Introduction to Laser Induced Breakdown Spectroscopy (LIBS) for Glass Analysis Module 4 José R. Almirall, Erica Cahoon, Maria Perez, Ben Naes, Emily Schenk and Cleon Barnett Department of Chemistry and Biochemistry International Forensic Research Institute Florida International University, Miami FL USA Outline LIBS theory and background LIBS setup and practice Glass as a model analysis matrix Comparison of LIBS to other elemental analysis methods in forensic science LIBS data analysis LIBS Background LIBS Developments First reported by Maker, Terhune and Savage in 1963 A focused laser pulse interacts with a target material to generate a practically totally ionized gas (plasma). The plasma then excites the substrate s atoms and ions. A characteristic emission is detected. The emission spectrum is spectrally resolved to provide qualitative and (semi) quantitative analysis of the material. Direct sampling of gases, liquids and solids to determine elemental composition. Number of publications over the last 40 years (but still less mature than ICP and XRF as an analytical method) Source: M. Sabsabi from Cremers and Radziemsk, 2006 Atomic Emission Spectroscopy LIBS Overview Ability to detect all elements Simultaneous multi-element detection Fast and easy to operate No sample preparation Almost non-destructive Good sensitivity for a wide range of elements (down to 5 ppm) Capability of field and stand-off analyses Remote sensing Potential hazardous materials at long distance(80m) Aerosol identification Quality control Pharmaceutical Steel and alloy company Non destructive analysis on materials Art pieces Precious gems Biological and environmental safety Discrimination of bacterial species Environmental pollution in fish, plant, and paint
Plasma as an Excitation Source Non-radiative process * Not on same scale LIBS Laser Plasma: ICP Plasma: ~ mm in length ~ cm in length created with ns laser pulse sustained and controlled with gas flow ~ microseconds lifetime n e ~ 1 x 10 15 /cm 3 n e ~ 1 x 10 16 /cm 3 Temperature ~ 8000 0 K Temperature ~ 10000 0 K Jablonski diagram Fluorescence: S 1 S 0 Vibrational relaxation Three Non-radiative Processes 1. Internal conversion 2. Intersystem crossing Source of photo: Cremers and Radziemski 2006 Phosphorescence: T 1 S 0 3. Vibrational relaxation 8 2. www.shsu.edu/.../ JABLONSKI.html ATOMIC SPECTRA EMISSION LINES HIGH SELECTIVITY GAS PHASE ATOMS, NO VIBRATIONS & ROTATIONS SHARP LINES (~ 5 pm WIDE) M + * (II) LINES, +1 ION M + + e - M* M E i STATE j (I) LINES, NEUTRAL ATOM *Intensity of line from level j population of level j e -Ej/kT Laser-sample interaction time scale Plasma temporal analysis 100 fs laser nanosecond laser Russo, et al, Anal. Chem. 2001, 74, 70A-77A Source: Cremers and Radziemski 2006
Plasma creation Plasma Evolution Laser Pulse hot, high-pressure Strongly absorbing Plasma Shock Wave Radiation sample 14 Experimental Setup Continuum MiniLite Nd:YAGs Two lasers (PIV) system 2 nd harmonic 532nm 22 mj max energy per pulse 0.67 Hz Rep Rate New Wave Tempest 4th harmonic 266 nm 27 mj max energy per pulse 0.67 Hz Rep Rate Focal length = 150 mm Varying focus positions wrt sample surface Delay between laser pulses varied from 0.0-10.0 µs. Spectrometer Mechelle 200-900nm Resolving power 5000 Detector Andor iccd Camera FIU Setup Advantages of LIBS Qualitative and (semi) quantitative? analysis Almost non-destructive direct solid sampling Minimal (or no) sample preparation Speed, versatility, ease of operation and portability Good detection limits (~ 5 ppm - 50 ppm) Good discrimination power??? Affordability in comparison to LA-ICPMS Challenges of LIBS Calibration for quantitative analysis Matrix effects
Some Analytical Applications of LIBS Plano-convex lenses: pos. focal length (75mm), collimates and focuses beam Trace metal detection (1999) Trace metal accumulation in teeth (1999) Glass composition (2000) Detecting gunshot residue (2002) Microanalysis of tool steel (2003) Detection of gunshot residues on the hands of a shooter (2003) Analysis of energetic materials (2003) Hair tissue mineral analysis (2003) Detection of trace elements in liquids (2003) UV 45º Fused Silica Mirrors, damage threshold, angle of incidence IR Plano-concave lens: neg. focal length 1 (-50), diverges beam Plano-convex lens: pos. focal length 2 (100), Collimates Beam D f1-f2 = F 1 +F 2 =-50+150=100 mm apart Fiber optic cable leading to Mechelle 5000 spectrometer, 200-950 nm Plano-convex lens: pos. focal length 2 (150mm), focuses collimated light Commercial LIBS Systems Avantes Ocean Opics Foster and Freeman PhotonMachines NewWave Research Avantes Spectrometer NIST 614 (~ 2 ppm)
NIST Standard Reference Materials 610 = 515 ppm Sr 1831 = 112 ppm Sr NIST 1831 Float Glass Standard 1064 nm 10 laser shots 220-950 nm spectral range Resolution ~ 5000 over range Sr (II) 407.77 NIST 610 Glass Standard 1064 nm 10 laser shots [Sr] 515.5 ppm (~ 0.05%) Sr (II) 407.77 NIST 610 Glass Standard 266 nm 10 laser shots [Sr] 515.5 ppm (~ 0.05%) Sr (II) 407.77 NIST 1831 Float Glass Standard 1064 nm 10 laser shots [Sr] 89.1 ppm
Sr (II) 407.77 NIST 1831 Float Glass Standard 266 nm 10 laser shots [Sr] 89.1 ppm Sr (II) 407.77 NIST 621 Container Glass Standard 266 nm 10 laser shots [Sr] 106 ppm XRF spectra and figures of merit Rh x-ray tube 40 kev beam potential 300 micron diameter monocapillary focusing collimator Li drifted silicone EDS with beryllium window beam current adjusted to achieve a 35% dead time factor (approximately 760 microamps) 17 microsecond time constant resolution approximately 156 ev LIBS spectra (NIST Glass) Courtesy of Scott Ryland, FDLE, Orlando, FL LIBS spectra dual pulse single pulse dual pulse single pulse LIBS & LA-ICP-MS (strontium) Comparison of Means dual pulse single pulse inten./conc. 350000 300000 250000 200000 150000 100000 50000 0 LIBS (single) LIBS (dual) LA-ICP-MS (1000x) 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 sample #
Double pulsed LIBS: UV followed by IR reheating Double Pulse enhancement for NIST 614 Glass 30 ppm certified value for K [Sr] in NIST Glasses LIBS & LA-ICP-MS (strontium) SP 1064nm Correlation of LA-ICPMS and XRF 60000 XRF Intensity vs LA-ICP-MS ( XRF data from Ryland) 20 50000 18 40000 y = 319.66x - 1088.5 R 2 = 0.9206 16 14 R 2 = 0.9911 30000 1064nm SP Linear (1064nm SP) 12 10 20000 8 6 10000 4 2 0 0 20 40 60 80 100 120 140 concentration (ppm) 0 0 20 40 60 80 100 120 140 [Sr] LA-ICP-MS Results (ppm) LA-ICP-MS, XRF and LIBS 210 ways to compare 6 element ratios between pairs 150 combinations (of the possible 210) produced no Type I or Type II errors B. Naes, S. Umpierrez, S. Ryland, C. Barnett and JR Almirall;, Spectro. Acta Part B: Atomic Spectroscopy, 2008.
325 s delay 400 s delay 117.1 pl volume, 60.7 µm diameter per drop Using a 1000 ppm Sr solution 1 drop contains ~ 117pL and 117 pg of Sr 43 44 Target for deposition/ablation 325 s delay 50 m diameter nozzle 104.5 pl volume, 58.5 µm drop diameter ( 1%) Using a 500 ppm Sr solution, 1 drop contains ~ 52.3 pg of Sr Jetlab IV by MicroFab Technologies, TX 45 ~250 m diameter, ~12 m deep 46 Deposition of ~ 117 pg of Sr on an Al surface Signal accumulation over 20 laser shots Sr II 407.7 nm S/N ~ 70 for ~ 100 pg deposited LoD ~ 4.3 pg Sr 47 48
Deposition of 1, 2, 4, 6, 8 and 12 drops of 500 ppm [Sr] on Al Microdrop printing of standards 49 50 215 m spot size (20 shot accumulation) 26 ng 0ng 51 Future of LIBS LIBS Components Move towards standardization of the technique Combined techniques- (Raman/LIBS, LIBS/Mirowave) Micro-LIBS - spatial mapping of elemental composition (3-10 m diameter craters) Portable LIBS Laser Fluence : Energy/Area (J/cm 2 ) F 1 > F 2 > F 3 Laser : (Nd:YAG -1064nm, 532nm, 355nm, 266nm) Damage threshold of optics (mirrors & lens) Mirror (polarization, angle of incidence,coatings) Antireflection Coatings (AR coatings on lens) Optical Transmission of materials BK7: 350-2100nm UV-Fused Silica: 170nm-2100nm