare earth metal thin film.

43. The method of claim 36, wherein the hydrogen-permeable material comprises a metal selected from the group consisting of palladium, platinum, iridium, silver, gold, cobalt, and alloys thereof.

44. The method of claim 36, wherein the hydrogen-interactive thin film comprises a metal selected from the group consisting of lanthanum and yttrium, and the hydrogen-interactive thin film is formed on the substrate by chemical vapor deposition utilizing a corresponding precursor, wherein said precursor is selected from the group consisting of tris(cyclopentadienyl)lanthanum, tris(cyclopentadienyl)yttrium, β

-ketoamine complexes of lanthanum, β

-ketoamine complexes of yttrium, β

-diketonate complexes of lanthanum, β

-diketonate complexes of yttrium, β

-diiminate complexes of lanthanum, β

-diiminate complexes of yttrium;

lanthanum amides, and yttrium amides.

45. The method of claim 34, wherein the hydrogen-interactive thin film is doped with a dopant.

46. The method of claim 42, wherein the dopant is deposited on the hydrogen-interactive thin film from a precursor, and said precursor is selected from the group consisting of Mg(thd)₂, Ca(thd)₂, dimethyl aluminumhydride, Ba(thd)₂, Sr(thd)₂, (COD)Ir(hfac) and Co(thd)₂.

47. The method of claim 36, wherein the hydrogen-interactive thin film comprises yttrium, formed on the substrate by chemical vapor deposition utilizing as a precursor Y(NSiMe₃)₃.

26. A hydrogen sensor device, comprising:

A hydrogen-interactive thin film sensor element comprising a rare earth metal and /or a rare earth metal dihydride;

a micro-hotplate structure Coupled to said hydrogen-interactive sensor element for selective heating of the sensor element;

a hydrogen-permeable material overlaying said hydrogen-interactive sensor element for selective permeation of hydrogen, wherein said hydrogen-permeable material comprises an alloy to suppress a phase change in said rare earth metal or rare metal dihydride; and

a detector coupled with said hydrogen-interactive sensor element for sensing a detectable change of physical property of the sensor element on exposure to hydrogen and generating a correlative output indicative of hydrogen presence.

36. A method of fabricating a hydrogen sensor on a substrate, comprising:

constructing on the substrate a micro-hotplate structure; and

forming on the micro-hotplate structure a hydrogen-interactive thin film comprising a rare earth metal and/or a rare earth metal dihydride that upon exposure to hydrogen exhibits a detectable change of at least one physical property, and wherein the hydrogen-interactive thin film is arranged to be heated by the micro-hotplate structure; and

forming on the hydrogen-interactive thin film a protective over layer comprising a hydrogen-permeable material for selective permeation of hydrogen, wherein said hydrogen-permeable material comprises an alloy to suppress a phase change in said rare earth metal or rare metal dihydride.