Standardizing and calibrating a spectrometric instrument

• US 5,303,165 A
• Filed: 02/12/1992
• Issued: 04/12/1994
• Est. Priority Date: 02/12/1992
• Status: Expired due to Term

• Current Assignee: Perkin-Elmer Llc (Revvity, Inc.)
• Original Assignee: The Perkin-Elmer Corporation (Thermo Fisher Scientific Incorporated)
• Inventors: Tracy, David H., Ganz, Alan M., Hoult, Robert A.
• Primary Examiner(s): Harvey, Jack B.
• Assistant Examiner(s): Stamber, Eric W.
• Application Number:
  US07/834,448
• Time in Patent Office: 790 Days
• Field of Search: 364/571.01, 364/571.02, 364/571.03, 364/571.04, 364/571.05, 364/571.07, 364/571.08, 364/498, 364/581, 364/582, 364/572, 356/319, 356/323, 356/325, 356/326, 356/328, 356/331, 356/334, 250/252.1 A
• US Class Current: 356/319
• CPC Class Codes: G01J 2003/2866 Markers; Calibrating of scan
• CPC Class Codes: G01J 3/28 Investigating the spectrum using colour filters G01J3/51
• CPC Class Codes: G01J 3/2803 using photoelectric array detector

Abstract

A spectrometric instrument which exhibits an intrinsic profile for a sharp spectral line produces profile data for narrow spectral lines. The spectral lines are effected with a high finesse etalon of gold coated polymer. A transformation filter is computed for transforming the profile data to a gaussian profile. A wavelength calibration is combined with the filter to effect a correction matrix which is applied to sample data to generate calibrated standardized data. Iteratively a correction matrix is applied to calibration data to generate standardized calibration data which is utilized for the wavelength calibration. Calibration is effected with an optical standard, an interference etalon and a fringe formula. Etalon effective thickness is first estimated and then precisely determined so that fringe peaks calibrate wavelength.

Claims

1. A method of standardizing a spectrometric instrument having a characteristic intrinsic profile of spectral line shape for a hypothetically thin spectral line in each segment of a selected spectral range, each intrinsic profile having an associated intrinsic width, the instrument including a line source of at least one narrow spectral line in at least one selected segment of the spectral range, and each narrow spectral line having an associated line width substantially narrower than the intrinsic width for a corresponding selected segment, the method comprising:

specifying a target profile of spectral line shape for a hypothetically sharp spectral line in each selected segment, initially operating the instrument with the line source to produce a set of profile data for each narrow spectral line such that each set of profile data is representative of the intrinsic profile for a corresponding selected segment, computing a transformation filter for transforming each set of profile data to a corresponding target profile for each selected segment, and saving the transformation filter for future application to sample data.

2. The method of claim 1 further comprising normally operating the instrument with a sample source to produce sample data representative of a sample spectrum, and applying the transformation filter to the sample data in each selected segment to generate standarized sample data representative of the sample spectrum.

3. The method of claim 2 further comprising preliminarily operating the instrument to store nominal background data, and correcting the profile data and the sample data with the nominal background data.

4. The method of claim 3 wherein the steps of correcting comprise dividing the profile data and the sample data by the nominal background data.

5. The method of claim 3 wherein the step of normally operating includes further operating the instrument to produce normal background data associated with the sample data, the step of applying includes further applying the transformation filter to the normal background data to generate standardized background data, and the method further comprises correcting the standardized sample data with the standardized background data.

6. The method of claim 2 further comprising calibrating the profile data according to a preselected spectral intensity calibration prior to the step of computing, and calibrating the sample data according to the intensity calibration prior to the step of applying.

7. The method of claim 1 wherein the target profile has a profile width nominally equal to the intrinsic width.

8. The method of claim 1 wherein the target profile is Gaussian.

9. The method of claim 1 wherein the at least one selected segment comprises a plurality of tandem segments across the selected spectral range, each tandem segment having at least one narrow spectral line.

10. The method of claim 9 wherein the line source is a high finesse Fabry-Perot etalon.

11. The method of claim 1 further comprising establishing a wavelength calibration for the instrument, and combining the wavelength calibration with the transformation filter to effect a correction matrix, wherein the step of saving comprises saving the correction matrix for future application to sample data.

12. The method of claim 11 further comprising normally operating the instrument with a sample source to produce sample data representative of a sample spectrum, and applying the correction matrix to the sample data to generate calibrated standardized data representative of the sample spectrum.

13. The method of claim 11 wherein the step of establishing comprises operating the instrument with a wavelength calibration source of radiation to produce calibration data, applying the transformation filter to the calibration data to generate standardized calibration data constituting the wavelength calibration.

14. The method of claim 13 further comprising preliminarily operating the instrument to store nominal background data, and correcting the calibration data, the profile data and the sample data with the nominal background data.

15. The method of claim 14 wherein the steps of correcting comprise dividing the calibration data, the profile data and the sample data by the nominal background data.

16. The method of claim 11 wherein the instrument has a nominal calibration of spectral wavelength versus spectral locations in the spectral range, the instrument further includes a calibration source of a primary spectral peak of precisely identified wavelength and a multiple source of a multiplicity of secondary peaks spaced across the spectral range, each secondary peak has an integer order number identified by a correlation function to a peak wavelength in accordance with a correlation constant, and the step of establishing a wavelength calibration comprises:

additionally operating the instrument with the calibration source to produce calibration data representative of the primary spectral peak, and further additionally operating the instrument with the multiple source to produce secondary data representative of the multiplicity of secondary peaks;

ascertaining from the calibration data a primary peak location with respect to the spectral locations, and further ascertaining from the secondary data a set of secondary peak locations with respect to the spectral locations;

estimating with the correlation function the correlation constant in accordance with order number differential for at least two peak wavelengths determined by the nominal calibration;

identifying with the correlation function a calibration order number for at least one selected secondary peak located adjacent the primary peak, said identifying being effected in accordance with the estimated correlation constant and a preliminary wavelength determined for the selected secondary peak by the nominal calibration;

interpolating from the selected secondary peak a precise relative positioning of the selected secondary peak and the primary peak;

calculating with the correlation function a precise correlation constant from the calibration order number, the precisely identified wavelength and the relative positioning; and

utilizing the precise correlation constant with the correlation function to assign calibrated wavelengths to associated order numbers and thereby to secondary peak locations with respect to the spectral locations.

17. The method of claim 16 wherein the multiple source comprises a source of radiation and a first optical element inserted in the radiation, the first optical element has an index of refraction (n) related to wavelength, and the order number (m) is identified to peak wavelength (L) in accordance with the correlation constant (T'"'"') by the correlation function m=nT'"'"'/L.

18. The method of claim 17 wherein the multiple source is a Fabry-Perot low finesse etalon disposed to transmit the radiation in a fringe pattern comprising the multiplicity of secondary peaks.

19. The method of claim 18 wherein the low finesse etalon comprises a plate of uncoated fused silica.

20. The method of claim 16 wherein the calibration data define a calibration profile, and the step of ascertaining comprises storing the calibration profile, estimating a centroid wavelength of the calibration profile with respect to the spectral locations, reversing the calibration profile about the centroid wavelength to create a reversed profile, adding the calibration profile and the reversed profile to create a combined profile, and fitting the calibration data to the combined profile to determine an offset between the estimated centroid wavelength and the primary spectral peak, whereby the offset defines the primary peak location with respect to the spectra locations.

21. The method of claim 20 wherein the calibration source is a neodymium doped yttrium aluminum garnet filter.

22. A method of establishing a precision wavelength point in a spectrometric instrument including a calibration source of a spectral peak of precisely identified wavelength, the instrument having a nominal calibration of spectral wavelength versus spectral locations in a spectral range, the method comprising operating the instrument with the calibration source to produce calibration data defining a calibration profile representative of the spectral peak, storing the calibration profile, estimating a centroid wavelength of the calibration profile with respect to the spectral locations, reversing the calibration profile about the estimated centroid wavelength to create a reversed profile, adding the calibration profile and the reversed profile to create a combined profile, and fitting the calibration data to the combined profile to determine an offset between the estimated centroid wavelength and the spectral peak, whereby the offset defines a primary peak location with respect to the spectral locations.

23. The method of claim 22 wherein the calibration source is a neodymium doped yttrium aluminum garnet filter.

24. A method of precisely calibrating wavelength in a spectrometric instrument having a nominal calibration of spectral wavelength versus spectral locations in a selected spectral range, the instrument including a calibration source of a primary spectral peak of precisely identified wavelength and a multiple source of a multiplicity of secondary peaks spaced across the spectral range each secondary peak having an integer order number identified by correlation function to a peak wavelength in accordance with a correlation constant, the method comprising:

additionally operating the instrument with the calibration source to produce calibration data representative of the primary spectral peak, and further additionally operating the instrument with the multiple peak source to produce secondary data representative of the multiplicity of secondary peaks;

ascertaining from the calibration data a primary peak location with respect to the spectral locations, and further ascertaining from the secondary data a set of secondary peak locations with respect to the spectral locations;

estimating with the correlation function the correlation constant in accordance with order number differential for at least two peak wavelengths determined by the nominal calibration;

identifying with the correlation function a calibration order number for at least one selected secondary peak located adjacent the primary peak, said identifying being effected in accordance with the estimated correlation constant and a preliminary wavelength determined for the selected secondary peak by th nominal calibration;

interpolating from the selected secondary peak a precise relative positioning of the selected secondary peak and the primary peak

calculating with the correlation function a precise correlation constant from the calibration order number, the precisely identified wavelength and the relative positioning; and

utilizing the precise correlation constant with the correlation function to assign calibrated wavelengths to associated order numbers and thereby to secondary peak locations with respect to the spectra locations.

25. The method of claim 24 wherein the multiple source comprises a source of radiation and a first optical element inserted in the radiation, the first optical element has an index of refraction (n) related to wavelength, and the order number (m) is identified to peak wavelength (L) in accordance with the correlation constant (T'"'"') by the correlation function m=nT'"'"'/L.

26. The method of claim 25 wherein the multiple source is a Fabry-Perot low finesse etalon disposed to transmit the radiation in a fringe pattern comprising the multiplicity of secondary peaks.

27. The method of claim 26 wherein the low finesse etalon comprises a plate of uncoated fused silica.

28. The method of claim 24 wherein the calibration data define a calibration profile, and the step of ascertaining comprises storing the calibration profile, estimating a centroid wavelength of the calibration profile with respect to the spectral locations, reversing the calibration profile about the centroid wavelength to create a reversed profile, adding the calibration profile and the reversed profile to create a combined profile, and fitting the calibration data to the combined profile to determine a offset between the estimated centroid wavelength and the primary spectral peak, whereby the offset defines the primary peak location with respect to the spectral locations.

29. The method of claim 28 wherein the calibration source is a neodymium doped yttrium aluminum garnet filter.

30. A spectrometric instrument having a characteristic intrinsic profile for a hypothetically thin spectral line in each segment of a selected spectral range, each intrinsic profile having an associated intrinsic width, the instrument including a line source of at least one narrow spectral line in at least one selected segment of the spectral range, and each narrow spectral line having an associated line width substantially narrower than the intrinsic width for a corresponding selected segment, and the instrument further including a standardizing system comprising:

specifying means for specifying a target profile for a hypothetically thin spectral line in each selected segment, initial means for initially operating the instrument with the line source to produce a set of profile data for each narrow spectral line such that each set of profile data is representative of the intrinsic profile for a corresponding selected segment, computing means for computing a transformation filter for transforming each set of profile data to a corresponding target profile for each selected segment, operating means for normally operating the instrument with a sample source to produce sample data representative of a sample spectrum, and application means for applying the transformation filter to the sample data in each selected segment to generate standardized sample data representative of the sample spectrum.

31. The apparatus of claim 30 further comprising background means for preliminarily operating the instrument to store nominal background data, and correcting the profile data and the sample data with the nominal background data.

32. The apparatus of claim 30 wherein the line source is an etalon structure comprising a high finesse Fabry-Perot etalon.

33. The apparatus of claim 32 wherein the etalon comprises a thin polymer film having a semitransparent gold coating on each side thereof, each coating being sufficient to provide between 1% and 10% transmission.

34. The apparatus of claim 33 wherein the film is between 10 and 25 micrometers thick.

35. The apparatus of claim 33 wherein the film is nitrocellulose.

36. The apparatus of claim 33 wherein the etalon structure further comprises a pair of planar glass windows with the etalon sandwiched therebetween.

37. The apparatus of claim 30 further comprising calibration means for establishing a wavelength calibration for the instrument, combining means for combining the wavelength calibration with the transformation filter to effect a correction matrix, operating means for operating the instrument with a sample source to produce sample data representative of a sample spectrum, and application means for applying the correction matrix to the sample data to generate calibrated standardized data representative of the sample spectrum.

38. The apparatus of claim 37 wherein the instrument further includes a wavelength calibration source of radiation, and the calibration means comprises means for operating the instrument with the wavelength calibration source to produce calibration data, and applying the transformation filter to the calibration data to generate standardized calibration data constituting the wavelength calibration.

39. The apparatus of claim 38 further comprising background means for preliminarily operating the instrument to store nominal background data, and correcting the calibration data, the profile data background data and the sample data with the nominal background data.

40. The apparatus of claim 37 wherein the instrument has a nominal calibration of spectral wavelength versus spectral locations in the spectral range, the instrument further includes a calibration source of at least on primary spectral peak of precisely identified wavelength and a multiple source of a multiplicity of secondary peaks spaced across the spectral range, each secondary peak has an integer order number identified by correlation function to a peak wavelength in accordance with a correlation constant, and the calibration means comprises:

additional means for additionally operating the instrument with the calibration source to produce calibration data representative of the primary spectral peak, and further additionally operating the instrument with the multiple peak source to produce secondary data representative of the multiplicity of secondary peaks;

ascertaining means for ascertaining from the calibration data a primary peak location with respect to the spectral locations, and further ascertaining from the secondary data a set of secondary peak locations with respect to the spectral locations;

estimating means for estimating with the correlation function the correlation constant in accordance with order number differential for at least two peak wavelengths determined by the nominal calibration;

identifying means for identifying with the correlation function a calibration order number for at least one selected secondary peak located adjacent the primary peak, said identifying being effected in accordance with the estimated correlation constant and a preliminary wavelength determined for the selected secondary peak by the nominal calibration;

interpolating means for interpolating from the selected secondary peak a precise relative positioning of the selected secondary peak and the primary peak;

calculating means for calculating with the correlation function a precise correlation constant from the calibration order number, the precisely identified wavelength and the relative positioning; and

utilizing means for utilizing the precise correlation constant with the correlation function to assign calibrated wavelengths to associated order numbers and thereby to secondary peak locations with respect to the spectral locations.

41. The apparatus of claim 40 wherein the multiple source is a Fabry-Perot low finesse etalon disposed to transmit the radiation in a fringe pattern comprising the multiplicity of secondary peaks.

42. The apparatus of claim 41 wherein the low finesse etalon comprises a plate of uncoated fused silica.

43. The apparatus of claim 40 wherein the calibration source comprises an optical standard of neodymium doped yttrium aluminum garnet.

44. A spectrometric instrument including a calibration source of at least one primary spectral peak of precisely identified wavelength, and a multiple source of a multiplicity of secondary peaks spaced across the spectral range, each secondary peak having an integer order number identified by correlation function to a peak wavelength in accordance with a correlation constant, the instrument having a nominal calibration of spectral wavelength versus spectral locations in a selected spectral range, and the instrument further including calibration means comprising:

additional means for additionally operating the instrument with the calibration source to produce calibration data representative of the primary spectral peak, and further additionally operating the instrument with the multiple peak source to produce secondary data representative of the multiplicity of secondary peaks;

ascertaining means for ascertaining from the calibration data a primary peak location with respect to the spectral locations, and further ascertaining from the secondary data a set of secondary peak locations with respect to the spectra locations;

estimating means for estimating with the correlation function the correlation constant in accordance with order number differential for at least two peak wavelengths determined by the nominal calibration;

identifying means for identifying with the correlation function a calibration order number for at least one selected secondary peak located adjacent the primary peak, said identifying being effected in accordance with the estimated correlation constant and a preliminary wavelength determined for the selected secondary peak by the nominal calibration;

interpolating means for interpolating from the selected secondary peak a precise relative positioning of the selected secondary peak and the primary peak;

calculating means for calculating with the correlation function a precise correlation constant from the calibration order number, the precisely identified wavelength and the relative positioning; and

utilizing means for utilizing the precise correlation constant with the correlation function to assign calibrated wavelengths to associated order numbers and thereby to secondary peak locations with respect to the spectral locations.

45. The apparatus of claim 44 wherein the multiple source comprises a source of radiation and a first optical element inserted in the radiation, the first optical element has an index of refraction (n) related to wavelength, and the order number (m) is identified to peak wavelength (L) in accordance with the correlation constant (T'"'"') by the correlation function m=nT'"'"'/L.

46. The apparatus of claim 45 the multiple source is a Fabry-Perot low finesse etalon disposed to transmit the radiation in a fringe pattern comprising the multiplicity of secondary peaks.

47. The apparatus of claim 46 wherein the low finesse etalon comprises a plate of uncoated fused silica.

48. The apparatus of claim 46 wherein the calibration source is a neodymium doped yttrium aluminum garnet filter.

49. An etalon structure including a high finesse etalon for passing near infra-red spectral lines, the etalon comprising a thin polymer film having a semitransparent gold coating on each side thereof, each coating being sufficient to provide between 1% and 10% transmission, the etalon structure further including a pair of planar glass windows with the etalon sandwiched therebetween.

50. The etalon structure of claim 49 wherein the film is between 10 and 25 micrometers thick.

51. The etalon structure of claim 49 wherein the film is nitrocellulose.