laser ablation applications in environment, medicine and ...€¦ · centre d’etudes et de...
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Laser ablation applications in environment, medicine and materials science
Cristian FOCSA
Centre d’Etudes et de Recherches Lasers et Applications (CERLA),
Laboratoire de Physique des Lasers, Atomes et Molécules (UMR CNRS 8523),
Université de Lille 1 Sciences & Technologies, 59655 Villeneuve d’Ascq cedex, France
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Centre d’Etudes et de Recherches Lasers et Applications
EMRS 2016 Spring Meeting
2-6 May 2016 in Lille, FR
Syposium C: Laser – Materials Interactions for Tailoring Future’s Applications
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Centre d’Etudes et de Recherches Lasers et Applications
LASER SOURCES : - nanosecond (QUANTEL, CONTINUUM)
Nd:YAG : 1064, 532, 355, 266 nm+ tunable (dye, 225 – 900 nm)5-10 ns, < 1 J/pulse< 1011 W/cm2
- femtosecond (Spectra Physics)Ti:Sa : 800 nm ( + tunable OPAs)40 fs, 120 fs, 2 ps, < 2 mJ/pulse< 1014 W/cm2
- continuous wave (IPG)fiber laser, 1070 nm< 300 W< 106 W/cm2
APPLICATIONS :
- Environment ice, soot particles, biogenic &
secondary organic aerosol …
- Materials plasma space propulsion
thin film deposition
fundamental (plasma dynamics)
- Medicine MALDI-MS mapping / cancer markers
« intelligent » laser scalpel
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Laser desorption / ablation / plasmaLaser – matter interaction … transient plasma generation
Pulsed laser beam106 - 1014 W/cm2
Photons, electrons, atoms, ions, molecules, clusters, nanoparticles
1. Laser energy absorption in the material … temperature increase … heat diffusion … phase transition
2. Matter ejection in the gas phase … fast expansion (1-10 km/s) … shock wave
3. Interaction ejected matter – laser pulse (ns) … inverse Bremsstrahlung … plasma heating
4. Target cooling … recombination processes … re-condensation on the surface
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Projects related to environmental issues
1. Heterogeneous processes at the surface / in the volume of
ice : diffusion, incorporation mechanisms, …
2. Study of the adsorbed phase of soot particles generated
by combustion processes
3. Formation of secondary organic aerosol
PhD students: Claudia Mihesan (2003-2007), Adriana Oancea (2006-2010), Cornelia Irimiea (2013-…)
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Projects related to environmental issues
Projects with Romania
2006-2008 ARCUS PhyCAFOR (FR/RO/CZ/HU, 200 k€)
2007-2008 ECO-NET (40 k€)
Summer schools organized in Romania
2006 Iasi, UAIC, 2 weeks, 194 participants
2008 Constanta, U. Ovidius, 1 week, 98 participants
PhD students: Claudia Mihesan (2003-2007), Adriana Oancea (2006-2010), Cornelia Irimiea (2013-…)
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Sample
Desorption
Ionization
Detection
Laser Desorption (LD) :
• IR OPO, λ = 2.5 → 4 µm, 10 ns, 10 Hz, Emax= 20 mJ/pulse
• Nd:YAG (1ω – 4ω), 10 ns, 10 Hz, Emax= 0.1 – 1 J/pulse
Laser Ionisation (LI) :
• 4th harmonic Nd:YAG, λ= 266 nm, 10 ns, 10 Hz, Emax= 100 mJ/pulse
• Tunable dye laser (225 – 900 nm, REMPI), 10 ns, 10 Hz
• NEW 118 nm source (9th harmonic Nd:YAG)
Detection :
Reflectron Time-of-Flight Mass Spectrometer(ReTOF-MS)
Experimental Technique – L2MS (Two-step Laser MS)
HAP SootIce (doped)
Laser Desorption / Laser Ionization / Mass Spectrometry
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Motivation
Carcinogenic potential
Indirect effects,Cloud formation
Environmental pollution
direct effects,radiation absorption
CLIMATE EFFECTS
HEALTH EFFECTS
SOOT: unburned residue of the combustion process
PAHs - adsorbed on the soot matrix
ENVIRONMENT
Analysis of soot particles generated by combustion processes
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• Airplane engine soot• SaM146 campaign : Mermose project (DGAC/ONERA/SNECMA/CNRS)
Four engine regimes: 30 %, 70%, 85%, 100% LTOSampled on quartz paper filters (Pallflex QAT-UP 2500)and Si wafers
• Laboratory model soot – PC2A, CORIA, IRSN• miniCAST soot - standard generator
Propane fuel various oxidation air flowsSampled on quartz paper and borosilicate filters
• Kerosene, Diesel, … soot: laboratory flames sampled at different heights above the burner (HAB)
• Field campaigns• Road traffic – Paris, Grenoble (INERIS, A. Albinet)• Maritime traffic – Atmospheric Soot Network (Moldanova et al., Atmos. Environ. 2009)• Car & Van – Biodiesel … BIOTOX project (FR/CZ/RU)
Airplane
CAST
Kerosene flame
Borosilicate filter
Analyzed samples
ENVIRONMENT
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240 260 280 300 320 340 360 380
370 372 374 376 378 380 382
Ethylene sootmass spectrum
0 100 200 300 400 5000,0
0,4
0,8
1,2
1,6
2,0
m/Z (amu)
Signal
(V)
Benzo[qr]naphtho[2,1,8,7-fghi]pentacene
L2MS Performances Mass detected typically up to 800 amu (for soot)
Mass resolution ~1000
High sensitivity to PAHs … LOD ~ 10 attomol per laser shot (~10-5 ML)
thanks to the resonant absorption at 266 nm (REMPI)
Control the fragmentation degree
ENVIRONMENT
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L2MS Performances Mass detected typically up to 800 Th (for soot)
Mass resolution ~1000
High sensitivity to PAHs … LOD ~ 10 attomol per laser shot (~10-5 ML)
thanks to the resonant absorption at 266 nm (REMPI)
Control the fragmentation degree
Control the desorption depth
(Semi)quantitative approach possible
through external standard calibration,
ionization cross section corrections
Pyrene / activated carbon, 9.52∙10-8 mol/g, 600 m2/g
Faccinetto et al., Combust. Flame, 158, 227 (2011)
Environ. Sci. Technol. 49, 10510 (2015)
ENVIRONMENT
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New ionization source118 nm (10.5 eV)9th harmonic of the Nd:YAG lasergenerated by frequency tripling of the 3rd harmonic in a low-pressure Xe cell
Desgroux et al., Proc. Combust. Inst. 34 (2013)
1713
… Looking for aliphatics – L2MS
+ single-photon thresholdionization … synchrotron SOLEIL / DESIRS / PEPICO
Xe supplyto thepumping unit
Xe bottle
pumpingunit
355 nm beam
cell
TOF-MS
ENVIRONMENT
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LASER − MATTER INTERACTION … PhLAM LABORATORY
MATERIALS :
- simple model targets (Al, Cu, …)fundamental interestfractal hydrodynamic modelcollab. U. Asachi & U. Cuza, Iasi, Romania
- ceramics (BNSiO2, Al2O3, MgO, … )plasma space propulsioncollab. SNECMA/CNES/U. Orléans, France
- chalcogenides (Ga/Ge/Sb/S/La/Te/As/Se)thin films pulsed laser deposition (PLD)wavelength conversion, IR laser sources, ...collab. Rennes (France), Pardubice (Czech R.)
- RE-doped ferrites (Er, Gd, La, … - CoFe2O4)thin films pulsed laser deposition (PLD)sensors (position, torsion, pressure)collab. U. Cuza, Iasi, Romania
PhD students: Cristian Ursu (cotutelle UAIC, 2006-2010),
Oana Pompilian (2009-2013), Stefan Irimiciuc (cotutelle UAIC, 2014-…)
Invited professors: S. Gurlui, M. Agop, P. Nica,
I. Mihaila, L. Leontie
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LASER ABLATION EXPERIMENTAL SET-UP
ICCD camera
Nd:YAG & Ti:Sa lasersns, ps & fs regimes
Targets:20 mm diameter, 2 mm thick disksplaced in vacuum (10-6 Torr) on an XYZ micrometric translation stage
Plasma imaging and OES:PI MAX ICCD camera (1024X1024 pixels, gating time 2 ns)PI Acton monochromator (f=50 cm, 2400 l/mm & 300 l/mm gratings) Fast response photomultiplier(Hamamatsu)
Langmuir probes & target currentmeasurements
Signal acquisition & processing:2 GHz oscilloscope (LeCroyWaveRunner 6200A) + LabView
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Plasma/Materials Fundamental studies on the dynamics of transient plasmas
generated by high-fluence laser ablation
Optical (fast gate ICCD imaging, optical emission spectroscopy) andelectrical (Langmuir probes, MS) methods
Systematic studies in various temporal regimes (ns/ps/fs) on a series ofmetals and oxides … influence of the target physical parameters
First observation of oscillations in the dynamics of the laser ablationplasma
Development of a new theoretical model based on a fractal approach(collaboration U. Asachi, UAIC Iasi)
Support: PHC Brâncuşi, Institut Français de Bucarest (PhD cotutelle)
280 300 320 340 360 380 400 420 440 460 4800
15
30
45
60
75
90
105
394.25 394.30 394.35 394.40 394.45 394.50 394.55
Al II
(466.3
0 nm)
Al III
(452
.92 nm
)Al
III (4
51.25
nm)
Al III
(447
.99 nm
)
Al III
(414
.99 nm
)
Al I (
396.1
5 nm)
Al I (
394.4
0 nm)
Al III
(371
.31 nm
)Al
II (36
5.49 n
m)Al
III (3
61.24
nm)
Al III
(360
.16 nm
)Al
II (35
8.75 n
m)
Al I (
327.5
8 nm)
Al IV
(324
.61 nm
)
Al I (
309.2
7 nm)
Al I (
308.2
1 nm)
Al II
(299.8
1 nm)
Al I (
293.6
0 nm)
Al III
(290
.70 nm
)
I [u.a.
]
λ [nm]
Al II
(288.1
4 nm)
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Fundamental studiesFractal hydrodynamic model
S. Gurlui, M. Agop, P. Nica, M. Ziskind, C. Focsa, Phys. Rev. E, 78, 026405 (2008)
P. Nica et al., Jpn. J. Appl. Phys., 48, 066001 (2009), 51, 106102 (2012)
∂∂
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Plasma charge state distribution (collisional radiative model)
)]1()1([)()()1( 3 +++=+ ZnZZSZfZf ber αα
ne - electron density, S, αr, α3b - collision ionization, radiative and three-bodyrecombination rates
V – complex speed field,
D – fractal/nonfractal transition
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Erosion of dielectric walls in Hall effect plasma thrusterSupport: CPER CIA, GdR « Propulsion Spatiale à Plasma »
a
Thruster annular chamber dielectric (BNSiO2) walls erosion …lifetime limitation
Simulation by ns & cw laser irradiation … generation oftopological and thermal defects … laboratory studies, thenimplementation on the national ground facility PIVOINE 2G(ICARE, Orléans)
First experimental validation of the actinometric hypothesis usedfor erosion monitoring … opens the way for in-flight monitoringby on-board micro-spectrometer
Plasma/Materials
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Experiments on the French national facility PIVOINE
GdR « Plasma Space Propulsion » CNES/SNECMA/CNRS/Universités
PIVOINE-2G
ICARE laboratory (Orléans, France)
Large vacuum chamber (diameter 2 m, length 7 m)
cryogenic pumping system (150 000 L/s)
Pressure: 2. 10-5 mbar(with 5 mg/s Xe flow)
Collaboration: PhLAM, GREMI, ICARE, CEMHTI,
LPGP, SNECMA, CNES, U. Paris 6
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Synthesis and characterization of thin films (Pulsed Laser Deposition)Support: CPER CIA, PHC Barrande (FR/CZ) & Brâncuşi (FR/RO)
Optimisation of PLD parameters by systematic fundamental studies(OES, ICCD, Langmuir)
Thin film synthesis
Cobalt ferrite doped with rare earth ions (Gd, La, Dy) …G. Dascalu (UAIC, PhD, post-doc)
Amorphous chlcogenides (GeSbTe, GaLaS) doped with rare earthions (Pr, Er) … O. Pompilian (INFLPR, PhD)
Thin film characterization: Raman, XRD, SEM, EDX, SIMS,ellipsometry, profilometry, spectrophotometry, VSM etc.
-10 -5 0 5 10
-150
-100
-50
0
50
100
150 Gd doped cobalt ferrite thin film deposited at 400oC Paralel Perpendicular
H (kOe)
Mag
netiz
ation
(em
u/cm
3 )
Plasma/Materials
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MALDI: Matrix-Assisted Laser Desorption Ionization Fundamental mechanisms, sensitivity/resolution, mapping
I. Dissection II. Transfer
III. Matrix deposition
(Cryostat, Microtome)
IV. MALDI Analysis
I. Fournier (PRISM, Lille 1), G. Bolbach (Paris 6)
Biology/Medicine
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φimpact≈300 µm
1. Masks & Grids
Improving MALDI sensitivity and spatial resolution
Si masks superposed on the analyzedsample
2. Laser desolvatation of clusters
Sensitivity (x 2 - 5) spatial resolution (< 20 µm)improvement
Implementation of a second laser to dissociate theclusters in the plume … increased analyte ionsproduction … resonant excitation (IR, O-H, C-Hstretchings ~3 µm)
Analyte signalimprovement (x 3)
Collaborations: PRISM, l’IEMN (Lille1), Laboratoire des BioMolécules (Paris6)
Biology/Medicine
Diologent et al., Anal. Chem. 86 1404 (2014)
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• Objective : develop an « intelligent » laser scalpel with real-time analysis• Techniques :
-Resonant IR Laser Desorption (OPO, Fiber Optics coupling)
Laser desorption of biological material : on-line & in vivo analysis
Collaboration : PRISM, Oncovet Clinical Research (Lille1), Department of Gynecology Oncology, Cancer CenterOscar Lambret, Lille, Département Universitaire de Gynécologie Obstétrique, Hôpital Jeanne de Flandre, CHRUde Lille, ANAXA VIDA, Villeneuve d’Ascq (bio-informatics), Faculty of Medicine, Department of Surgery & Cancer(Imperial College London)
-Ejecta transfer to ion source (Venturi / Droplet capture)
-Mass Analysis (Electrospray / Rapid Evaporative Ionization Mass Spectrometry)
• Preliminary results : proof of concept for LADC technique
Venturipump
StepwaveTMguide
Collision surface
(a)
(b)
Opticfiber
Ablation plume
3 mm
Venturi tube
Aspiration to interface device to
MS analyzer
Irradiated tissue
Figure 2: Schematic representation of the laserablation fibered system.
Figure 3: Pictures representing the specific modifiedinterface for the instrument design by Partner 3. (a)large view of the interface to the MS system and (b)zoomed view on the modified ion source.
Detection of standard compounds by LADC Comparison of spectra recorded from two regions of the same tissue
Biology/Medicine
Fatou et al., Nature Scientific Reports 5, 18135 (2015)
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painless non invasive
impact
Laser
Genre
Specific profiles - gender / medication / cosmetic treatment
Principal Component Analysis
Crème Hydratante
Analgesique
Homme/Femme
Application Pharmaceutique et Cosmétique
FemmeHomme
phalangesnon
traitées
phalanges+ produit
phalangesnon
traitées
phalanges
+ produit
National Research Agency (ANR): ANR Santé-Bien Etre CE17,
REALITY’MS since 2014
National Institute of Health (INSERM): Programme PhysiCancer since
2015
National Maturation Program (MATWIN) : Best Breakthrough
Innovation Award in 2015
Accelerating Technology Transfer (SATT Nord) : 500 k€ since 2014
Support
Perspectives et Objectives
On-going:
Fiber coupling optimization, Miniaturization(collaboration Thermo-Fisher)
Bio-informatics – database, interface (collaborations COL, Jeanne-de Flandres, Anaxa-Vida)
Short/medium term :
Veterinary clinic tests (Collaboration Oncovet) RobotizationApplications to other fields in bio & envrionementPrototype … start-up … market
SPIDERMASS – Instrument for real-time analysis of biological tissues ex vivo & in vivo
B. Fatou, Ph. Saudemont, T. Maulouet, M.Wisztorski, M. Salzet, I. Fournier, M.Ziskind, C. Focsa
ex-vivo analysis of ovarian cancer biopsy
Results
Specific profiles recorded in real time on benign/malign regions
in-vivo analysis Analysis of fruits
Possible application in food industry
Patent WO 2016/046748A1 Fatou et al., Nature Scientific Reports, in press (2016)
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AcknowledgmentsU. Lille 1, FR: B. Chazallon, M. Ziskind, Y. Carpentier, C. Pirim, I. Fournier, M. Salzet, B. Fatou, L.
Diologent, JL. Destombes, M. Cordonnier, A. Faccinetto, P. Desgroux, E. Therssen, C. Mihesan, A. Oancea, C. Irimiea, R. Ikhenazene, S. Facq, T. Maulouet, S. Irimiciuc, C. Ursu …
U. Orléans, FR: S. Pellerin, N. Pellerin, L. Balika, P. Lasgorceix, P. Echégut
U. Paris 6, FR: M. Dudeck, G. Bolbach
U. Rennes, FR: V. Nazabal
U. Marseille, FR: D. Ferry, Ph. Parent
LPGP Orsay, FR: D. Pagnon
U. Pardubice, CZ: P. Nemec, R. Boidin
U. Moscow, RU: O. Popovicheva
UAIC Iasi: S. Gurlui, G. Popa, O. Caltun,
G. Dascalu, I. Mihaila, L. Leontie, G. Singurel
U. Asachi, Iasi: M. Agop, P. Nica, N. Cimpoesu
U. Craiova: M. Osiac INFLPR Bucharest: O. Pompilian, C. Lungu
Colaborare cu România
• 3 proiecte comune• > 40 luni de profesor invitat la Lille• 6 doctoranzi români, din care 2 in
cotutela (Lille – UAIC Iasi)• >10 doctoranzi români la Lille
(stagii 2-8 luni)• >20 masteranzi români la Lille• 5 masteranzi francezi trimisi in
Romania (2 Iasi + 3 INFLPR)
Diapositive numéro 1Diapositive numéro 2Diapositive numéro 3Diapositive numéro 4Diapositive numéro 5Diapositive numéro 6Diapositive numéro 7MotivationDiapositive numéro 9Diapositive numéro 10Diapositive numéro 11Diapositive numéro 12Diapositive numéro 13Diapositive numéro 14Diapositive numéro 15Diapositive numéro 16Diapositive numéro 17Diapositive numéro 18Diapositive numéro 19Diapositive numéro 20Diapositive numéro 21Diapositive numéro 22Diapositive numéro 23Acknowledgments�