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

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

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

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

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-…)

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-…)

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

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

• 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

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

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

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

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

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

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)

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)

∂∂

+∂

∂−=

∂∂

+∂∂

+∂

∂∂∂

−=∂∂

+∂∂

+∂

∂∂∂

−=∂∂

+∂∂

+∂

∂

=∂∂

+∂∂

+∂∂

zv

rru

rpnve

zrnue

rrtne

zpnv

zrnuv

rrtnv

rpnuv

zrnu

rrtnu

nvz

rnurrt

n

)(1)()(1)(

)()(1)(

)()(1)(

0)()(1

2

2

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

∆−∇⋅+∂∂

= iDtdt

Vδ

22

220

)/2()/2(),(

αααα

DttxDvtxv

++

=

+−

−+

= 22

20

22 )/2()(

exp))/2((

1),(ααααπ

ρDt

tvx

Dttx

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

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

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

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

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)

• 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)

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)

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�