Spectroscopic chemical analysis methods and apparatus

• US 8,395,770 B1
• Filed: 08/21/2009
• Issued: 03/12/2013
• Est. Priority Date: 10/05/2004
• Status: Active Grant

• Current Assignee: Photon Systems (ABB Limited)
• Original Assignee: Photon Systems (ABB Limited)
• Inventors: Hug, William F., Reid, Ray D., Bhartia, Rohit
• Primary Examiner(s): LAUCHMAN, LAYLA G
• Application Number:
  US12/545,772
• Time in Patent Office: 1,299 Days
• Field of Search: 356/317, 356/318, 356/301, 356/326, 356/417
• US Class Current: 356/317
• CPC Class Codes: G01J 3/10 Arrangements of light sources specially adapted for spectrometry or colorimetry
• CPC Class Codes: G01J 3/36 Investigating two or more bands of a spectrum by separate detectors
• CPC Class Codes: G01J 3/44 Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
• CPC Class Codes: G01N 2021/6421 Measuring at two or more wavelengths
• CPC Class Codes: G01N 2021/6471 Special filters, filter wheel
• CPC Class Codes: G01N 21/645 Specially adapted constructive features of fluorimeters
• CPC Class Codes: G01N 21/65 Raman scattering
• CPC Class Codes: G01N 2201/0612 Laser diodes
• CPC Class Codes: G01N 2201/067 Electro-optic, magneto-optic, acousto-optic elements
• CPC Class Codes: G01N 27/44721 by optical means

Abstract

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Claims

1. A method of providing a chemical analysis of a sample, comprising:

(a) supplying a sample to be analyzed;

(b) applying ultraviolet excitation radiation from a source directly or indirectly onto the sample to produce emission radiation in the form of Raman emission radiation within a first range of wavelengths and photoluminescence emission radiation within a second range of wavelengths;

(c) receiving the emission radiation, directly or indirectly, from the sample at at least one first spectral filter which is capable of passing the Raman emission radiation within at least a portion of the first range of wavelengths along a first optical path;

(d) receiving the emission radiation, directly or indirectly, from the sample at at least one second spectral filter which is capable of passing the photoluminescence emission radiation within at least a portion of the second range of wavelengths along a second optical path;

(e) measuring an amount of the Raman emission radiation using at least one first detector located directly or indirectly along the first optical path;

(f) measuring an amount of the photoluminescence emission radiation using at least one second detector located directly or indirectly along the second optical path; and

(g) correlating information concerning the amounts of the Raman emission radiation and photoluminescence emission radiation measured by the at least one first detector and the at least one second detector, respectively, with data associated with one or more chemical compounds of interest to provide at least a partial chemical analysis of the sample.

2. The method of claim 1 wherein the photoluminescence emission radiation comprises fluorescence emission radiation.

3. The method of claim 1 wherein the photoluminescence emission radiation comprises phosphorescence emission radiation.

4. The method of claim 1 wherein the photoluminescence emission radiation comprises both fluorescence and phosphorescence emission radiation which are each measured by the at least one second detector at difference times.

5. The method of claim 1 wherein the source comprises a source selected from the group consisting of:

(1) a semiconductor source, (2) a an electron beam pumped semiconductor laser;

(3) an electron beam pumped incoherent semiconductor source; and

(4) an electron beam pumped AlGaN source; and

(5) a hollow cathode laser.

6. The method of claim 1 wherein the excitation radiation has wavelength selected from the group consisting of (1) a wavelength less than 300 nm and (2) a wavelength less than about 250 nm.

7. The method of claim 1 wherein at least one of the at least one first spectral filter or at least one second spectral filter comprises a selected filter chosen from the group consisting of (1) a tunable filter;

(2) a dispersive device;

(3) an acousto-optic tunable filter; and

(4) a temperature tunable filter.

8. The method of claim 5 wherein the chemical analysis is performed in conjunction with one or more sample handling or separation methods selected from the group consisting of:

(1) capillary electrophoresis (CE), (2) capillary electrochromatography (CEC), (3) high performance liquid chromatography (HPLC), (4) microcapillary HPLC, (5) flow cytometry, (6) a liquid flow cell methods, (7) an air flow cell methods, and (8) a surface detection method.

9. The method of claim 5 wherein the selected filter comprises an angle tunable filter and the orientation of the angle tunable filter, with respect to received emission radiation, is adjustable so as to enable the Raman emission radiation or the photoluminescence radiation that reaches the at least one first detector or the at least one second detector, respectively, to vary in wavelength.

10. The method of claim 9 wherein the selected filter comprises a tunable filter and wherein the method further comprises repeating the receiving and measuring operations with the at least one tunable filter tuned to different wavelengths so as to obtain a plurality of measurements for a plurality of wavelengths, wherein the correlating comprises determining relative amounts of the measurements for at least two different wavelengths of the plurality of wavelengths and comparing the relative amounts with the data.

11. The method of claim 1 wherein the measuring of the amount of the Raman emission radiation and the measuring of the amount of the photoluminescence emission radiation occur simultaneously.

12. The method of claim 1 wherein the measuring of the amount of the Raman emission radiation and measuring of the amount of the photoluminescence emission radiation occur at different times.

13. The method of claim 1 wherein the measuring of the amount of an emission radiation selected from the group consisting of the Raman emission radiation and the photoluminescence emission radiation is repeated multiple times.

14. The method of claim 13 wherein at least one of the repeated multiple times occurs after irradiation of the sample has ended.

15. A method of providing a chemical analysis of a sample, comprising:

(a) supplying a sample to be analyzed;

(b) applying ultraviolet excitation radiation from a source directly or indirectly onto the sample to produce emission radiation in the form of photoluminescence emission radiation within a first range of wavelengths;

(c) receiving the emission radiation, directly or indirectly, from the sample at at least one first spectral filter which is capable of passing the photoluminescence emission radiation within at least a portion of the first range of wavelengths along a first optical path;

(d) measuring an amount of the photoluminescence emission radiation using at least one first detector located directly or indirectly along the first optical path; and

(e) correlating information concerning the amounts of the photoluminescence emission radiation measured by the at least one first detector with data associated with one or more chemical compounds of interest to provide at least a partial chemical analysis of the sample,

wherein the source comprises a source selected from the group consisting of;

(1) a semiconductor source, (2) a an electron beam pumped semiconductor laser;

(3) an electron beam pumped incoherent semiconductor source; and

(4) an electron beam pumped AlGaN source; and

(5) a hollow cathode laser.

16. The method of claim 15 wherein the photoluminescence emission radiation comprises fluorescence emission radiation.

17. The method of claim 15 wherein the photoluminescence emission radiation comprises phosphorescence emission radiation.

18. The method of claim 15 wherein the photoluminescence emission radiation comprises both fluorescence and phosphorescence emission radiation which are each measured by the at least one first detector at difference times.

19. The method of claim 15 additionally comprising:

(f) receiving photoluminescence emission radiation, directly or indirectly, from the sample at at least one second spectral filter which is capable of passing photoluminescence emission radiation within a second range of wavelengths, which is different from the first range of wavelengths, along a second optical path;

(g) measuring an amount of the photoluminescence emission radiation within the second range of wavelengths using at least one second detector located directly or indirectly along the second optical path;

(h) correlating information concerning the amount of photoluminescence emission radiation within the second range of wavelengths measured by the at least one second detector with data associated with one or more chemical compounds of interest to provide at least partial chemical analysis of the sample.

20. The method of claim 19 wherein the at least portion of the first range of wavelengths corresponds to fluorescence emission radiation and the at least portion of the second range of wavelengths corresponds to phosphorescence emission radiation.

21. The method of claim 15 additionally comprising:

(f) receiving Raman emission radiation, directly or indirectly, from the sample at at least one second spectral filter which is capable of passing Raman emission radiation within a second range of wavelengths, which is different from the first range of wavelengths, along a second optical path;

(g) measuring an amount of the Raman emission radiation within the second range of wavelengths using at least one second detector located directly or indirectly along the second optical path;

(h) correlating information concerning the amount of Raman emission radiation within the second range of wavelengths measured by the at least one second detector with data associated with one or more chemical compounds of interest to provide at least partial chemical analysis of the sample.

22. The method of claim 15 wherein the excitation radiation has wavelength selected from the group consisting of (1) a wavelength less than 300 nm and (2) a wavelength less than about 250 nm.

23. The method of claim 19 wherein at least one of the at least one first spectral filter or at least one second spectral filter comprises a selected filter chosen from the group consisting of (1) a tunable filter;

(2) a dispersive device;

(3) an acousto-optic tunable filter; and

(4) a temperature tunable filter.

24. The method of claim 15 wherein the chemical analysis is performed in conjunction with one or more sample handling or separation methods selected from the group consisting of:

(1) capillary electrophoresis (CE), (2) capillary electrochromatography (CEC), (3) high performance liquid chromatography (HPLC), (4) microcapillary HPLC, (5) flow cytometry, (6) a liquid flow cell methods, (7) an air flow cell methods, and (8) a surface detection method.

25. The method of claim 15 wherein a selected one of the at least one first spectral filter comprises at least one angle tunable filter and the orientation of the at least one angle tunable filter, with respect to received emission radiation, is adjustable so as to enable the photoluminescence emission radiation that reaches the selected one of the at least one first detector to vary in wavelength.

26. The method of claim 25 wherein the method further comprises repeating the receiving and measuring operations with the at least one tunable filter tuned to different wavelengths so as to obtain a plurality of measurements for a plurality of wavelengths, wherein the correlating comprises determining relative amounts of the measurements for at least two different wavelengths of the plurality of wavelengths and comparing the relative amounts with the data.

27. The method of claim 15 wherein the measuring of the amount of photoluminescence emission radiation using the at least one first detector is repeated multiple times after the irradiation of the sample has ended.

28. The method of claim 27 wherein the photoluminescence emission radiation comprises phosphorescence emission radiation and wherein the correlation of information comprises the use of measured phosphorescence emission radiation from a plurality of different times after irradiation of the sample has ended.

29. The method of claim 27 wherein the photoluminescence emission radiation comprises fluorescence emission radiation and wherein the correlation of information comprises the use of measured fluorescence emission radiation from a plurality of different times after irradiation of the sample has ended.