Laser-Induced Breakdown Spectroscopy
(LIBS)


Content
•Introduction to fundamentals of LIBS
•Basic instrumentation and configurations
•Double pulse LIBS (instrumentation)
•
•Depth profiling (zinc coated steel, ceramic tiles)
•Elemental mapping (teeth, plants, urinary stones ...)
2

•LIBS techniques for powder materials (pressed pellets)
•LIBS techniques for liquid samples (algae suspension)
•LIBS technique for nanoparticles (QDs)
•Remote analysis by LIBS (identification of biominerals)
•Conclusion
•
Content
3

laser beam
Laser beam - solid sample interaction
deposit
crater
solid sample
crumbling
shock
wave
heating, melting,
vaporization, explosion
absorption of radiance
in plasma
vaporization
atomization
excitation
ionization
atoms, ions,
particles, aerosol
LIBS
aerosol
ICP-OES
 ICP-MS
microplasma
    hν
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Laser beam - solid sample interaction
Plasma ignition:  ns laser (107 – 1011 W/cm2 )
    fs laser (1012 – 1017 W/cm2 )
Thermal vaporization (10-9 – 10-8 s)
Non-thermal ablation (10-9 – 10-8 s)
Plasma shielding (10-9 – 10-8 s)
Plasma expansion and cooling:
Shockwave propagation
Plasma expansion (10-11 – 10-6 s)
Plasma radiation cooling (10-6 – 10-4 s)
Particle ejection and condensation:
Ejection of liquid droplet (10-8 – 10-6 s)
Solid exfoliation (10-8 – 10-6 s)
Nano particles formation (10-4 – 10-3 s)
Laser-Induced Breakdown Spectroscopy Jagdish P. Singh & Surya N. Thakur
© 2007 Elsevier
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Laser-Induced Breakdown Spectroscopy (LIBS), Fundamentals and Applications Andrzej W. Miziolek,
Vincenzo Palleschi, Israel Schechter © 2006  Cambridge
Important time periods after plasma formation
td  - delay time, tb – gate pulse width
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Handbook of Laser-Induced Breakdown Spectroscopy D. Cremers and L. Radziemski
© 2006 John Wiley & Sons, Ltd
LIBS - lasers
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LIBS2
x
y
z
Laser
Spectrometer
PC
Sample (x,y,z stage)
Basic configurations
ICCD
1. Experimental setup with pierced mirror
Triggering
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INSTRMalagy
Laser
Sample
Dichroic mirror
Basic configurations
Spectrometer
 University of Malaga 2006
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LIBS
Sample
Optical fiber
Laser
Spectrometer
Collecting optics
PC
Basic configurations
2. Experimental setup with optical fiber
ICCD
Triggering
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DSCN1873
Basic configurations
 University of Jyvaskyla 2007
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LIBS3
Sample
Spectrometer
Laser
Adapter
Probe
Basic configurations
3. Experimental setup with optical fiber
(portable LIBS, underwater measurements)
Optical fiber
ICCD
PC
Triggering
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Basic configurations
3. Experimental setup with telescope
(Stand-off measurements)
Spectrometer
ICCD
Triggering
PC
Laser
Telescope
Sample
H:\skola\prezentace\kurz ablace 12\1.jpg
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komora
Nd:YAG   Brilliant
10 Hz   5 ns
triax
Control unit
(laboratory made)
PMT Hamamatsu R928
Gated  Socket Assembly
Hamamatsu C1392
Jobin Yvon – Triax 320
osciloskop
Triggering – Q switch
Triggering oscilloscope
OSCILLOSCOPE
Tektronix TDS 1012
DELAY TIME
sample
MU setup - 1st generation
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C:\Codl\Download\libs\P3050019.JPG C:\Codl\Download\libs\P3050018.JPG
x,y stage   OWIS
Nd:YAG  Brilliant (Quantel)
glass lens
optical fiber
Monochromator TRIAX 320 (Czerny – Turner 320 mm)
PMT Hamamatsu R928
Control of the PMT by Q – switch pulse
Oscilloscope TDS 1012
MU setup - 1st generation
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komora
Nd:YAG   Brilliant
10 Hz   5 ns
triax
Jobin Yvon – Triax 320
Flashlamp control
sample
ICCD Jobin Yvon Horiba
Q – switch control
MU setup - 2nd generation
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monochromator Hlavice komora
Nd:YAG   Brilliant
10 Hz   5 ns
Ar, He
sample
LA-ICP-OES
ICP-OES Jobin Yvon – 170 Ultrace
polychromator
POLYCHROMATOR
MONOCHROMATOR
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Double pulse technique (DP-LIBS)
C:\DATA\Codl\Codl\Prijate clanky\Ces Cas Fyz\Obr5\IMG_0021.jpg C:\DATA\Codl\Codl\Prijate clanky\Ces
Cas Fyz\Obr5\IMG_0031.jpg
Novotny, K.; Lutzky, F.; Galiova, M.; Kaiser, J.; Malina, R.; Kanicky, V.; Otruba, V., Double pulse
laser ablation and plasma: time resolved spectral measurements.
Chemicke Listy 2008, 102, S1399-S1402.
Single Pulse
Double Pulse
Emission enhancement
•plasma volume increasing
•higher temperature
•longer decay time
•S/N enhancement
Decreasing of LOD up to two orders of magnitude
MU setup - 3rd generation
New Wave, UP 266 MACRO
Nd:YAG laser @ 266 nm (4-th harmonic frequency)
Second laser pulse Nd:YAG (Quantel Brilliant) @1064 nm
Comparison of the single and double-pulse signals in spectral
region of selected iron lines
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SIMULTANEOUS DP-LIBS AND LASER ABLATION ICP-OES SYSTEM
designed by utilizing a modified commercially available laser ablation system (New Wave, UP 266
MACRO)
C:\Users\novotny\Desktop\nova komora\Clanek\Odeslana verze\Fig4.jpg
For LA-ICP-OES experiments the original ablation chamber was replaced with a special laboratory
made chamber
•window for entering the second orthogonal laser pulse
•window for collection of LIP emission
•stage for sample height alignment
•no modification of the original optics - possible to use all advantages of the original
arrangement
•spot ablation for depth profiling, line scanning for lateral analysis and raster scanning for bulk
or surface analysis.
•second re-heating laser pulse (Quantel Brilliant) is delivered orthogonally
        (periscope arrangement allowing precise laser beam positioning)
•two digital delay generators DG 645
•collection optics for emission transport to the monochromator Triax 320 (Jobin-Yvon)
•ICCD Princeton Instruments PI MAX-3
•sample holders
(different size and shape)
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MU setup - 3rd generation

C:\Users\novotny\Desktop\nova komora\Clanek\Odeslana verze\Fig1.jpg
ALATION CHAMBER FOR SIMULTANEOUS
DP-LIBS AND LA- ICP-OES/MS
C:\Users\novotny\Desktop\zprava CzUS\Za rok 2010\Fotky\A.jpg C:\Users\novotny\Desktop\zprava
CzUS\Za rok 2010\Fotky\B.jpg
Construction in cooperation with Institute of Physical Engineering
BUT Brno (prof. J. Kaiser)
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Instrumentation - Summary
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Depth profiling
depth
16 %
84 %
Δz
x
A
B
layer A
layer B
kraterns kraterfs
ns - laser
fs - laser
K. Niemax, Laser ablation – reflection on a very complex technique for solid sampling, Fresenius J.
Anal. Chem. (2001) 370:332-340)
Δz – depth resolution
defined by convention: depth range over which the signal changes from 84 to 16% of its full value
Δz = Δp AAR
Δp – number of laser shots needed to reach 84 and 16% of signal
AAR – averaged ablation rate
Depth profiling by LIBS
•from nanometer to millimeter scale
•no or minimal sample preparation
•without restrictions on the shape, size or conductivity
•under atmospheric conditions
•on-line and in situ measurement
•
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(zinc-coated iron sheets)
Depth profiling
Novotny, K.; Vaculovic, T.; Galiova, M.; Otruba, V.; Kanicky, V.; Kaiser, J.; Liska, M.; Samek, O.;
Malina, R.; Palenikova, K., The use of zinc and iron emission lines in the depth profile analysis
of zinc-coated steel. Applied Surface Science 2007, 253, 3834-3842.
Different manufactures and different zinc-coating thicknesses:
previously analyzed by glow discharge optical emission spectrometry
Hoesch Stahl (20 µm)
electroplated Zn coating, Sollac (10 µm)
Aluzink, SSAB (24 µm)
Galfan, Voest Alpine (6 µm)
Galvanneal, British Steel (9 µm)
Optimized parameters
•laser pulse energy
•focusing condition
•different surrounding gases
•delay time
air
Ar
He
Depth profile of electroplated Zn in helium focusing at -20 mm. Comparison of LIBS signals of Zn(I)
280.08 nm and Fe(I) 344.06 nm at 5 and 10 ms delay times. Ablation was performed with an energy of
100 mJ/pulse.
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Depth profiling
Hrdlicka, A.; Zaoralkova, L.; Galiova, M.; Ctvrtnickova, T.; Kanicky, V.; Otruba, V.; Novotny, K.;
Krasensky, P.; Kaiser, J.; Malina, R.; Palenikova, K., Correlation of acoustic and optical emission
signals produced at 1064 and 532 nm laser-induced breakdown spectroscopy (LIBS) of glazed wall
tiles. Spectrochimica Acta Part B-Atomic Spectroscopy 2009, 64, 74-78.
Model sample of glazed silicate ceramics
•well-defined average contents of constituents
•reproducible production series
(ceramic tiles)
decrease in the optical emission
during ablation was successfully compensated by normalization to the acoustic signal
Depth profile of the green tile acquired for Al(I) 309.271 nm, Cr(I) 295.368 nm and Ti(II( 334.904
nm.
http://www.ahhuateng.com/wp-content/uploads/2013/04/Installing-Ceramic-Tile.jpg DSCN0209 IMG_0008
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Ti
Zn
Cr
Normalized intensity
Position on the sample
Position on the sample
Mapping and depth profiling
(ceramic tiles)
Ti(II) 334.9 nm
Cr(II) 336.8 nm
Zn(I) 330.29nm
Zn
Cr
Ti
ORANGE4
Zn
Ti
ablation craters
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Mapping of elemental distribution
(plant samples)
Cleaning of metal contaminated soil  - PHYTOREMEDIATION
resistant, strong tolerance, effective plant-transport mechanisms, high accumulation,
high biomass, fast growth
herbs: Zea mays, Helianthus annuus ...
trees: Betula pendula, Populus tremula ...
Samples from naturally growing trees
recultivated sludge bed in locality Smolník (Slovakia)
Laboratory cultivated plants
Department of Chemistry and Biochemistry, Mendel University in Brno
mapa1
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Mapping of elemental distribution
(plant samples)
Copper distribution in the needle of pine tree (Pinus sylvestris) obtained by LIBS single pulse.
Copper distribution in central vein of the aspen leaf (Populus tremula) obtained by LIBS single
pulse; two laser pulses on each point.
Smolník
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Mapping of elemental distribution
(plant samples)
Example of copper and calcium distribution maps on cross sections of spruce twigs (Picea abies)
cultivated in 50 mmol.l-1 CuCl2 obtained by LIBS double pulse.
Point distance = 150 µm
Krajcarova, L.; Novotny, K.; Babula, P.; Provaznik, I.; Kucerova, P.; Adam, V.; Martin, M.Z.;
Kizek, R.; Kaiser, J., Copper Transport and Accumulation in Spruce Stems (Picea abies (L.) Karsten)
Revealed by Laser-Induced Breakdown Spectroscopy. International Journal of Electrochemical
Science,2013, 8, 4485-4504.
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Mapping of elemental distribution
(plant samples)
Galiova, M.; Kaiser, J.; Novotny, K.; Hartl, M.; Kizek, R.; Babula, P., Utilization of
Laser-Assisted Analytical Methods for Monitoring of Lead and Nutrition Elements Distribution in
Fresh and Dried Capsicum annuum L. Leaves. Microscopy Research and Technique 2011, 74, 845-852.
(a) Set of C. annuum L. samples used for monitoring of effects of lead(II) ions. (b) Example of the
investigated C. annuum L. leaves.
The maps of K obtained from the studied area of the 2 days 10 mmol L-1 Pb(NO3)2 treated C. annuum
L. leaf. The K distribution in fresh (frozen) and dried samples measured by (a) LIBS and (b)
LA-ICP-MS.
The maps of Pb obtained from the studied area of the 2 days 10 mmol L-1 Pb(NO3)2 treated C. annuum
L. leaf. The K distribution in fresh (frozen) and dried leaf measured by (a) LIBS and (b)
LA-ICP-MS.
Mapping of accumulation and distribution of heavy metal (lead)
and nutrition elements (potassium) in leaves of
Capsicum annuum L. samples.
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Elemental mapping
(geological sample)
Novotny, K.; Kaiser, J.; Galiova, M.; Konecna, V.; Novotny, J.; Malina, R.; Liska, M.; Kanicky, V.;
Otruba, V., Mapping of different structures on large area of granite sample using laser-ablation
based analytical techniques, an exploratory study. Spectrochimica Acta Part B-Atomic Spectroscopy
2008, 63, 1139-1144.
Comparison study:
multi-element (Ca, Al, Fe, Mn) mappings of a granite sample surface
performed by LIBS and subsequently by LA-ICP-MS analysis
Typical LA-ICP-MS signal for Fe monitoring obtained for ~40 ablation craters.
Set of normalised spectrums obtained by six subsequent pulses from the different places of the
sample.
The 2 x 2 cm2 area of the granite was sampled with a spatial resolution of 200 mm (the distance of
the LIBS and LA-ICP-MS craters).
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Elemental mapping
(geological sample)
100×100 individual sample points to map an area of 20×20 mm2
LIBS
LIBS
LA-ICP-MS
LA-ICP-MS
Novotny, K.; Kaiser, J.; Galiova, M.; Konecna, V.; Novotny, J.; Malina, R.; Liska, M.; Kanicky, V.;
Otruba, V., Mapping of different structures on large area of granite sample using laser-ablation
based analytical techniques, an exploratory study. Spectrochimica Acta Part B-Atomic Spectroscopy
2008, 63, 1139-1144.
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Elemental mapping
(teeth)
strolling_reindeer DSCN1638
Upper palaeolithic reindeer tooth
locality at Moravany-Lopata, Western Slovakia
bear_01.tif 126.jpg Koren_LIBS.tif
Fossil brown bear (Ursus arctos) was excavated at Dolní Věstonice II-Western Slope, South Moravia,
Czech Republic.
Protemnodon - an extinct species of a kangaroo that lived about 50 000 years ago, found in
Australian swamps
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Elemental mapping
(teeth)
ETHOLOGY OF THE STUDIED FOSSIL BROWN BEAR
The seasonal fluctuations of the Sr/Ca and Sr/Ba detected by DP LIBS evidenced the migration of
this bear between his hibernaculum’s location and the place where the fossils were found.
barevna skala.tif pomerMg_koren_rada.TIF
The estimation of the sample hardness via magnesium ionic to atomic line intensity. The estimated
hardness characteristic was proved by microhardness measurements.
Sr/Ca and Sr/Ba ratios derived from LIBS line scan and LA-ICP-MS mapping; dotted lines represent
the different regions (white, summer bands; brown, winter bands) of the tooth cross section. The
bar has a length of 500 μm.
Galiova, M.; Kaiser, J.; Fortes, F. J.; Novotny, K.; Malina, R.; Prokes, L.; Hrdlicka, A.;
Vaculovic, T.; Fisakova, M. N.; Svoboda, J.; Kanicky, V.; Laserna, J. J., Multielemental analysis
of prehistoric animal teeth by laser-induced breakdown spectroscopy and laser ablation inductively
coupled plasma mass spectrometry. Applied Optics 2010, 49, C191-C199.
Sr_Ca_koren_DP.tif Sr_Ba_koren_DP.tif
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Elemental mapping
(fossil snake vertebrae)
Galiova, M.; Kaiser, J.; Novotny, K.; Ivanov, M.; Fisakova, M. N.; Mancini, L.; Tromba, G.;
Vaculovic, T.; Liska, M.; Kanicky, V., Investigation of the osteitis deformans phases in snake
vertebrae by double-pulse laser-induced breakdown spectroscopy. Analytical and Bioanalytical
Chemistry 2010, 398, 1095-1107.
Elemental mapping of pathological bony tissue (osteitis deformans phases in fossil vertebrae)
SR-μCT slices of a healthy and b pathological fossil snake vertebra together with c the 3D
rendering of the investigated fossil snake vertebra segment
The photographs of the studied a fossil (N. natrix) snake vertebrae.
The investigated healthy (the left images) and pathological (the right images) bones are shown.
Lower Ca/P ratio indicating the later stage of the osteitis deformans.
Na content can be caused by metabolic derangement (“acidosis”).
The fossil material:
Natrix natrix
Mladeč Caves excavation II
(Czech Republic),
Early Pleistocene
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Elemental mapping
(urinary stones)
Mineralized tissues and bio-mineral structures are “archives” related to living habits, nutrition
and exposure
to changing environmental conditions.
Line scans of the urinary concrement cross-sections may provide information about the accumulation
history of the elements of interest.
Four categories of urinary stones: a) oxalates b) phosphates c) uric acid and d) cystine.
Correlation between calcium and phosphorus indicates the presence of apatite.
Distribution of iron is connected with accumulation of blood clot during the growth of urinary
stones in the urinary bladder.
Sample no. 10806: oval, ellipsoidal, pale yellow-brown zone.
The main components:
uric acid (90%)
 weddellite CaC2O4·2 H2O (10%)
Ca distribution
5 mm
5 mm
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Powder samples
C:\DATA\Marketa\WC\Obrázky\P1010016a.JPG
Novotny, K.; Stankova, A.; Haekkaenen, H.; Korppi-Tommola, J.; Otruba, V.; Kanicky, V., Analysis of
powdered tungsten carbide hard-metal precursors and cemented compact tungsten carbides using
laser-induced breakdown spectroscopy. Spectrochimica Acta Part B-Atomic Spectroscopy 2007, 62,
1567-1574.
powdered tungsten carbide hard-metal precursors (WC/Co)
Samples: Pramet Tools, Šumperk, Czech Republic
The elemental composition of powders samples:


preparation of pressed pellets with or without binder  (binder powdered silver)
element
content
% (m/m)
W
57–88
C
4.8–7.5
Co
3–10
Ti
0.04–9.6
Ta
0.1–8.2
Nb
0.05–3.4
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calibration pellets (urinary stones)
Stepankova, K.; Novotny, K.; Vasinova Galiova, M.; Kanicky, V.; Kaiser, J.; Hahn, D.W., Laser
ablation methods for analysis of urinary calculi: Comparison study based on calibration pellets.
Spectrochimica Acta Part B-Atomic Spectroscopy, 2013, 81, 43-49.
Powder samples
Mineralogical composition of calibration pellets
Comparison of
LIBS and LA LIBS
Laser ablation LIBS (LA-LIBS)
(analytical LIBS plasma is completely separated from LA)
Problems with elements present in high content are related mainly to the LIBS technique and most
probably they are connected to the processes in the LIP and self-absorption.
Comparison of LIBS and LA-LIBS calibration curves for Sr in phosphate matrix pellets.
Comparison of LIBS and LA-LIBS calibration curves for Mg in phosphate matrix pellets.
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Investigation of liquid samples or bio-fluids   (algae suspension)
Instrumentation at Institute of Physical Engineering BUT Brno (prof. J. Kaiser)
Liquid samples
C:\Users\novotny\Desktop\SOC\Fotky double pulse+kapaliny\kapaliny\lumix\P1000658.JPG
 Porizka, P.; Prochazka, D.; Pilat, Z.; Krajcarova, L.; Kaiser, J.; Malina, R.; Novotny, J.;
Zemanek, P.; Jezek, J.;  Sery, M.; Bernatova, S.; Krzyzanek, V.; Dobranska, K.; Novotny, K.;
Trtilek, M.; Samek, O., Application of laser-induced breakdown spectroscopy to the analysis of
algal biomass for industrial biotechnology. Spectrochimica Acta Part B-Atomic Spectroscopy, 2012,
74-75, 169-176.
LIBS system employing laminar water jet setup
Segments of LIBS spectra of algae suspensions recorded using water jet liquid arrangements
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Nanoparticles (QDs)
Spatial distribution of quantum dots (QDs)
•cadmium containing QDs – CdS, CdTe
•injection onto the carrier material (chromatographic paper, polystyrene ...)
Calibration graphs for injection of 5 µl CdS GSH and CdS MPA solution injected on the
chromatographic paper .
Cd signal was obtained by LIBS on emission line Cd(I)  508.58 nm and signal intensity was
summarized by counting pixels and all points of raster.
CdS QDs spatial distribution after injection of different volumes and different concentrations on
chromatographic paper, 6 x 6 points with spacing 600 µm, emission line Cd (I) 508.58 nm and
fluorescence  (excitation wavelength 460 nm, emission wavelength 700 nm).
39

Remote analysis
Stand-off identification of biominerals
Instrumentation developed at Institute of Physical Engineering
BUT Brno (prof. J. Kaiser)
Vitkova, G.; Novotny, K.; Prokes, L.; Hrdlicka, A.; Kaiser, J.; Novotny, J.; Malina, R.; Prochazka,
D., Fast identification of biominerals by means of stand-off laser-induced breakdown spectroscopy
using linear discriminant analysis and artificial neural networks. Spectrochimica Acta Part
B-Atomic Spectroscopy 2012, 73, 1-6.
Comparison of linear discriminant analysis (LDA) and artificial neural networks (ANN)
input data  - PCA scores
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Conclusion
Radziemski, L. ; Cremers D.,  A brief history of laser-induced breakdown spectroscopy: From the
concept of atoms to LIBS 2012 , Spectrochimica Acta Part B-Atomic Spectroscopy 2013, 87, 3-10
Self-portrait of Curiosity in Gale Crater on the surface of Mars
(October 31, 2012)
•rapid progress during the last two decades
•significant improving of LIBS measurement
     (advanced lasers, detection systems and data processing)
•improving precision and accuracy
      (process monitoring, on-line/on-situ screening)
•further improving to be accepted  as an analytical technique for quality control
•commercialization
•rapidly expanding field of LIBS applications
Perspectives at the Department of chemistry PřF MU:
•further development of instrumentation and methodology
•applications on real samples to solve the real scientific problems
•cooperation with the Institute of Physical Engineering BUT Brno, Department of Chemistry and
Biochemistry Mendel University in Brno, etc.
•involvement in the project CEITEC
•continuation of international cooperation with many universities and research teams around the
world
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