1. EMISSION SPECTROSCOPIC STUDIES OF LASER-INDUCED GRAPHITE PLASMAS László Nemes Research Laboratory for Materials and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Pusztaszeri út 59-67, Budapest, Hungary e-mail address: nemesl@chemres.hu

2. The LIBS lab at RLMEC/ HAS

3. TEA CO 2 laser TEA CO 2 laser

4. EXPERIMENTAL A home-built TEA CO 2 laser and a miniature YAG laser were used for plasma generation from spectroscopically pure graphite targets. The CO 2 laser provided 2 microsec long individual pulses at energies around 15- 20 J, while the YAG laser pulses at 1064 nm had energy around 30 mJ and duration 10 ns. The YAG laser could be operated with pulse sequences (separation about 10 microsec). The focussed laser power was around 0.5-2 GW/cm 2 and 200 MW/cm 2 for the CO 2 and YAG lasers, resp. Single pulse spectral events were captured by OceanOptics PC1000 and PC2000 fiber-optic spectrometers for which home-made trigger units provided synchronization with the lasers. Spectral accumulation was started before the laser pulses, all LIBS spectra shown were taken with time integration for durations 8 and 50 ms, for the PC1000 and PC2000, resp. Spectral resolution for the PC2000 spectrometer was 1.5 nm. Relative irradiance spectra were obtained using a calibrated spectral lamp

5. SHORT SUMMARY Pulsed CO 2 and YAG lasers were used to create plasma breakdown spectra (LIBS) from a room temperature graphite target in the range 350-900 nm with a resolution of 15 A. Emission was captured from single pulses by a small, fiber-optic CCD spectrometer in a time-integrated fashion. Spectra were taken in vacuo, and in helium and carbon dioxide atmospheres. LIBS spectra are dominated by the Swan bands of C 2 as well as atomic lines due to neutral and ionised C and He. In addition a broad continuum due partially to small carbon particles is observed. The LIBS show dependence on the position of observation. Plasma temperature was inferred by spectral simulation of the Swan bands and was found in the range 5200-10000 K. At the expected location of the cometary band of C 3 (near 403 nm) overlapping (atomic) features were observed. Some considerations on the observability of this band in laser plasmas are given.

7. Swan bands in LIBS in vacuum

8. Swan bands in LIBS in vacuum 2

9. Swan bands in LIBS at ambient pressure of CO 2 p=100 mmHg

10. Swan bands in LIBS at CO 2 pressure 630 mmHg

11. Effect of distance from target in He, p = 100 mmHg

12. Effect of ablated particles from C 60 on the background continuum

13. Graphite plasmas induced by a TEA CO 2 laser

14. Graphite plasma induced by a TEA CO 2 laser

15. Background in CO 2 laser induced LIBS in vacuo

16. The LIBS cell for room temperature graphite target

17. YAG laser induced graphite plasmas

18. The mini-YAG laser LIBS setup

19. On the observability of the 403 nm C 3 band in LIBS In high temperature carbon vapour sources the band is clearly seen using LIF (ref.1). In laser-induced carbon LIBS, using a room temp. graphite target and a pulsed YAG laser the band is observed as a broad continuum (ref.2). In carbon nanotube growing by laser ablation using a hot graphite furnace the same broad continuum is observed with one or two YAG lasers applied (ref.3). ref.1.: D.M. Mann, J. Appl.Phys. 49 (1978) 3485-3489 ref.2.: P. Monchicourt, Phys. Rev. Lett., 66 (1991) 1430-1433 ref. 3.: S. Arepalli, C.D. Scott: Chem.Phys. Lett., 302 (1999) 139-145

20. The C 3 403 nm band in comet spectra

21. The Hyakutake comet spectrum

22. Possibility of seeing the C 3 cometary band (?)

23. CONCLUSIONS LIB spectra from room temperature graphite targets in vacuum, He and CO 2 gases are characterized by C 2 Swan bands, and atomic lines from C and He. The background continuum underlying the Swan bands is at least partially due to small carbon particles. LIB spectra are sensitive to the location of observation, atomic lines appear closer to the target. The temperature obtained by spectral fitting to C 2 Swan transitions is between 5000 and 10000 K, closer to the target the temperature is significantly higher. Plasmas obtained by a TEA CO 2 laser (vs. YAG) contain highly ionised carbon and stronger continuum background. In time integrated spectra, due to the presence of atomic lines near 400 nm, the cometary C 3 band could not be identified

24. Developments under way EXPERIMENTAL: Use of a Quantel Brilliant YAG laser at 1064, 532 and 355 nm. Use of a new miniature CCD spectrometer with 3 A resolution in the 350-650 nm range and NIST traceable intensity. Determination of plasma lifetimes by a fast Si detector. Construction of a laser-oven for hot graphite targets. THEORETICAL: Development of a plasma kinetic / chemical kinetic model for electron, atomic and molecular kinetics in LIBS spectra, with special emphasis for C 2 and C 3

25. ACKNOWLEDGEMENT Support for the present work was provided by the Hungarian Research Fund (OTKA) under contract number # T032549, travel funds from the Hungarian Ministry of Education were applied for. We also acknowledge the help provided by Dr. James O. Hornkohl, University of Tennessee Space Institute, U.S.A., in Swan band spectral simulations for for temperature determination.