Photo-induced sensitivity and selectivity of semiconductor gas sensors

• US 20080110241A1
• Filed: 11/15/2007
• Published: 05/15/2008
• Est. Priority Date: 05/17/2004
• Status: Abandoned Application

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Rothschild, Avner, Tuller, Harry
• Application Number:
  US11/985,502
• Publication Number:
  US 20080110241A1
• Time in Patent Office: Days
• US Class Current: 73/31.06
• CPC Class Codes: G01N 27/125 Composition of the body, e.g. the composition of its sensitive layer

Abstract

A selective gas sensor comprises a semiconducting substrate, a radiation source that directs narrowband radiation to the semiconducting substrate; and a plurality of electrodes coupled to the semiconducting substrate, whereby a gas is selectively sensed. A method of selectively sensing a gas comprises the steps of contacting the semiconducting substrate with a gas, directing narrowband radiation to the semiconducting substrate and sensing the resistance of the semiconducting substrate, thereby selectively sensing the gas.

Claims

1. A selective gas sensor, comprising:

a semiconducting substrate;

a narrow band radiation source that directs narrowband radiation to the semiconducting substrate, wherein the mean energy of the narrowband radiation is less than the bandgap energy of the semiconducting substrate;

a plurality of electrodes coupled to the semiconducting substrate,

whereby a gas is selectively sensed; and

a controller that sequentially directs distinct narrow band radiation to the semiconductor substrate and measures the resistance of the substance through the electrodes, whereby distinct gases are sensed as a function of time.

2. The sensor of claim 1, wherein the semiconducting substrate includes an inorganic semiconductor selected from family II-VI, III-V semiconductors;

column IV semiconductors;

metal oxides;

sulfides, selenides, and nitrides.

3. The sensor of claim 2, wherein the semiconducting substrate includes an inorganic semiconductor selected from CdTe, CdSe, CdS, ZnS, GaAs, GaN, AlGaN, InGaN, GaP, InP, InAsP, Si, Ge, ZnO, SnO₂, TiO₂, Cr₂, TiO₃, WO₃, SiC, MoO₃, Fe₂O₃, In₂O₃, Ga₂O₃, SrTiO₃, BaTiO₃, CaTiO₃, (La,Sr)FeO₃, and (La,Sr)CoO₃.

4. The sensor of claim 3, wherein the semiconducting substrate is SnO₂, TiO₂, ZnO, WO₃, Fe₂O₃, In₂O₃, Ga₂O₃, SrTiO₃, BaTiO₃, CdS, GaN, or Si.

5. The sensor of claim 1, wherein the semiconducting substrate includes an organic semiconductor selected from carbon nanotubes, fullerenes, polyacetylene, polythiophene, polyphenylene, poly(para-phenylene)vinylene, poly(para-pyridyl)vinylene, polyaniline, and polypyrrole.

6. The sensor of claim 1, wherein the narrowband radiation source is integrated with the semiconducting substrate.

7. The sensor of claim 1, wherein at least about 95% of the narrowband radiation has an energy less than the bandgap energy of the semiconducting substrate.

8. The sensor of claim 1, wherein the narrowband radiation is selectively absorbed by a complex, the complex comprising the semiconducting substrate and the gas to be selectively sensed.

9. The sensor of claim 8, wherein the narrowband radiation source is a narrowband filter coupled to a broadband radiation source.

10. The sensor of claim 8, wherein the narrowband radiation source is a solid state device.

11. The sensor of claim 10, wherein the narrowband radiation source is a laser.

12. The sensor of claim 10, wherein the narrowband radiation source is a light emitting diode.

13. The sensor of claim 1, further including at least two gas sensing sites, wherein the electrodes are coupled to the semiconducting substrate to selectively sense at least one distinct gas at each site.

14. The sensor of claim 13, further including a distinct semiconductor composition at each gas sensing site.

15. The sensor of claim 13, further including a distinct catalyst composition at each gas sensing site.

16. The sensor of claim 13, wherein the narrowband radiation source directs distinct narrowband radiation to each gas sensing site.

17. The sensor of claim 13, further comprising an array of gas sensing sites.

18. The sensor of claim 1, wherein the narrowband radiation source directs radiation having energy greater than the bandgap energy of the semiconducting substrate to the semiconducting substrate, whereby gas contacting the substrate can be desorbed.

19. A method of selectively sensing a gas, comprising the steps of:

contacting a semiconducting substrate that is coupled to a plurality of electrodes with a gas having distinct gas components;

sequentially directing distinct narrowband radiation to the semiconducting substrate, wherein the mean energy of the narrowband radiation is less than the bandgap energy of the semiconducting substrate; and

measuring the resistance of the substrate through the electrodes, whereby the distinct gases are sensed as a function of time.

20. The method of claim 19, wherein the semiconducting substrate includes an inorganic semiconductor selected from family II-VI, III-V or column IV semiconductors/insulators;

metal oxides; and

metal nitrides.

21. The method of claim 20, wherein the semiconducting substrate includes a semiconductor selected from CdTe, CdSe, ZnS, AlGaN, InGaN, GaP, InP, InAsP, Ge, Cr_2-xTi_xO₃, SiC, MoO₃, CaTiO₃, (La,Sr)FeO₃, (La,Sr)CoO₃, SnO₂, TiO₂, ZnO, WO₃, Fe₂O₃, In₂O₃, Ga₂O₃, SrTiO₃, BaTiO₃, CdS, GaN, GaAs, and Si.

22. The method of claim 21, wherein the semiconducting substrate is SnO₂, TiO₂, ZnO, WO₃, Fe₂O₃, In₂O₃, Ga₂O₃, SrTiO₃, BaTiO₃, CdS, GaN, GaAs, or Si.

23. The method of claim 21, wherein the semiconducting substrate includes an organic semiconductor selected from carbon nanotubes, fullerenes, polyacetylene, polythiophene, polyphenylene, poly(para-phenylene)vinylene, poly(para-pyridyl)vinylene, polyaniline, and polypyrrole.

24. The method of claim 19, further including directing the narrowband radiation to the semiconducting substrate from a narrowband radiation source that is integrated with the semiconducting substrate.

25. The method of claim 19, wherein at least about 95% of the narrowband radiation has an energy less than the bandgap energy of the semiconducting substrate.

26. The method of claim 19, further including selecting the wavelength of the narrowband radiation to match an absorption maxima of a complex, the complex comprising the semiconducting substrate and the gas that is selectively sensed.

27. The method of claim 26, further including filtering the narrowband radiation from a broadband radiation source.

28. The method of claim 26, further including directing the narrowband radiation from a solid state narrowband radiation source.

29. The method of claim 28, further including directing the narrowband radiation from a laser.

30. The method of claim 28, further including directing the narrowband radiation from a light emitting diode.

31. The method of claim 19, further including sensing each distinct gas at a distinct gas sensing site.

32. The method of claim 19, wherein each distinct gas sensing site includes a distinct semiconductor.

33. The method of claim 19, further including directing distinct narrowband radiation to each distinct gas sensing site.

34. The method of claim 33, further including selecting the wavelength of the narrowband radiation for each site to match an absorption maxima of a complex, the complex comprising the distinct semiconductor at each distinct gas sensing site and the distinct gas that is selectively sensed at that site.

35. The method of claim 34, further including detecting the distinct gases with an array of distinct selective gas sensing sites.

36. The method of claim 19, further including directing to the semiconducting substrate radiation having photon energy greater than the bandgap energy of the semiconducting substrate, thereby desorbing gas contacting the substrate.

37. The method of claim 19, further including detecting carbon monoxide in a background of hydrogen.

38. The method of claim 19, further including detecting a toxic gas.

39. The method of claim 19, further including detecting a combustible gas.

40. The method of claim 19, further including detecting a gas in an exhaust stream from an internal combustion engine.

41. The method of claim 19, further including detecting a gas in an exhaust stream from a smokestack.

42. The method of claim 19, further including detecting a gas from a chemical process.

43. The method of claim 19, further including detecting a gas from a fermentation process.

44. The method of claim 19, further including detecting a gas from a food source.

45. The method of claim 44, further including detecting a gas from a food processing source.

46. The method of claim 19, further including detecting a gas from a subject that is indicative of the subject'"'"'s health.

47. The method of claim 19, further including detecting a gas to monitor indoor air quality.

48. The method of claim 19, further including detecting a chemical warfare agent, or a chemical precursor or decomposition product thereof.

49. The method of claim 19, further including detecting a chemical indicative of a high explosive.

50. A selective gas sensor, comprising:

a semiconducting substrate;

a solid state narrowband radiation source integrated with the semiconducting substrate that directs narrowband radiation to the semiconducting substrate, wherein

the mean energy of the narrowband radiation is less than the bandgap energy of the semiconducting substrate;

the narrowband radiation is selectively absorbed by a complex, the complex comprising the semiconducting substrate and the gas to be selectively sensed; and

a plurality of electrodes coupled to the semiconducting substrate, whereby a gas is selectively sensed; and

a controller that sequentially directs distinct narrowband radiation to the semiconductor substrate and measures radiation through the electrodes, whereby distinct gases are sensed as a function of time.

51. The sensor of claim 50, further including at least two gas sensing sites, wherein the electrodes are coupled to the semiconducting substrate to selectively sense at least one distinct gas at each site.

52. The sensor of claim 50, wherein the semiconducting substrate is SnO₂, TiO₂, ZnO, WO₃, Fe₂O₃, In₂O₃, Ga₂O₃, SrTiO₃, BaTiO₃, CdS, GaAs, GaN, or Si.

53. A method of selectively sensing a gas, comprising the steps of:

contacting a semiconducting substrate that is coupled to a plurality of electrodes with a gas having distinct gas components;

sequentially directing distinct narrowband radiation to the semiconducting substrate from a solid state narrowband radiation source integrated with the semiconducting substrate, wherein

the mean energy of the narrowband radiation is less than the bandgap energy of the semiconducting substrate;

the narrowband radiation is selectively absorbed by a complex, the complex comprising the semiconducting substrate and the gas; and

measuring the resistance of the substrate through the electrodes, whereby the distinct gases are sensed as a function of time.

54. The method of claim 53, further including selecting the wavelength of the narrowband radiation to match an absorption maxima of a complex for each gas, each complex comprising a distinct semiconductor for each gas and the respective gas.