Method and apparatus for double modulation spectroscopy

• US 4,594,511 A
• Filed: 03/29/1985
• Issued: 06/10/1986
• Est. Priority Date: 03/29/1985
• Status: Expired due to Term

• Current Assignee: SRI International, Inc.
• Original Assignee: SRI International, Inc.
• Inventors: Cooper, David E., Gallagher, Thomas F.
• Primary Examiner(s): Anderson, Bruce C.
• Assistant Examiner(s): Hannaher, Constantine
• Application Number:
  US06/717,356
• Time in Patent Office: 438 Days
• Field of Search: 250/351, 250/341, 250/339, 250/338 R, 250/372, 378/53, 356/300, 356/318, 356/349
• US Class Current: 250/339.07
• CPC Class Codes: G01J 3/4338 Frequency modulated spectrometry

Abstract

A spectroscopic technique in which the sample under investigation is probed with a generally monochromatic beam of light which has been modulated at two distinct modulation frequencies. The double modulation produces a plurality of sidebands, and the two modulation frequencies are related to one another such that a selection of sidebands falls into two groups of closely spaced component sidebands. A first group is disposed in frequency at the spectral feature of interest and serves to probe the spectral feature. The other group is disposed in frequency remote from the feature and serves as a reference group. Within each group the component sidebands are offset from one another by a characteristic offset frequency, which can be considerably less than the width of the spectral feature under investigation. After interaction with the sample the doubly modulated beam is passed on to a photodetector, which in combination with appropriate signal processing apparatus detects a signal at the characteristic offset frequency representative of the spectral feature.

Claims

1. Apparatus for detecting a spectral feature of a sample, said feature having a characteristic width, comprising:

a source of a generally monochromatic beam of light having a characteristic linewidth at most comparable with the width of said spectral feature;

modulation means for modulating said beam at first and second modulation frequencies related to one another so as to provide a plurality of sidebands including a first, probe group and a second, reference group of component sidebands offset from one another within each group by a characteristic offset frequency at most comparable with the width of said feature, said probe and reference groups being disposed in frequency at said spectral feature and remote from said spectral feature, respectively;

a photodetector disposed to receive said beam after interaction with said sample, said photodetector providing an output signal representative of the received beam; and

detection means connected to receive said output signal and detect therein a component signal at said characteristic offset frequency representative of said spectral feature.

2. The apparatus of claim 1 wherein said photodetector has a predetermined bandwidth less than each of said first and second modulation frequencies, and said modulation frequencies are so related to one another that said offset frequency is less than said photodetector bandwidth.

3. The apparatus of claim 2 wherein said generally monochromatic beam has a characteristic linecenter, said first modulation frequency has a magnitude 2ω

+σ

, and said second modulation frequency has a magnitude ω

, where ω

is approximately the frequency difference between said beam linecenter and said spectral feature and σ

is less than said photodetector bandwidth and at most comparable with the width of said spectral feature, whereby σ

equals said offset frequency.

4. The apparatus of claim 1 wherein said modulation means comprises first and second frequency modulators for frequency-modulating the beam at said first and second modulation frequencies respectively.

5. The apparatus of claim 4, further including means for driving said first frequency modulator at a power level corresponding to a modulation index not exceeding unity and for driving said second frequency modulator at a power level corresponding to a modulation index greater than unity.

6. The apparatus of claim 4 wherein said generally monochromatic beam has a characteristic linecenter, said first modulation frequency has a magnitude 2ω

+σ

, and said second modulation frequency has a magnitude ω

, where ω

is approximately the frequency difference between said beam linecenter and said spectral feature and σ

is less than said photodetector bandwidth and at most comparable with the width of said spectral feature, whereby σ

equals said offset frequency.

7. The apparatus of claim 1 wherein said modulation means comprises a frequency modulator for frequency modulating the beam at said first modulation frequency and an amplitude modulator for amplitude modulating the beam at said second modulation frequency.

8. The apparatus of claim 7, further including means for driving said frequency modulator and said amplitude modulator at power levels corresponding to modulation indices not exceeding unity.

9. The apparatus of claim 7 wherein said generally monochromatic beam has a characteristic linecenter, said first modulation frequency has a magnitude 2ω

+σ

, and said second modulation frequency has a magnitude ω

, where ω

is approximately the frequency difference between said beam linecenter and said spectral feature and σ

is less than said photodetector bandwidth and at most comparable with the width of said spectral feature, whereby σ

equals said offset frequency.

10. The apparatus of claim 1, further comprising sweep means for selectively varying the frequency at which said probe sideband group is disposed whereby said probe sideband group is caused to sweep through said spectral feature.

11. The apparatus of claim 10 wherein said generally monochromatic beam has a characteristic linecenter, and said sweep means selectively varies the frequency thereof.

12. The apparatus of claim 10 wherein said sweep means selectively varies said first and second modulation frequencies in relation to one another so as to cause said probe sideband group to sweep through said spectral feature.

13. Apparatus for detecting a spectral feature of a sample, said feature having a characteristic width, comprising:

a source of a generally monochromatic beam of light having a characteristic linecenter and a characteristic linewidth at most comparable with the width of said spectral feature;

first and second frequency modulators for frequency-modulating said beam at first and second modulation frequencies related to one another so as to provide a plurality of sidebands including a first, probe group and a second, reference group of component sidebands offset from one another within each group by a characteristic offset frequency at most comparable with the width of said feature, said probe and reference groups being disposed in frequency above and below said linecenter at said spectral feature and remote from said spectral feature, respectively;

means for exposing said sample to the modulated beam;

a photodetector disposed so as to receive said beam after interaction with said sample, said photodetector providing an output signal representative of the received beam; and

detection means connected to receive said output signal and detect therein a component signal at said offset frequency representative of said spectral feature.

14. The apparatus of claim 13 wherein said monochromatic beam source comprises an incoherent beam source.

15. The apparatus of claim 14 wherein said photodetector is provided by a photomultiplier tube.

16. The apparatus of claim 13 wherein said monochromatic beam source comprises a tunable laser.

17. The apparatus of claim 16 wherein said laser is tunable in the infrared portion of the spectrum.

18. The apparatus of claim 13, further comprising means for pulsed operation of said modulated beam.

19. The apparatus of claim 18 wherein said photodetector is provided by a photomultiplier tube, which in cooperation with said pulsed operation can be exposed to higher light levels than in continuous operation.

20. The apparatus of claim 13, further comprising first and second oscillators coupled to said first and second modulators for generating said first and second modulation frequencies.

21. The apparatus of claim 20, further comprising means coupled to said first and second oscillators for providing a reference signal having a frequency equal to said offset frequency for comparison with said photodetector output signal.

22. The apparatus of claim 13, further comprising:

a first oscillator for generating a first oscillation frequency equal to said offset frequency;

a second oscillator for generating a second oscillation frequency; and

means coupled to said first and second oscillators for deriving said first and second modulation frequencies from said first and second oscillation frequencies.

23. The apparatus of claim 22, further comprising means coupled to said first oscillator and to said photodetector for comparing said photodetector output signal with said offset frequency.

24. The apparatus of claim 22 wherein said second oscillator is provided by a sweep oscillator for synchronously sweeping said first and second modulation frequencies.

25. Apparatus for detecting a spectral feature of a sample, said feature having a characteristic width, comprising:

a source of a generally monochromatic beam of light having a characteristic linecenter and a characteristic linewidth at most comparable with the width of said spectral feature;

a first frequency modulator for frequency-modulating said beam at a first modulation frequency;

an amplitude modulator for amplitude-modulating said beam at a second modulation frequency related to said first modulation frequency so as to provide a plurality of sidebands including a first, probe group and a second, reference group of component sidebands offset from one another within each group by a characteristic offset frequency at most comparable with the width of said feature, said probe and reference groups being disposed in frequency above and below said linecenter at said spectral feature and remote from said spectral feature, respectively;

means for exposing said sample to the modulated beam;

a photodetector disposed so as to receive said beam after interaction with said sample, said photodetector providing an output signal representative of the received beam; and

detection means connected to receive said output signal and detect therein a component signal at said offset frequency representative of said spectral feature.

26. The apparatus of claim 25 wherein said amplitude modulator comprises:

a second frequency modulator for modulating said beam at said second modulation frequency; and

first and second polarizers oriented with the polarization axes thereof perpendicular to one another, said polarizers being disposed in the path of said beam before and after said second frequency modulator.

27. The apparatus of claim 26 wherein said second frequency modulator comprises an electro-optic crystal having a natural birefringence, and said apparatus further comprises means for applying an electrical potential across said crystal for counteracting said birefringence.

28. The apparatus of claim 26, further comprising a pulsed cavity oscillator coupled to said second frequency modulator for effecting pulsed operation of said modulated beam.

29. The apparatus of claim 28 wherein said photodetector is provided by a photomultiplier tube, which in cooperation with said pulsed operation can be exposed to higher light levels than in continuous-wave operation.

30. The apparatus of claim 25 wherein said monochromatic beam source comprises an incoherent beam source.

31. The apparatus of claim 30 wherein said photodetector is provided by a photomultiplier tube.

32. The apparatus of claim 25 wherein said monochromatic beam source comprises a tunable laser.

33. The apparatus of claim 32 wherein said laser is tunable in the infrared portion of the spectrum.

34. The apparatus of claim 25, further comprising first and second oscillators coupled to said first frequency modulator and to said amplitude modulator for generating said first and second modulation frequencies.

35. The apparatus of claim 34, further comprising means coupled to said first and second oscillators for providing a reference signal having a frequency equal to said offset frequency for comparison with said photodetector output signal.

36. The apparatus of claim 25, further comprising:

a first oscillator for generating a first oscillation frequency equal to said offset frequency;

a second oscillator for generating a second oscillation frequency; and

means coupled to said first and second oscillators for deriving said first and second modulation frequencies from said first and second oscillation frequencies.

37. The apparatus of claim 36, further comprising means coupled to said first oscillator and to said photodetector for comparing said photodetector output signal with said offset frequency.

38. The apparatus of claim 36 wherein said second oscillator is provided by a sweep oscillator for synchronously sweeping said first and second modulation frequencies.

39. Apparatus for detecting a spectral feature of sample, said feature having a characteristic width, comprising:

a source of a generally monochromatic beam of light having a characteristic linewidth at most comparable with the width of said spectral feature and having a characteristic linecenter removed from said spectral feature by a frequency displacement greater than said characteristic spectral feature width, said beam being disposed so as to expose said sample thereto;

a first oscillator for generating a first modulation frequency (ω

) approximately equal to said frequency displacement;

a second oscillator for generating a second modulation frequency (2ω

±

σ

) differing from twice said first modulation frequency by an offset frequency (σ

) small in comparison with said characteristic spectral feature width;

means coupled to said first and second oscillators for modulating said beam at said first and second modulation frequencies;

a photodetector disposed so as to receive said beam after interaction with said sample, said photodetector providing an output signal representative of the received beam;

means receiving said first and second modulation frequencies and deriving therefrom a reference signal having a frequency equal to said offset frequency; and

means receiving said reference signal and said photodetector output signal and deriving therefrom the component of said photodetector output signal at said offset frequency representative of said spectral feature.

40. The apparatus of claim 39 wherein said means for modulating said beam comprises first and second frequency modulators, whereby said beam is frequency-modulated at said first and second modulation frequencies.

41. The apparatus of claim 40 wherein said means deriving said reference signal comprises:

a frequency doubler receiving said first modulation frequency (ω

) and providing a signal of frequency (2ω

) equal to twice said first modulation frequency; and

a mixer receiving said second modulation frequency (2ω

±

σ

) and said frequency (2ω

) from said frequency doubler and providing said reference signal at said offset frequency (σ

).

42. The apparatus of claim 41, further comprising signal averaging means receiving said component of said photodetector output signal at said offset frequency and providing an average value thereof.

43. The apparatus of claim 42 wherein said monochromatic beam source comprises a tunable laser.

44. The apparatus of claim 39 wherein said means for modulating said beam comprises a frequency modulator and an amplitude modulator, whereby said beam is frequency-modulated at one of said first and second modulation frequencies and is amplitude-modulated at the other of said modulation frequencies.

45. The apparatus of claim 44 wherein said means deriving said reference signal comprises:

a frequency doubler receiving said first modulation frequency (ω

) and providing a signal of frequency (2ω

) equal to twice said first modulation frequency; and

a mixer receiving said second modulation frequency (2ω

±

σ

) and said frequency (2ω

) from said frequency doubler and providing said reference signal at said offset frequency (σ

).

46. The apparatus of claim 45, further comprising signal averaging means receiving said component of said photodetector output signal at said offset frequency and providing an average value thereof.

47. The apparatus of claim 46 wherein said monochromatic beam source comprises a tunable laser.

48. Apparatus for detecting a spectral feature of sample, said feature having a characteristic width, comprising:

a source of a generally monochromatic beam of light having a characteristic linewidth at most comparable with the width of said spectral feature and having a characteristic linecenter removed from said spectral feature by a frequency displacement greater than said characteristic spectral feature width, said beam being disposed so as to expose said sample thereto;

a first oscillator for generating a first modulation frequency (ω

) approximately equal to said frequency displacement;

a second oscillator for generating an offset frequency (σ

) small in comparison with said characteristic spectral feature width;

frequency synthesis means receiving said first modulation frequency (ω

) and said offset frequency (σ

) and deriving therefrom a second modulation frequency (2ω

±

σ

) differing from twice said first modulation frequency by said offset frequency (σ

);

means coupled to said first oscillator and to said frequency synthesis means for modulating said beam at said first and second modulation frequencies;

a photodetector disposed so as to receive said beam after interaction with said sample, said photodetector providing an output signal representative of the received beam; and

means receiving said offset frequency and said photodetector output signal and deriving therefrom the component of said photodetector output signal at said offset frequency representative of said spectral feature.

49. The apparatus of claim 48 wherein said first oscillator is provided by a sweep oscillator for synchronously sweeping said first and second modulation frequencies.

50. The apparatus of claim 49 wherein said means for modulating said beam comprises first and second frequency modulators, whereby said beam is frequency-modulated at said first and second modulation frequencies.

51. The apparatus of claim 49 wherein said means for modulating said beam comprises a frequency modulator and an amplitude modulator, whereby said beam is frequency-modulated at one of said first and second modulation frequencies and is amplitude-modulated at the other of said modulation frequencies.

52. An incoherent, single-beam spectrometer for use in detecting a spectral feature of a sample, said feature having a characteristic width, comprising:

an incoherent source of a single beam of generally monochromatic light having a characteristic linewidth at most comparable with the width of said spectral feature;

modulation means for modulating said beam at first and second modulation frequencies related to one another so as to provide a plurality of sidebands including a first, probe group and a second, reference group of component sidebands offset from one another within each group by a characteristic offset frequency at most comparable with the width of said feature, said probe and reference groups being disposed in frequency at said spectral feature and remote from said spectral feature, respectively;

means for exposing said sample to the modulated beam;

a photodetector disposed so as to receive said beam after interaction with said sample, said photodetector having a predetermined bandwidth less than each of said first and second modulation frequencies and greater than said offset frequency and providing an output signal representative of the received beam; and

detection means connected to receive said output signal and detect therein a component signal at said offset frequency representative of said spectral feature.

53. The spectrometer of claim 52 wherein said means for exposing said sample to the beam comprises an absorption cell disposed such that the beam received by said photodetector represents absorption by said sample.

54. The spectrometer of claim 53 wherein said photodetector is responsive to an incident optical power of at least 16 nanowatts.

55. The spectrometer of claim 54 wherein said photodetector is provided by a photomultiplier tube.

56. The spectrometer of claim 54 wherein said incoherent beam source comprises an incoherent light source and means for narrowing the spectral range thereof.

57. The spectrometer of claim 56, further comprising sweep means for selectively varying the frequency at which said probe sideband group is disposed whereby said probe sideband group is caused to sweep through said spectral feature.

58. The spectrometer of claim 57 wherein said generally monochromatic beam has a characteristic linecenter, and said sweep means selectively varies the frequency thereof.

59. The spectrometer of claim 56 wherein said modulation means comprises first and second frequency modulators for frequency-modulating the beam at said first and second modulation frequencies.

60. The spectrometer of claim 56 wherein said modulation means comprises a frequency modulator for frequency-modulating the beam at the first modulation frequency, and an amplitude modulator for amplitude-modulating the beam at the second modulation frequency.

61. A method of detecting a spectral feature of a sample, said spectral feature having a characteristic width, comprising the steps of:

providing a generally monochromatic beam of light having a characteristic linewidth at most comparable with the width of said spectral feature;

modulating said beam at first and second modulation frequencies related to one another so as to provide a plurality of sidebands including a first, probe group and a second, reference group of component sidebands offset from one another within each group by a characteristic offset frequency at most comparable with the width of said feature, said probe and reference groups being disposed in frequency at said spectral feature and remote from said spectral feature, respectively;

directing said beam at said sample so as to interact therewith;

photodetecting said beam after it has interacted with said sample to detect therein a signal at said characteristic offset frequency representative of said spectral feature.

62. A method of measuring the absorption spectrum of a sample having a spectral feature of characteristic width comprising the steps of:

providing a generally monochromatic beam of incoherent light having a characteristic linewidth at most comparable with the width of said spectral feature;

modulating said beam at first and second modulation frequencies related to one another so as to provide a plurality of sidebands including a first, probe group and a second, reference group of component sidebands offset from one another within each group by a characteristic offset frequency at most comparable with the width of said feature, said probe and reference groups being disposed in frequency at said spectral feature and remote from said spectral feature, respectively;

directing said beam at said sample so as to interact therewith;

photodetecting in the beam transmitted by said sample only the spectral component frequencies thereof below a predetermined cutoff frequency less than each of said first and second modulation frequencies; and

detecting within the photodetected spectral component frequencies below said cutoff a component at said offset frequency representative of the absorption by said spectral feature.

63. The method of claim 62 wherein the characteristic linewidth of said beam and said characteristic offset frequency are substantially less than the width of said spectral feature, further comprising the step of causing said probe group to sweep through said spectral feature.