Laser induced breakdown spectroscopy (LIBS) apparatus based on high repetition rate pulsed laser

• US 9,909,923 B2
• Filed: 09/04/2015
• Issued: 03/06/2018
• Est. Priority Date: 09/05/2014
• Status: Expired due to Fees

• Current Assignee: Metrohm Spectro Incorporated
• Original Assignee: BWT Property, Inc.
• Inventors: Wang, Sean Xiaolu, Li, Qun
• Primary Examiner(s): Geisel, Kara E
• Assistant Examiner(s): Bologna, Dominic J
• Application Number:
  US14/845,980
• Publication Number:
  US 20160069745A1
• Time in Patent Office: 914 Days
• CPC Class Codes: G01J 3/0208 using focussing or collimating elements, e.g. lenses or mirrors; performing aberration correction
• CPC Class Codes: G01J 3/06 Scanning arrangements arrangements for order-selection
• CPC Class Codes: G01J 3/10 Arrangements of light sources specially adapted for spectrometry or colorimetry
• CPC Class Codes: G01J 3/28 Investigating the spectrum using colour filters G01J3/51
• CPC Class Codes: G01J 3/443 Emission spectrometry

Abstract

This invention discloses a laser induced breakdown spectroscopy (LIBS) apparatus based on a high repetition rate pulsed laser. The laser produces a train of laser pulses at a high repetition rate in the kHz or even higher range. When the laser beam hits the sample, it generates several thousands of micro-plasmas per second. Synchronized miniature CCD array optical spectrometer modules collect the LIBS signal from these micro-plasmas. By adjusting the integration time of the spectrometer to cover a plurality of periods of the laser pulse train, the spectrometer integrates the LIBS signal produced by this plurality of laser pulses. Hence the intensity of the obtained LIBS spectrum can be greatly improved to increase the signal-to-noise ratio (SNR) and lower the limit of detection (LOD). In addition, the influence of pulse to pulse variation of the laser is minimized since the obtained LIBS spectrum is the spectrum of a plurality of micro-plasmas produced by a plurality of laser pulses. The high repetition rate laser also makes it possible for fast scanning the laser beam over the sample surface such that an average spectrum of the sample is collected to overcome the sample non-uniformity issue or for performing spectral imaging of the sample by correlating the obtained LIBS spectrum with the position of the scanning laser beam.

Claims

1. A laser induced breakdown spectroscopy (LIBS) apparatus for measuring the LIBS spectrum of a subject, the LIBS apparatus comprising:

a high repetition rate pulsed laser light source configured to produce a laser beam in the form of a plurality of laser pluses at a high repetition rate;

an optical focusing element configured to focus the laser beam onto a surface of the subject;

a vibration device configured to vibrate the optical focusing element to scan the laser beam over an area on the surface of the subject, wherein the laser beam produces a plurality of plasma emissions from a plurality of measurement points on the surface of the subject; and

an optical spectrometer device configured to measure an optical spectrum of the plurality of plasma emissions to obtain a LIBS spectrum;

wherein the vibration device vibrates the optical focusing element in a direction perpendicular to the surface of the subject.

2. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the optical spectrometer device is set to an integration time which covers a plurality of periods of the high repetition rate laser pulses.

3. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the repetition rate of the laser pulse is greater than 100 Hz.

4. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the repetition rate of the laser pulse is greater than 1000 Hz.

5. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the laser pulses have a pulse width of less than 10 nanoseconds (ns).

6. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the laser pulses have a pulse width of less than 1 nanosecond (ns).

7. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the pulsed laser light source is a Q-switched laser.

8. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the pulsed laser light source is a mode locked laser.

9. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the pulsed laser light source is a passively Q-switched diode pumped solid state (DPSS) laser.

10. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the optical focusing element comprises an optical lens.

11. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the optical focusing element comprises an optical mirror.

12. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the optical focusing element comprises a Bessel beam generator.

13. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the vibration device vibrates the optical focusing element in a direction parallel with the surface of the subject.

14. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the vibration device produces a 1-dimentional (1-D) vibration pattern.

15. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the vibration device produces a 2-dimentional (2-D) vibration pattern.

16. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the vibration device produces a 3-dimentional (3-D) vibration pattern.

17. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, wherein the vibration device produces a random vibration pattern.

18. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, further comprising a camera device configured to monitor and record a position of the laser beam on the surface of the subject.

19. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 1, further comprising a forced air flow generator configured to produce a forced air flow between the optical focusing element and the surface of the subject.

20. The laser induced breakdown spectroscopy (LIBS) apparatus of claim 19, further comprising an insert gas supplier for supplying inert gas to the forced air flow generator.

21. A laser induced breakdown spectroscopy (LIBS) apparatus for measuring the LIBS spectrum of a subject, the LIBS apparatus comprising:

a high repetition rate pulsed laser light source configured to produce a laser beam in the form of a plurality of laser pluses at a high repetition rate;

an optical focusing element configured to focus the laser beam onto a surface of the subject;

a vibration device configured to vibrate the optical focusing element to scan the laser beam over an area on the surface of the subject, wherein the laser beam produces a plurality of plasma emissions from a plurality of measurement points on the surface of the subject;

an optical spectrometer device configured to measure the plurality of plasma emissions to obtain a plurality of LIBS spectra; and

a processor unit configured to perform a predefined sorting or mathematical post-processing of the plurality of LIBS spectra to obtain optimum LIBS spectra of the subject;

wherein the processor unit provides feedback control to the vibration device based on a quality of the plurality of LIBS spectra.