INFRARED SPECTROMETER

• US 20080315102A1
• Filed: 08/25/2008
• Published: 12/25/2008
• Est. Priority Date: 11/30/2006
• Status: Active Grant

• Current Assignee: UK Research and Innovation
• Original Assignee: Science and Technology Facilities Council
• Inventors: WEIDMANN, Damien
• Granted Patent: US 7,994,479 B2
• Time in Patent Office: Days
• US Class Current: 250/339.01
• CPC Class Codes: G01J 3/02 Details
• CPC Class Codes: G01J 3/0286 Constructional arrangements for compensating for fluctuations caused by temperature, humidity or pressure, or using cooling or temperature stabilization of parts of the device; Controlling the atmosphere inside a spectrometer, e.g. vacuum
• CPC Class Codes: G01J 3/08 Beam switching arrangements
• CPC Class Codes: G01J 3/42 Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry beam switching arrangements G01J3/08
• CPC Class Codes: G01N 2021/399 Diode laser
• CPC Class Codes: G01N 21/276 with alternation of sample and standard in optical path
• CPC Class Codes: G01N 21/3504 for analysing gases, e.g. multi-gas analysis
• CPC Class Codes: G01N 21/39 using tunable lasers

Abstract

Method and apparatus for detecting, by absorption spectroscopy, an isotopic ratio of a sample, by passing first and second laser beams of different frequencies through the sample. Two IR absorption cells are used, a first containing a reference gas of known isotopic ratio and the second containing a sample of unknown isotopic ratio. An interlacer or reflective chopper may be used so that as the laser frequencies are scanned the absorption of the sample cell and the reference cell are detected alternately. This ensures that the apparatus is continuously calibrated and rejects the baseline noise when phase sensitive detection is used.

Claims

1. An infrared, IR, spectrometer comprising:

a first tunable IR laser for providing a first beam at a first wavelength;

a second tunable IR laser for providing a second beam at a second wavelength;

a first absorption cell arranged to receive both first and second beams;

a second absorption cell arranged to receive both first and second beams;

a first optical absorption detector arranged to detect said first wavelength; and

a second optical absorption detector arranged to detect said second wavelength.

2. The IR spectrometer of claim 1 further comprising:

an interlacer arranged to alternately block said first and said second absorption cells.

3. The IR spectrometer of claim 2, wherein said interlacer is an optical chopper comprising at least one reflective blade angled to direct transmitted IR radiation from one of said optical absorption cells on to both of said optical absorption detectors.

4. The IR spectrometer according to claim 2, wherein the wavelengths of said first and second tunable IR lasers are changeable after said first and said second optical absorption detectors have been blocked.

5. The IR spectrometer according to claim 3, wherein the first and second IR tunable lasers are arranged to vary the first and second wavelengths in synchronisation with the optical chopper.

6. The IR spectrometer of claim 5, wherein the first and second wavelengths are arranged to vary stepwise.

7. The IR spectrometer of claim 5, wherein the first and second wavelengths are arranged to vary smoothly.

8. The IR spectrometer of claim 6, wherein the first and second wavelengths are arranged to be varied across a selection of absorption lines of a sample being measured.

9. The IR spectrometer of claim 5, wherein the optical chopper is arranged to direct transmitted IR radiation from one of said optical absorption cells on to both of said optical absorption detectors at a frequency.

10. The IR spectrometer of claim 9, wherein the first and second optical absorption detectors are arranged to detect at the frequency.

11. The IR Spectrometer of claim 10, wherein the detection is maintained at the frequency by phase detection of the chopper frequency.

12. The IR Spectrometer according to any of claims 2, wherein the interlacer alternatively blocks said first and said second absorption cells at or above 1 KHz.

13. The IR spectrometer of claim 1 further comprising a beam combiner arranged to combine said first beam with said second beam to form a combined beam such that said first absorption cell and said second absorption cell each receive a portion of said combined beam.

14. The IR spectrometer of claim 1, wherein said beam combiner comprises a dichroic mirror.

15. The IR spectrometer of claim 1, further comprising a beam splitter arranged to direct a portion of the combined beam into each of said first and second absorption cells.

16. The IR spectrometer of claim 1 further comprising a beam separator arranged to separate said first wavelength from said second wavelength such that said first wavelength is detected by said first detector and said second wavelength is detected by said second detector.

17. The IR spectrometer of claim 1, wherein said first tunable IR laser is a diode laser.

18. The IR spectrometer of claim 17, wherein said diode laser is tunable between about 2 μ

m and about 12 μ

m.

19. The IR spectrometer of claim 1, wherein said second tunable IR laser is a quantum cascade laser.

20. The IR spectrometer of claim 19, wherein said quantum cascade laser is tunable between about 4 μ

m and about 24 μ

m.

21. The IR spectrometer of claim 1 further comprising a data logger for recording data generated by said first and second optical absorption detectors.

22. The IR spectrometer of claim 1, wherein said first absorption cell contains a reference sample and said second absorption cell contains a sample.

23. The IR spectrometer of claim 1, wherein the first wavelength is different to the second wavelength.

24. The IR spectrometer of claim 1, wherein said first and second absorption cells contain a sample consisting of one of ¹²CO₂/¹³CO₂, C¹⁶O₂/¹⁶OC¹⁸O, H₂¹⁶O/H₂¹⁸O, ¹²CH₄/¹³CH₄, ¹²CH₄/¹²CDH₃, ¹⁴N₂O/¹⁴N¹⁵NO and H₂O/HDO

25. An infrared, IR, spectrometer comprising:

a first tunable IR laser for providing a first beam at a first wavelength;

a second tunable IR laser for providing a second beam at a second wavelength;

a first absorption cell arranged to receive both first and second beams;

a second absorption cell arranged to receive both first and second beams;

a first optical absorption detector arranged to detect said first wavelength;

a second optical absorption detector arranged to detect said second wavelength; and

an interlacer arranged such that said first and said second absorption cells are alternately switched from receiving said first and said second beams.

26. A method of isotopic ratio determination comprising the steps of:

(a) passing a first tunable IR laser beam through a first absorption cell;

(b) passing a second tunable IR laser beam through a second absorption cell;

(c) detecting the absorption due to a first sample contained within said first cell; and

(d) detecting the absorption due to a second sample contained within said second cell such that the isotopic ratio of said second sample is determined.

27. The method of claim 26 further comprising the step of:

(ii) alternately switching said first and second IR laser beams such that the detecting steps (c) and (d) occur in turn.

28. The method of claim 26 further comprising the step of:

(i) combining said first tunable IR laser beam with said second tunable IR laser beam before passing both laser beams through both cells.

29. The method of claim 26 further comprising the step of varying the wavelength of each tunable IR laser beam following each sequence of step (c) and (d).

30. The method of claim 29, wherein the wavelength of each tunable IR laser is varied stepwise.

31. The method of claim 29, wherein the wavelength of each tunable IR laser is varied smoothly.

32. The method of claim 29, wherein the wavelength is varied across a selection of absorption lines of a sample being measured.

33. The method of claim 29, wherein the first and second IR laser beams are alternatively switched at a frequency and detecting the absorption due to the first and second samples occurs at the frequency.

34. The method of claim 33, wherein the detection is maintained at the frequency by phase detection.

35. The method of claim 33, wherein the frequency is at or above 1 KHz.

36. A method of selecting a pair of isotopic spectroscopic lines for a sample suitable for use in isotopic ratio determination comprising the step of:

(a) selecting a pair of isotopic spectroscopic lines of similar intensities such that a suitable pair of isotopic spectroscopic lines is selected.

37. The method of claim 36 further comprising the step of:

(b) comparing the thermal characteristics of said pair of isotopic spectroscopic lines and rejecting said pair if the thermal characteristics are significantly different.

38. The method of claim 37, wherein the thermal characteristics are determined to be significantly different if the line intensity or wavelength varies significantly with temperature.

39. The method of claim 37, wherein the isotopic spectroscopic lines are spaced far apart.

40. The method of claim 36, wherein the sample is selected from the group consisting of ¹²CO₂/¹³CO₂, C¹⁶O₂/¹⁶OC¹⁸O, H₂¹⁶/H₂¹⁸O, ¹²CH₄/¹³CH₄, ¹²CH₄/¹²CDH₃, ¹⁴N₂O/¹⁴N¹⁵NO and H₂O/HDO

41. A method for detecting an isotopic ratio of a sample comprising the steps of

(a) passing a first laser beam and a second laser beam of different frequencies through a sample;

and

(b) detecting the optical absorption due to the sample such that a first absorption line and a second absorption line are measured.

42. A method for detecting an isotopic ratio of a sample by measuring the relative intensities of at least one of the following pairs of absorption lines:

3601.4210 cm<sup>−

1</sup>/2294.4811 cm<sup>−

1</sup>, 3599.7027 cm<sup>−

1</sup>/2295.8456 cm<sup>−

1</sup>, and 3597.9626 cm<sup>−

1</sup>/2297.1862 cm<sup>−

1</sup>.