Scientificreport2015-2018PSC:PhysicsandConfinedSystemInthisdocument,youwillfindsomeshortsummaryofthedifferentachievementsandup-goingresearchdevelopedwithinthefollowingaxes:Sub-axes:

- Nanostructures- Surfaces,Interfaces- UltrafastPhenomena

These researches are conducted within the three teams NNM (NanoMagnetism andModeling), PIMS (Physics of Interfaces and StructuredMaterials), NOVA (NanoOptics,Vibrations,andAcoustics).

Nanostructures2015-20181-NanostructureinfluenceonmagneticpropertiesPSCgroupaxes:NanostructuresResearchers:N.Yaacoub,J-M.Grenèche,Y.Labaye,F.Calvayrac,R.Busselez

❖ Exploring the Magnetic Disorder in Ultrathin Iron Oxide HollowNanoparticles

Abstract: Magnetic nanoparticles are of special interest in the field of storageinformation and nanomedicine (hyperthermia, medical imagery, …). Due to thenanometricsizeoftheparticlestheycanbeguidedusingamagneticfield.Unfortunately,reducing the size of the nanomagnets leads to magnetic instability incompatible totechnological applications. Modifying the shape of the nanoparticles (core-shellparticles,Hollowparticles,…) lead toanexaltationof surface/interfaceeffects andan

Figure1:PropertiesofHollowmagneticnanoparticle.

enhancement of the magnetic anisotropy and the apparition of dynamical effect(superparamagnetic). As an example, by use of in-field Mössbauer spectrometry, wehave shown the existence of complex non-collinear magnetic structure in iron oxidehollow nanoparticles. Indeed, this structure consists in a ferrimagnetic layer of fewatomic planes confined between two layerswith canted structure resulting from twoantiferromagneticcoupledsperomagneticstructures.Suchamagneticstructureleadstoan increaseof themagneticcouplingbetweenthe interfacialmomentsof themagneticphases.Theexchangebiascouplingfinallytendstoincreasethemagneticanisotropyofthenanoparticlesandindefinitivethemagneticstabilityofthenanostructure.Projects:ANRObnarem,PicsFrance-ItalieRelatedpapers:

● F.Sayed,N.Yaacoub,Y.Labaye,R.S.Hassan,G.Singh,P.A.Kumar,J.M.Greneche,R.Mathieu,G.C.Hadjipanayis,E.AgostinelliandD.Peddis,SurfaceEffectsinUltrathinIronOxideHollowNanoparticles: Exploring Magnetic Disorder at the Nanoscale, J. Phys. Chem. C, 2018, 122,7516–7524.

● G. Muscas, N. Yaacoub, G. Concas, F. Sayed, R. Sayed Hassan, J. M. Greneche, C. Cannas, A.Musinu, V. Foglietti, S. Casciardi, C. Sangregorio and D. Peddis, Evolution of the magneticstructurewithchemical composition in spinel ironoxidenanoparticles,Nanoscale, 2015,7,13576–13585.

● T. Gaudisson, R. Sayed-Hassan, N. Yaacoub, G. Franceschin, S. Nowak, J.-M. Grenèche, N.Menguy,P.SainctavitandS.Ammar,Ontheexactcrystalstructureofexchange-biasedFe3O4–CoOnanoaggregatesproducedbyseed-mediatedgrowthinpolyol,CrystEngComm,2016,18,3799–3807.

● F.Sayed,Y.Labaye,R.SayedHassan,F.ElHajHassan,N.YaacoubandJ.M.Greneche,Sizeandthicknesseffectonmagneticstructuresofmaghemitehollowmagneticnanoparticles,JournalofNanoparticleResearch,2016,18,279.

● Y.Prado,N.Daffé,A.Michel,T.Georgelin,N.Yaacoub,J.-M.Grenèche,F.Choueikani,E.Otero,P.Ohresser,M.-A.Arrio,C.Cartier-dit-Moulin,P.Sainctavit,B.Fleury,V.Dupuis,L.Lisnardand J. Fresnais, Enhancing the magnetic anisotropy of maghemite nanoparticles via thesurfacecoordinationofmolecularcomplexes,NatureCommunications,2015,6,10139.

❖ Spin disorder versus Exchange bias coupling in magnetic nanoparticleswithcomplexarchitecture(Hollow,shell/shell,…)

Abstract: An important relevant features of the size effect inmagnetic nanoparticles(NPs) is the occurrence of non-collinear spin structures (spin canting, magneticfrustration, spin disorder). Indeed, the non-collinear spin structures could stronglymodify the magnetic properties of the magnetic NPs, for example as it was shownrecently by us which found a strong correlation between complex spin disorder andexchangebias(EB)featuresinironoxidehollowNPs.AlthoughthemacroscopicmodelofEBeffectexistedfornearlysixdecades,themicroscopicoriginofthisphenomenonisstillrequiringfurtherinvestigationinsomespecificsystemsatnanoscales.Eveninthecaseof verywell-studiedand investigatednanomaterials suchas spinel ferrites, a fullunderstandingofthecorrelationbetweenspinstructure,surface/interfaceeffectandEBcoupling isstill lacking. In thiscontext,wepropose to investigate thisphenomenon in

systems presenting high spin disorder like Hollow NPs with different sizes and shellthickness and extended this study to a system of shell/shell that consists of twomagnetic phases: a ferrimagnetic phase and an antiferromagnetic one. The idea is todiscriminatetheEBresultingfromsurfacespindisorderfromthatresultingfromspinsinterface coupling between two different magnetic phases. Figure below show theMössbauerspectraforhollow(g-Fe2O4)andshell/shell(g-Fe2O4/NiO)NPswithsameexternal diameter and thickness (15 nm and 7.5 nm). As a preliminary result, weobservethatthespindisorderisbiggerintheshell/shellthaninthehollowone.Ontheother hand theEBobserved in shell/shellNPs is bigger than that observed in hollowNPs.Thisraisesthequestionabouttheeffectoftheantiferromagneticphaseonthespindisorder and the EB coupling in this kind of nanoscale systems ? Finally, In order toavoidtheeffectofdipolarinteractionandstudyitseffectsonspindisorderandEBweproposetodispersethesesystemsinnonmagneticmatrix.

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Figure2: In-fieldMössbauerspectraofmagneticNPswithdifferentarchitectures:γ-Fe2O3,(hollow)andγ-Fe2O3/NiO(Shell/shell)

❖ ClassicalMagneticmodels:towardsamulti-scaleapproach

Abstract: Phenomenological magnetic models are able to bridge a gap between themicroscopicmagnetic properties and local organization ofmagnetic sites from a firstpartandtheoverallmagneticpropertiesofbulkornanosizedmaterialsfromasecondpart.

Figure3:Left:Influenceofdopaminefunctionalizationonmagneticproperties.Right:Influenceofstructurerelaxationonmagneticproperties

In thecaseofHeisenbergmodel, themagneticHamiltonian isgovernedby fewcriticalparameters, namely the magnetic moments of sites, the exchange energy betweenneighbors, the volume anisotropy constant and for finite size objects, the surfaceanisotropyconstantandinterfaceanisotropyconstants.Accuracyoftheresultsemergingfromtheclassicalmodel is thenintimatelyrelatedtothe theoretical or experimental determination of the underlyingmagnetic parametersand microscopic site organization of the system. This level of knowledge is notnecessarily fulfilled in the case of complex structures or unusual compounds. Using anumericmulti-scale approach coupling ab-initio, molecular dynamics and Heisenbergsimulations, access to a finer level of description. Fromonepart theuseofmoleculardynamicssimulation,permits torelaxthestructureofnano-sizedorbulksystemsandthentoreproducethemagneticsitespositionanddistributioninamorerealisticway.From another side, adjustments of ab-initio calculations and Heisenberg model on alargestatisticalsampleofrepresentativelocalenvironmentsallowustodeterminethemicroscopicmagneticparameters.Project:ANRObnaremRelatedPapers:

● K.BrymoraandF.Calvayrac,Surfaceanisotropyof ironoxidenanoparticlesandslabs fromfirstprinciples:InfluenceofcoatingsandligandsasatestoftheHeisenbergmodel,JournalofMagnetismandMagneticMaterials,2017,434,14–22.

● F.Sayed,Y.Labaye,R.SayedHassan,F.ElHajHassan,N.Yaacouband J.M.Greneche,Sizeand thickness effect onmagnetic structures ofmaghemite hollowmagnetic nanoparticles,JournalofNanoparticleResearch,2016,18,279.

● Z.Nehme,Y.Labaye,R.SayedHassan,N.YaacoubandJ.M.Greneche,ModelingofhysteresisloopsbyMonteCarlosimulation,AIPAdvances,2015,5,127124.

2-TayloringofmagneticandmultiferroicphasesPSCgroupaxes:NanostructuresResearchers:N.Randriantonandro,F.Calvayrac

❖ RareEarthfreepermanentmagnetsAbstract:Amongcurrentlyinvestigatedrare-earth-freemagnets,ferromagneticτ-MnAlisapotentialcandidatehavingpromisingintrinsicmagneticproperties.Mn(Fe)AlCwassynthesized by mechanical alloying method. Effects of carbon on microstructure andmagneticpropertiesweresystematicallyinvestigated.Itwasfoundthathighpurityofτ-MnAl(C) could be obtained at 2 at.% C doping, showing clearly stabilizing effect ofcarbon.Mn54.2Al43.8C2hasthebestmagneticproperties:magnetizationat2TM2T=414kA.m-1,remanentmagnetizationMr=237kA.m-1,coercivityHC=229k.Am-1,and|BH|max= 11.2 kJ.m-3. HC increased inversely with the crystallite size of τ phase andproportionally with C content. Moreover, first principle calculation showed bothstabilizing effect andpreferable interstitial positionsof carbon in tetragonal τ-MnAl.Mn51-xFexAl47C2 (x= 0.25, 0.5, 1, 2, 4, 6) alloys were also synthesized by mechanicalalloyingmethod,showingthehighpurityofτphaseupto2at.%Fedoping.AddingofFeonMnAl(C) reduced bothmagnetization and TC but likely increased slightly HC. 57FeMössbauerspectrometryat300Kwasusedtoprobelocalenvironmentinε-,τ-,β-,andγ2-MnFeAl(C). In which, γ2-, ε-, and β-MnFeAl(C) exhibited a quadrupolar structure

while τ -Mn50.5Fe0.5Al47C2 spectrum showed a rather complex magnetic hyperfinesplitting. The interaction between Fe and Mn examined by in-field Mössbauermeasurementat10Kand8T showedanon-collinearmagnetic structurebetweenFeandMnwithdifferentcantinganglesatdifferentsites. HyperfinefieldofMnFeAlalloycalculatedbyWien2ksupportedbothmagneticpropertiesandMössbauerresults.

Figure4: Changes inmagneticmomentwith substitution.Mössbauer spectra showing ferrimagnetic order.Magnetizationcurveofsubstitutedphases

Relatedpaper:

● V.TangNguyen,F.Calvayrac,A.BajorekandN.Randrianantoandro,Mechanicalalloyingandtheoretical studiesofMnAl(C)magnets, JournalofMagnetismandMagneticMaterials,2018,462,96–104

❖ MultiferroicMaterialsAbstract: Multiferroic materials constitute a class of multifunctional materialspresentinginthesametimecoupledpropertiesintermsofferromagnetic-ferroelectricand ferroelastic order. On a fundamental scale, the nature of the interactions and inparticular themagnetoelastic couplingmechanism is not fully understood despite theamountofexperiments.Ona technological level, thisclassofmaterial is interesting inthe field of information storage or for microelectromechanical systems development.Amongmultiferroicmaterials,BiFeO3isoneisoneofthefewwhichpresentsinthesametime both ferroelectric andmagnetic order above 300K.However despite this uniqueproperty, BiFeO3 also presents a magnetic helicoïdal structure of Fe3+ magneticmoments, this magnetic structure leads to weak magnetoelectric coupling. A drasticincrease of magnetoelectric coupling can be obtained through the breakdown ofhelicoïdal spiraleand the formationofanantiferromagnetic linear structureof typeGleadingtoanon-zeromeanmagnetization.Multipleswayscanbefollowedtobreakdownthishelicoidalstructureamongthem:

1. Reducing the size of thematerial dimension to a value lower than the cycloidperiod (~64 nm). This can be obtained by a polyol method for synthetizingBiFeO3nanoparticles.

2. SubstitutingBi3+andFe3+byTi4+andZr4+usingaceramicsynthesis inordertopartiallybreakhelicoïdalstructureofFe3+magneticmoments

Equi-atomic -MnAl

-Mn1+xAl1-x

Fe doped Mn1+xAl1-x

Figure5:Left:MEBpictureofBiFeO3particlesobtainedwithpolyolprocess.Right:Modificationofhelicoïdalmagneticorderandapparitionofferromagneticorder

Surfaces,Interfaces1.PlasmonicsandEnhancedVibrationalSpectroscopiesPSCaxe:SurfacesetInterfacesFonctionnellesResearchers: Jean-François Bardeau, Alain Bulou, Philippe Daniel, Nicolas Delorme,Mathieu Edely, Nicolas Errien, Alain Gibaud, Fabienne Lagarde, Marc Lamy de LaChapelle.Abstract:Themetallic nanoparticles or nanostructures can strongly interactwith light.Theycanprovidesomehugeenhancementofthenearfieldatthevicinityofthemetallicsurface due to the excitation of the localised surface plasmon (LSP). The plasmonicproperties depend on geometrical parameters (size, shape, coupling...) of thenanopatterned metals and can be finely controlled and tuned on a wide range ofwavelength.

v FieldenhacementandSERSoptimizationWeworkontherelationbetweentheLSPandtheenhancementefficiencydependingonthegeometricalparametersofthededicatednanostructures.WenotablydeterminetheinfluenceoftheLSPonthesurfaceenhancedRamanscattering(SERS).

Moreover, in the team, we developed strong skills in the structuration of metallicsurfaces atmicro/nanoscales to create nanostructured substrates for highly sensitiveSERSapplications.

Projets:ANRNanoBiosensor,ANRLouise,ANRPiranexPublication(s),bookchapter(s),patent(s):

• MathieuEdely,NicolasDelorme,DavidSiniscalco,andJean-FrançoisBardeau,Adv.Mater.Technol.2018,1800134-DOI:10.1002/admt.201800134

• N.Quilis,M.Lequeux,P.Venugopalan,I.Khan,W.Knoll,S.Boujday,M.LamydelaChapelle,J. Dostalek, Tunable laser interference lithography preparation of plasmonic nanoparticlearraystailoredforSERS,Nanoscale,10,10268,2018

• R.Gillibert,F.Colas,R.Yasukuni,G.Picardi,M.LamydelaChapelle,PlasmonicPropertiesofAluminiumNanocylindersintheVisibleRange,J.Phys.Chem.C121(4),2402,2017

• R. Gillibert, T. Tafer,M. Lamy de la Chapelle, Strong coupling between localized surfaceplasmon and Braggmode on aluminium nanocylinders grating deposited on aluminium film,PhysicaStatusSolidia,214(8),1600793,2017

• F.Colas,M.Cottat,R.Gillibert,N.Guillot,N.Djaker,N.Lidgi-Guigui,T.Toury,D.Barchiesi,A.Toma, E.Di Fabrizio, P. G. Gucciardi,M. Lamy de la Chapelle, Red-Shift Effects in SurfaceEnhancedRamanSpectroscopy:SpectralorIntensityDependenceoftheNear-Field?,J.Phys.Chem.C120(25),13675,2016

• R.Gillibert,M.Sarkar,J.F.Bryche,R.Yasukuni,J.Moreau,M.Besbes,G.Barbillon,P.Gogol,B,Bartenlian, M. Canva, M. Lamy de la Chapelle, Directional Surface Enhanced RamanScatteringongoldnano-gratings,Nanotechnology27/11,115202,2016

• R.Gillibert,M.Sarkar, J.Moreau,M.Besbes,M.Canva,M. Lamy de la Chapelle,NearFieldEnhancementLocalizationonPlasmonicGratings,J.Phys.Chem.C120(48),27562,2016

• J. F. Bryche, R. Gillibert, G. Barbillon, P. Gogol, J. Moreau, M. Lamy de la Chapelle, B.Bartenlian,M.Canva,Plasmonicenhancementbyacontinuousgoldunderlayer:applicationtoSERSsensing,Plasmonics,11/2,601,2016

• J. F. Bryche, A. Tsigara, B. Bélier, M. Lamy de la Chapelle, M. Canva, B. Bartenlian, G.Barbillon,SurfaceenhancedRamanscatteringimprovementofgoldtriangularnanoprismsbyagoldreflectiveunderlayerforchemicalsensing,SensorandactuatorB,228,31,2016

• Patent: Procédé de Fabrication d’un motif métallique nanostructuré et motif métallique-Inventeurs:M.Edely,N.Delorme,J.-F.Bardeau(2014-N°dedépôt:1461880)

v Molecularplasmonicsandthermoplasmonics

The plasmonic properties of metallic nanostructures can induced side effectssuchaslocalincreaseofthetemperature,knownasthermoplasmonicseffect,orthe formation of hot electrons that can react with molecules. We study andexploit such properties. For instance, we demonstrated that some chemicalreaction, such as the click chemistry, can be initiated and mediated by theplasmonorthatlargetemperaturescanbereachedatthenanostructuresurfacetoheatthelocalmedium.

Projets:X-TREM

Publication(s),bookchapter(s),patent(s):

• Tijunelyte,E.Guenin,N.Lidgi-Guigui,F.Colas,J.Ibrahim,T.Toury,M.Lamyde laChapelle,Nanoplasmonicstuned“clickchemistry”,Nanoscale,7/13,7105,2016

• S.Betelu,I.Tijunelyte,L.Boubekeur-Lecaque,I.Ignatiadis,J.Ibrahim,S.Gaboreau,C.Berho,T.Toury,E.Guenin,N.Lidgi-Guigui,N.Félidj,E.Rinnert,MarcLamydelaChapelle,EvidenceoftheGraftingMechanismsofDiazoniumSalts onGoldNanostructures, J. Phys. Chem.C, 120(32),18158,2016

• G. Picardi, F. Colas, R. Gillibert,M. Lamy de la Chapelle, Spectral Shift of the PlasmonResonancebetweentheOpticalExtinctionandAbsorptionofGoldandAluminumNanodisks,J.Phys.Chem.C,120(45),26025,2016

• Tijunelyte, I. Kherbouche, S. Gam-Derouich, M. Nguyen, N. Lidgi-Guigui, M. Lamy de laChapelle, A. Lamouri, G. Levi, J. Aubard, A. Chevillot-Biraud, C.Mangeney, N. Felidj, Multi-functionalizationoflithographicallydesignedgoldnanodisksbyplasmon-mediatedreductionofaryldiazoniumsalts,NanoscaleHorizon,3,53,2018

v Plasmonicapplicationsinsensing

The field enhancement canbe exploited for large enhancement of the spectroscopicalsignal of any molecules located at the vicinity of the nanoparticle surface. It is thenpossibletodetectmolecularspeciesatlowconcentrationandprovidehighsensitivitytothedetection.Thus,severalprojectsweredevotedtotheenhancementofRamansignal(SERS) allowing the detection and analysis ofmolecules in very small concentrations.Most applications are turned towards the detection of biomolecules in medecine,pollutantsinenvironment,contaminantsandmicro-organismsinfood.

Projets:Agrifood,ANRLouise,ANSESJFB,Nanoplastics

Publication(s),bookchapter(s),patent(s):

• R.Gillibert,M.Triba,MarcLamydelaChapelle,SurfaceEnhancedRamanScatteringSensorforHighlySensitiveandSelectiveDetectionofOchratoxinA,Analyst,143,339,2018.

• R.Gillibert, J.Q.Huang,Y.Zhang,W.L.Fu,M. Lamyde la ChapelleExplosivedetectionbySurfaceEnhancedRamanScattering,TrendinAnalyticalChemistry,105,166,2018

• R.Gillibert,J.Q.Huang,Y.Zhang,W.L.Fu,M.Lamyde laChapelleFoodqualitycontrolbySurfaceEnhancedRamanScattering,TrendinAnalyticalChemistry,105,185,2018

• M.Cottat,R.Yasukuni,Y.Homma,N.Lidgi-Guigui,N.Varin-Blank,M.LamydelaChapelle,C.Le Roy, Phosphorylation impact on Spleen Tyrosine kinase conformation by SurfaceEnhancedRamanSpectroscopy,ScientificReports7,39766,2017.

• Chauvet, R., F. Lagarde, T. Charrier, A. Assaf, G. Thouand, andP. Daniel. “MicrobiologicalIdentification by Surface-EnhancedRaman Spectroscopy.”AppliedSpectroscopyReviews 52,no.2(2017).https://doi.org/10.1080/05704928.2016.1209760

• I.Tijunelyte,S.Betelu,J.Moreau,I.Ignatiadis,C.Berho,N.Lidgi-Guigui,E.Guenin,C.David,S.Vergnole, E. Rinnert,Marc Lamy de la Chapelle, Diazonium Salt-Based Surface-EnhancedRamanSpectroscopyNanosensor:DetectionandQuantitationofAromaticHydrocarbons inWaterSample,Sensors,17(6),1198,2017

• M.Dribek,E.Rinnert,F.Colas,M.-P.Crassous,N.Thioune,C.David,M.LamydelaChapelle,C. Compère, Organometallic nanoprobe to enhance optical response on the polycyclicaromatichydrocarbonbenzo[a]pyreneimmunoassayusingSERStechnology,EnvironmentalScienceandPollutionResearch,24(35),27070,2017

• Alami,A.El,F.Lagarde,U.Tamer,M.Baitoul,andP.Daniel.“EnhancedRamanSpectroscopyCoupled to Chemometrics for Identification and Quantification of AcetylcholinesteraseInhibitors.” Vibrational Spectroscopy 87 (2016).https://doi.org/10.1016/j.vibspec.2016.09.005.

• EnhancedVibrationalSpectroscopiesasTools forSmallMoleculeBiosensing,S.Boujday,M.LamydelaChapelle,J.Srajer,W.Knoll,Sensors,15,21239,2015

• M. Cottat, C. D’Andrea, R.Yasukuni, N.Malashikhina, R. Grinyte, N. Lidgi-Guigui, B. Fazio, A.Sutton,O.Oudar,N.Charnaux,V.Pavlov,A.Toma,E.DiFabrizio,P.G.GucciardiM.Lamydela

Chapelle , High Sensitivity, High Selectivity SERS Detection of MnSOD Using OpticalNanoantennasFunctionalizedwithAptamers,J.Phys.Chem.C11915532,2015.

2.Physicsandstructuralpropertiesofsoftmatter

PSCaxe:SurfacesetInterfacesFonctionnellesResearchers: Jean-François Bardeau, Guillaume Brotons, Philippe Daniel, NicolasDelorme,MathieuEdely,NicolasErrien,AlainGibaud,FabienneLagarde,OlivierNoel.Severalprojectsofourteamaredevotedtothestudyofsoftmatterphysicalpropertiesastheirmechanical,thermalorstructuralpropertiesunderdifferentenvironments.

v Nano-mechanicsofsoftmatter

Projets:MecacellPublication(s),bookchapter(s),patent(s):

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Nano%mechanics,on,cell,membranes,

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Lateral,interac8ons,Normal,interac8ons,

Viscoelas8city,

Complex,biological,object,

• Et-Thakafy, O., N. Delorme, F. Guyomarc’h, and C. Lopez, Mechanical properties of milk

sphingomyelin bilayer membranes in the gel phase: Effects of naturally complex heterogeneity,saturationandacyl chain length investigatedon liposomesusingAFM. Chemistry and Physics ofLipids,2018.210:p.47-59,DOI:https://doi.org/10.1016/j.chemphyslip.2017.11.014.

• Et-Thakafy, O., N. Delorme, C. Gaillard, C. Mériadec, F. Artzner, C. Lopez, and F. Guyomarc’h,MechanicalPropertiesofMembranesComposedofGel-PhaseorFluid-PhasePhospholipidsProbedon Liposomes by Atomic Force Spectroscopy. Langmuir, 2017. 33(21): p. 5117-5126, DOI:10.1021/acs.langmuir.7b00363.

• Ayche,K.,A.Ventura,J.F.Bardeau,B.Minisini,J.F.Pilard,andN.Delorme,Naturalrubberbasedthin coating forMEMS encapsulation. Progress in Organic Coatings, 2016.99: p. 308-313, DOI:http://dx.doi.org/10.1016/j.porgcoat.2016.06.010.

v StructuralpropertiesofpolymersandcomplexcompositesfilmsSeveraltechniquesmasteredintheteamallowdeeppolymercharacterizationprovidingstructuralandphysicalinformation.SincebothinfraredandRamanspectroscopiesgivecomplementaryinformation,weusethesetechniquesaseffectivetoolstomonitorthemolecularstructureandpropertiesofpolymers.Coupledwithchemometrics,vibrationalspectroscopiesareusedintheteamto control polymer structure under different environments (thermal degradation, UVageing,mechanical deformation, very thin filmsbehaviors); todevelopnewbio-basedpolymers(cellulose,naturalrubber)andtoassessthedistributionoffillersincompositepolymers.WehavealsodevelopedastrongexpertiseinX-rayreflectivity....

Projets:Publication(s),bookchapter(s),patent(s):

• AnisotropicOne-DimensionalAqueousPolymerGelElectrolyteforPhotoelectrochemicalDevices:Improvement in Hydrophobic TiO2–Dye/Electrolyte InterfaceKK Sonigara, JV Vaghasiya, HKMachhi,JPrasad,AGibaud,SSSoni.ACSAppliedEnergyMaterials,2018

• Newprotonconductingmembranebasedonbacterialcellulose/polyanilinenanocomposite filmimpregnated with guanidinium-based ionic liquid, S. Rogalsky, J.-F. Bardeau, S. Makhno, N.Babkina,O.Tarasyuk,T.Cherniavska, I.Orlovska,N.Kozyrovska,O.Brovko,Polymer142,183-195(2018)

• 81. K. Taksapattanakul, T. Tulyapitak, P. Phinyocheep, P. Ruamcharoen, J. Ruamcharoen , F.Lagarde, M. Edely, P. Daniel. Raman investigation of thermoplastic vulcanizates based onhydrogenatednaturalrubber/polypropyleneblends.PolymerTesting.57107-114(2017)

• S. Ghamrawi, J.-P. Bouchara, O. Tarasyuk, S. Rogalsky, L. Lyoshina, O. Bulko, J.-F. Bardeau,Promisingsiliconesmodifiedwithcationicbiocidesforthedevelopmentofantimicrobialmedicaldevices,MaterialsScienceandEngineeringC75,969–979(2017)

• Taksapattanakul,T.Tulyapitak,P.Phinyocheep,P.Ruamcharoen,J.Ruamcharoen,F.Lagarde,P.Daniel The Effect of Percent Hydrogenation and Vulcanization System on Ozone Stability ofHydrogenatedNaturalRubberVulcanizatesusingRamanSpectroscopy.PolymerDegradationandStability,14158-68(2017)

• JV Vaghasiya, KK Sonigara, T Beuvier, A Gibaud, SS Soni, Iodine induced 1-D lamellar selfassembly in organic ionic crystals for solid state dye sensitized solar cells, Nanoscale 9 (41),15949-15957,2017

• Chebil,M.S.,G.Vignaud,J.K.Bal,T.Beuvier,N.Delorme,Y.Grohens,andA.Gibaud,Reversibilityin glass transition behavior after erasing stress induced by spin coating process. Polymer, 2017.122:p.45-51,DOI:https://doi.org/10.1016/j.polymer.2017.06.044.

• JV Vaghasiya, KK Sonigara, J Prasad, T Beuvier, A Gibaud, SS Soni, Role of aphenothiazine/phenoxazinedonorinsolidionicconductorsforefficientsolidstatedyesensitizedsolarcells,JournalofMaterialsChemistryA5(11),5373-5382,2017

• Unni,A.B.,G.Vignaud, J.P.Chapel, J.Giermanska, J.K.Bal,N. Delorme,T.Beuvier, S.Thomas,Y.Grohens,andA.Gibaud,ProbingtheDensityVariationofConfinedPolymerThinFilmsviaSimpleModel-Independent Nanoparticle Adsorption. Macromolecules, 2017. 50(3): p. 1027-1036, DOI:10.1021/acs.macromol.6b02617.

• BeenaUnni,A.,G.Vignaud,J.K.Bal,N.Delorme,T.Beuvier,S.Thomas,Y.Grohens,andA.Gibaud,SolventAssistedRinsing:Stability/InstabilityofUltrathinPolymerResidualLayer.Macromolecules,2016.49(5):p.1807-1815,DOI:10.1021/acs.macromol.5b02435.

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• K.Ayche,A.Ventura,J.-F.Bardeau,B.Minisini,J.-F.Pilard,N.Delorme,NaturalrubberbasedthincoatingforMEMSencapsulation,ProgressinOrganicCoating99,308-3013(2016)

• S.Rogalsky,J.-F.Bardeau,H.Wu,L.Lyoshina,O.Bulko,O.Tarasyuk,S.Makhno,T.Cherniavska,Y.Kyselov, J. H. Koo, Structural, thermal and antibacterial properties of polyamide 11/polymericbiocidepolyhexamethyleneguanidinedodecylbenzenesulfonatecomposites,JournalofMaterialsScience51,7716-7730(2016)

• D. Hodyna, J.-F. Bardeau, L. Metelytsia, S. Riabov, L. Kobrina, S. Laptiy, L. Kalashnikova, V.Parkhomenko,O.Tarasyuk,S.Rogalsky,Efficientantimicrobialactivityandreducedtoxicityof1-dodecy1-3-methylimidazolium tetrafluoroborate ionic liquid/beta-cyclodextrin complex,ChemicalEngineeringJournal284,1136-1145(2016)

• A.Gibaud,J.K.Bal,E.M.Gullikson,C.WangandG.Vignaud,AIPAdvances,6(9),095016,2016• J.K.Bal,T.Beuvier,A.B.Unni,E.Chavez,G.Vignaud,N.Delorme,M.Chebil,.Grohens,A.Gibaud,

ACSNano,9,8184,2015• Delorme,N.,M.S.Chebil,G.Vignaud,V.LeHouerou,J.F.Bardeau,R.Busselez,A.Gibaud,andY.

Grohens,ExperimentalevidenceofultrathinpolymerfilmstratificationbyAFMforcespectroscopy.Eur.Phys.J.E,2015.38:p.56.

• Bal, J.K., T. Beuvier, A.B. Unni, E.A. Chavez Panduro, G. Vignaud, N. Delorme, M.S. Chebil, Y.Grohens, and A. Gibaud, Stability of Polymer Ultrathin Films (<7 nm) Made by a Top-DownApproach.ACSNano,2015.9(8):p.8184-8193,DOI:10.1021/acsnano.5b02381.

3.Materials&surfacesforenvironmentandhealthPSCaxe:SurfacesetInterfacesFonctionnellesResearchers: Jean-FrançoisBardeau,GuillaumeBrotons, AlainBulou,PhilippeDaniel,NicolasDelorme,MathieuEdely,NicolasErrien,AlainGibaud,FabienneLagarde,MarcLamydeLaChapelle,OlivierNoel.Several projects of our institute are at the interface between physics, chemistry andbiology. We mostly investigate the physico-chemical behavior and properties ofmaterials and surfaces in complex environments or in interaction with cells andmicroorganisms.Wealsopropose theelaborationofmaterials, surfacesandprotocolsmainlydedicatedtosensingapplicationsinmedical,foodandenvironmentalfields.

v Surfacesininteractionwithacomplexenvironment

- Effect of the morphology and chemistry of TiO2 surfaces on the primaryadhesionofmicroorganisms(i.e.bacteriaandyeast).JFBardeau-Modelbilayerlipidmembranesandsensorsforprobingbiorelevantinterfaces.G.Brotons-Relationbetweenphysico-chemicalpropertiesofpolymermicrocarriersandtheadhesionanddifferenciationofMIAMIcellsinordertooptimizetheuseofstemcellsinneurodegenerativemedicine.N.Delorme- Interaction of micro and nanoplastics with marine biomolecules andmicroorganismsF.Lagarde,N.Errien,Ph.Daniel- Tribology and mechanical properties modifications of biological cells inassociated pathologies (cancer, dislipidemia,...); wear mechanisms at thenanoscale of metallic or composite materials to control emission of toxicmolecules.O.Noel

Immunofluorescence imageillustrating the adhesion ofMIAMIcellsonsurfaces of functionalizedmicrocarrier(PAM)

Projets:Meca-stem,Mat-Inno,Mecacell,PromptPublication(s),bookchapter(s),patent(s):• Vencl , P-E Mazeran , S. Bellafkih , O.Noël, Assessment of wear behaviour of copper-based

nanocompositeatthenanoscale,Wear414–415(2018)212–218• H. Fabre, D. Mercier, A. Galtayries, D. Portet,N. Delorme, and J.-F. Bardeau, Applied Surface

Science432,15(2018).• Ariunzaya. Ts, Solongo. B, Rentsenmyadag. D, Erdene-Ochir. G, Ninjbadgar. Ts, P. Daniel, A.

Gibaud.ComparisonStudyonAntimicrobialandPhotocatalyticActivityofDifferentShapedZnONanoparticles,acceptedforpublicationinSolidstatephenomena–October2018

• G.Ragchaa,B.Mongol,S.Munkhsaikhan,N.Tuvjargal1,J.Davaasambuu,S.Enkhtor,L.Enkhtor1,O.Tegus,P.Daniel,CarbonNanotubeFabricationBasedonAnimalRedBloodCells.SolidStatePhenomena,ISSN:1662-9779,27164-69(2018).

• SquillaceO,EsnaultC,PilardJFandBrotonsG.GraftingCommercialSurfactants(Brij,CiEj)andPEGtoElectrodesviaAryldiazoniumSalts.ACSApplMaterInterfaces.2017Dec6;9(48):42313-42326.

• I.Paul-pontetal.(incl.G.Brotons,F.Lagarde)(2018),constraintsandprioritiesforconductingexperimentalexposuresofmarineorganismstomicroplastics,frontiersinmarinescience5,DOI:10.3389/fmars.2018.00252.

• Noël,O.,Vencl,A.,Mazeran,P.-E.,Exploringwearatthenano-scalewiththecircularmodeAFM,BelsteinJournalofNanotechnology(2017)

• LagardeF,OlivierO,ZanellaM,DanielP,HiardS,CarusoA.Microplastic interactions withfreshwatermicroalgae:Hetero-aggregationandchangesin plasticdensityappearstronglydependentonpolymertype.EnvironPollut.2016;215.

v Detection,analysisandsensingforenvironmentandhealthVibrational spectroscopies allow the fast and reliable identification and detection ofmolecules in any sample (liquid, solid, gaz, complex matrix…) with the possibility tostronglyenhancethesignal(SERS)allowingthedetectionofverysmallconcentrations.Ourgroupdevelopedstrongskills inelaboratingstrategiesfortheimmobilization, fastdetectionandanalysisoforganicmoleculesormicroorganisms forenvironmentalandhealthapplications:organicpollutantsinwoodrecyclingindustry,microorganismsandantibioresistance, food contaminants, pesticides in waters, micro and nanoplastics inaquaticcompartmentsandbiota,biomarkersinbodyfluids….

Projets:SeaBioPack,Agrifood,ANRLouise,ANRNanoplastics,Miplaqua,ProjetANSESJFB,BASEMAN,MATIERES

Publication(s),bookchapter(s),patent(s):

• N.T.X.Nguyen,S.Sarter,N.HaiNguyen,P.Daniel.DetectionofmolecularchangesinducedbyantibioticsinEscherichiacoliusingRamanandIRspectroscopies.SpectrochimicaPartA:MolecularandBiomolecularSpectroscopy.183395-401(2017).

• N.N.Phuong;L.Poirier;F.Lagarde;A.Kamari;A.Zalouk-Vergnoux(2018),Abundanceandcharacteristics of microplastics in Atlantic coastal sediments, Environmental Pollution,243(PtA),DOI:10.1016/j.envpol.2018.08.0322018.

• R.Gillibert,M.Triba,MarcLamydelaChapelle,SurfaceEnhancedRamanScatteringSensorforHighlySensitiveandSelectiveDetectionofOchratoxinA,Analyst,143,339,2018.

• R.Gillibert, J.Q.Huang,Y.Zhang,W.L.Fu,M. Lamyde la ChapelleExplosivedetectionbySurfaceEnhancedRamanScattering,TrendinAnalyticalChemistry,105,166,2018

• R.Gillibert,J.Q.Huang,Y.Zhang,W.L.Fu,M.Lamyde laChapelleFoodqualitycontrolbySurfaceEnhancedRamanScattering,TrendinAnalyticalChemistry,105,185,2018

• N. N. Phuong; L. Poirier; Q. T. Pham; F. Lagarde; A. Zalouk-Vergnoux (2018), Factorsinfluencing the microplastic contamination of bivalves from the French Atlantic coast:Location, season and/or mode of life? Marine Pollution Bulletin, 129(2), 664-674,https://doi.org/10.1016/j.marpolbul.2017.10.054.

• M.Cottat,R.Yasukuni,Y.Homma,N.Lidgi-Guigui,N.Varin-Blank,M.LamydelaChapelle,C.Le Roy, Phosphorylation impact on Spleen Tyrosine kinase conformation by SurfaceEnhancedRamanSpectroscopy,ScientificReports7,39766,2017

• Nguyen,H.,F.Lagarde,G.Louarn,andP.Daniel.“ANewWaytoDiscriminatePollutedWoodby Vibrational Spectroscopies.” Talanta 167 (2017).https://doi.org/10.1016/j.talanta.2017.02.032.

• N.N.Phuong;A.Zalouk-Vergnoux;A.Kamari;C.Mouneyrac;F.Amiard;L.Poirier;F.Lagarde(2017),Microplastics inbluemussels(Mytilusedulis)of theFrenchAtlanticcoast:protocolset-up and preliminary data on the contamination, Environmental Science and PollutionResearch,DOI:10.1007/s11356-017-8862-3.

• Chauvet, R., F. Lagarde, T. Charrier, A. Assaf, G. Thouand, andP. Daniel. “MicrobiologicalIdentificationbySurface-EnhancedRamanSpectroscopy.”AppliedSpectroscopyReviews52,no.2(2017).https://doi.org/10.1080/05704928.2016.1209760.

• Alami,A.El,F.Lagarde,U.Tamer,M.Baitoul,andP.Daniel.“EnhancedRamanSpectroscopyCoupled to Chemometrics for Identification and Quantification of AcetylcholinesteraseInhibitors.” Vibrational Spectroscopy 87 (2016).https://doi.org/10.1016/j.vibspec.2016.09.005.

• N.N.Phuong,A.Zalouk-Vergnoux,L.Poirier,A.Kamari,A.Châtel,C.Mouneyrac,F.Lagarde(2016),Isthereanyconsistencybetweenthemicroplasticsfoundinthefieldandthoseusedinlaboratoryexperiments?,EnvironmentalPollution,211,Pages111–123.

• Peng-Ubol,T.,P.Phinyocheep,F.Lagarde,P.Daniel,J.-F.Pilard,W.Panbangred,G.Thouand,and M.-J. Durand-Thouand. “Functionalized Polyurethane Applied for Foodborne PathogenDetection.” Journal of Food Measurement and Characterization 9, no. 3 (2015).https://doi.org/10.1007/s11694-015-9230-y.

• M. Cottat, C. D’Andrea, R.Yasukuni, N.Malashikhina, R. Grinyte, N. Lidgi-Guigui, B. Fazio, A.Sutton,O.Oudar,N.Charnaux,V.Pavlov,A.Toma,E.DiFabrizio,P.G.GucciardiM.LamydelaChapelle , High Sensitivity, High Selectivity SERS Detection of MnSOD Using OpticalNanoantennasFunctionalizedwithAptamers,J.Phys.Chem.C11915532,2015.

v Organizationofsyntheticandnaturalmicroandnano-objectsInvestigation by X-ray holotomography of the 3D microstructure ofmicroorganismstounderstandtheirroleoftheirbiologicalfunctions.A.Gibaud

Projets:Publication(s),bookchapter(s),patent(s):• T.Beuvier,B.SuchérasMarx,L.Beaufort,I.Probert,Y.Chushkin,F.ZontoneandA.Gibaud,2018,

Nat.Com• AMcheik,SCassaignon, JLivage,AGibaud,SBerthier,PJLopez,Frontiers inMarineScience5,

123,2018• O.Cherkas,T.Beuvier,D.W.Breiby,Y.Chushkin,F.ZontoneandA.Gibaud,2017, 17 (8), pp 4183–

4188

UltrafastPhenomena2015-20181-Electronandphononultrafastdynamic in solidsexhibitingexoticcouplingbetweencharge,spinandstructure.

Researchers:V. Juvé,G.Vaudel,T.Pezeril,M.Edely,B.Arnaud,R.Busselez,P.Ruello.Coll.B.Dkhil,C.Paillard,SPMSCentraleSupelec, J.Szade,K.Balin, InstituteofPhysics,Katowice(Poland).LaboratoireInternationalAssociéFrance-Japon(LIA-IM-LED)

v Ultrafastphotostrictioninferroelectricsandmultiferroics

Abstract: The control of the photoinduced coherent acoustic phonon in ferroelectricandmultiferroiccompoundshavebeeninvestigatedinordertoinvestigatetheelectron-phononcouplingandthecoherentacousticphonondetectionprocesses.Thisresearchhaspermittedtorevealanoriginalultrafastoptical-lightmodeconversioninBiFeO3andLiNbO3.Wehave shown that itwaspossible to switch the lightpolarization from theordinary to the extraordinary component (and vice-versa) with coherent acousticphonon and this, up to hundreds of GHz (10ps). This mechanism is based on themodulation of the birefringence of the uniaxial crystal (BiFeO3, LiNbO3) induced,through the acousto-optic effect, by the coherent acoustic phonons (left panel in thefigure below) [1]. Thiswork has been selected by INPCNRS as a “highlight” [2]. Thisresearchisstillgoingonwithafocusonnewpossiblewaytogenerateacousticphonon[3] (transformation of light energy intomechanical energy)with an ANR project UP-DOWN(IMMMleader)thathasstartedinOctober2018.Theextensionofthecouplingbetween coherent acoustic phonons with the magnetic order and in particular withantiferromagnonswill be investigated in theANRSANTA (SPEC-CEALeader) thathasstartedinOctober2018aswell.

Ultrafast light-mode conversion in birefringentferrolectricmaterials.

Ultrafast electron and phonon dynamics inTopologicalinsulators

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Projets:LmacRégionPaysdelaLoire(Ferrotransducteur2015-2019),ANRUP-DOWN2018-2021.Publication(s),bookchapter(s),patent(s):

[1]Ultrafast acousto-optic mode conversion in optically birefringent ferroelectrics,Mariusz Lejman, Gwenaelle Vaudel, Ingrid C Infante, Ievgeniia Chaban, ThomasPezeril,MathieuEdely,GuillaumeFNataf,MaelGuennou,JensKreisel,VitalyiEGusev,BrahimDkhil,PascalRuello,Naturecomm.7,12345(2016)[2]http://www.cnrs.fr/inp/spip.php?article4895[3]Photothermaloptomechanics,PRuello,NaturePhotonics10(11),692(2016).

v Ultrafastelectronandphonondynamicsintopologicalinsulators.

Abstract: Inthisworkwehaveinvestigatedultrathinfilmsoftopological insulator(4-15nm). We have first studied the influence of the substrate and the microstructure(singleversuspolycrystallinestructureonthefemtosecondpulse-inducedelectronandphonondynamics.Whiletheopticalphonons(zerogroupvelocity)havefrequencyanddampingdynamicsnearlyunaffected,theacousticphononsignature(propagatingwave)is clearly different revealing the importance of acoustic phonon scattering on grainsboundaries and at interface between the nanometric film and the substrate [1]. In asecond study, we have in particular measured the dynamic of hot carriers in Bi2Te3compoundandhave shown theexistenceof a strongquantumconfinementappearingforthicknessasthinas5-6nm.Adramaticenhancementofthehotcarriersrelaxationisobserved(rightpanelinthefigureabove).SuchquantumconfinementisalsorevealedinathicknessdependenceoftheprocessofgenerationofcoherentacousticphononsandintheanomalousdampingofaRamanactivemodeA1gmode,togetherwithaslightA1gmodesoftening.Thesephenomenaevidenceadrasticevolutionoftheelectron-phononcoupling inahighlyconfinedsystem.Wehaveproposedwithasimplemodel, thatthebandgapincreaseswithdecreasingthethicknessisanindicationoftheincreaseoftheelectron-longitudinal acoustic phonon deformation potential. A more advancedtheoretical work is now required to extract a more precise microscopic picture.Nevertheless,theseexperimentalresultsareimportanttotailortheproperthicknessofsuchmaterialforfutureintegrationinmorecomplexdeviceswhereforexamplespin-to-chargeconversionwillbeinvestigated.Projets:French-Polishproject,BourseAmbassadedeFrance(M.Weis),thèseco-tutelle(LeMans,InsttutdePhysiqueKatowice).Publication(s),bookchapter(s),patent(s):-Ultrafastlight-inducedcoherentopticalandacousticphononsinfewquintuplelayersof the topological insulatorBi2Te3,MWeis,KBalin,RRapacz,ANowak, M Lejman, JSzade,PRuello,PhysicalReviewB92(1),014301(2015)

- Quantum size effect on charges and phonons ultrafast dynamics in atomicallycontrolled nanolayers of topological insulators Bi2Te3,M.Weis, BWilk,G Vaudel, K.Balin,R.Rapacz,ABulou,BArnaud,JSzade,PRuello,Sci.Rep.7,13782(2017)2-Nonlinearacousto-magneto-plasmonics

v Topologicalandnonlinearmagneto-plasmonicsResearchers:V.Juvé,G.Vaudel,V.V.Temnov;D.Kuzmin,I.Bychkov(ChelyabinskStateUniversity,CNRS-RFBRPRCpartneruniversity).Abstract: In functional magnetic nanostructures acoustic, magnetic and plasmonicexcitations can co-exist and interact on nanometer spatial and ultrafast time scales.Opticalspectroscopywithfemtosecondlaserpulseshighlightsavarietyofnonlinearandspatio-temporaldynamicalphenomena,whicharenotonlyused tomonitor individualexcitations in real time, but also to study their mutual interaction mechanisms [1].Hybridmetal-ferromagnetmultilayerstructures[2]ofperiodicallypatternedplasmonicthin films in various topological configurations [3] can display unique linear andnonlinearmagneto-opticalproperties;someofthemcanbeprobedbymagneticsecond-harmonic(SH)generation.Nonlinear magneto-plasmonic experiments on metal-ferromagnet multilayer filmsexploitasignificantdispersionofsurfaceplasmonpolaritons(SPPs)atfundamentalandSH frequencies, which can be excited at different incidence angles in Kretschmannconfiguration using femtosecond laser pulses [1,2]. This angular dependence andmagnetic control of second-order nonlinear-optical interactions at noble metal-ferromagnet interfaces enable the detailed study of phase-matching conditionsgoverningtheexcitationofSPPs.Periodicnanostructuringofmagnetic thin films introducesnewdegreesof freedom inmagneto-optical measurements allowing for the transition between optical gratings(largeperiodicitycomparedtoopticalwavelength)andmetasurfaces(smallperiodicity)tobeobserved.Asafirststepinunderstandingofthisnewclassoffunctionalmagneto-opticalnanomaterialswehaveinvestigatedtheWood’sdiffractionanomalyonperiodicarrays of nickel nanodimers. A periodic structure acting as a meta-surface at thefundamentalfrequencyandasadiffractiongratingatthedoubleSHfrequencyhasbeenidentifiedusingconceptsoflinearandnonlinearWood’sanomalies[4].Projets : This research is by now currently supported by a Strategie Internationale“NNN-TELECOM” de la Region Pays de la Loire (2015-2019), French-Russian CNRS-RFBRPRC“Acousto-magneto-plasmonics”(2017-2019),EuropeanCOSTactionMP1403“Nanoscale quantum optics”, the ITMO University St. Petersburg (Researchprofessorshipprogram2019-2021).

Nonlinearmagneto-plasmonics[1,2]

Topologicalplasmonics[3]

Publication(s),bookchapter(s),patent(s):[1]V.V.Temnovetal.,J.Opt.18,093002(2016)[2]I.Razdolskietal.,ACSPhotonics3,179(2016)[3]D.A.Kuzminetal.,ACSPhotonics4,1633(2017);Nanophotonics7,597(2018)[4]M.Tranetal.,Phys.Rev.B98,245425(2018)

v Ultrafastacousticsandmagneto-acousticswithsurfaceacousticwaves

Researchers:V.V.Temnov;V.S.Vlasov,A.Golov,L.N.Kotov(SyktyvkarStateUniversity,CNRS-RFBRPRCpartneruniversity),D.Seletsky,A.Leitenstorfer(KonstanzUniversity,ANR-DFGpartneruniversity).Abstract:Optical spectroscopy with femtosecond laser pulses highlights a variety of nontrivialspatio-temporaldynamics,whicharenotonlyusedtomonitorindividualexcitationsinreal time, but also study interaction mechanisms between them, often observed infrequencymixingphenomena.Inacousticsandmagnetismtheyareoftendominatedbyparametric resonances, where system parameters are modulated at frequenciescomparabletothenaturaloscillationfrequencies,typicallyintheMHz-GHzrange.In recent experiments [1,2] themagnetization in a Ni/glass sample is excited by twodistincttransientsurfaceacousticwaves(denotedasSAWandSSLW,respectively,andrecentlyquantifiedintime-resolvedx-raydiffractionexperiments[3]).Magnetictuningof the FMR frequency in resonance to their SHG, sum- and difference frequenciesdemonstrates the full variety of frequency mixing phenomena [2]. In contrast tononlinear optics, the frequency mixing is dominated by the parametric effect in theexternally driven FMR oscillator. An analytical model based on the resonantenhancement of frequency-mixed signals explains the experimental observations [2].The detailed understanding of magneto-interactions in nickel thin films motivatesrealisticconceptsforacousticmagnetizationswitchingatthenan-scale.Forexample,wehaveperformed realisticmodeling fornickelnanostructures to show that anellipticalnickelnanoparticleplacedinaweakexternalmagneticfieldcanbeswitchedwithsmall-amplitudepulsesofsurfaceacousticwaves[4].Extending our theoretical modeling beyond the acoustically-driven FMR precessionallows us to study intriguing interactions between ultrashort acoustic pulses andstanding spin waves (exchange magnons) in thin ferromagnetic films. A practical

applicationofthesefindingstomagneto-elasticswitchinginbi-stablesystems,i.e.nickelnanomagnets,isunderway[4].Projets : This research is by now currently supported by a Strategie Internationale“NNN-TELECOM” de la Region Pays de la Loire (2015-2019), French-Russian CNRS-RFBR PRC “Acousto-magneto-plasmonics” (2017-2019), French-German ANR-DFG“PPMI-NANO”(2015-2019),theITMOUniversitySt.Petersburg(Researchprofessorshipprogram2019-2021).

Parametricmagneto-acousticfrequencymixing[2] Elasticswitchingofnanomagnets[4]Publication(s),bookchapter(s),patent(s):

[1]J.Janusonisetal.,Phys.Rev.B94,024415(2016)[2]C.L.Changetal.,Phys.Rev.B95,060409(2017)[3]M.Sanderetal.,Phys.Rev.Lett.119,075901(2017)[4]V.S.Vlasovetal.,Crystals(toappearin2019)3-UltrafastterahertzspectroscopyResearchers:G.Vaudel,V.V.Temnov,P.Ruello,T.Pezeril,V.Juvé.Coll.JYCHauleau,M.Viret, CEA-SPEC, J. Szade Institute of Physics Katowice (Poland), LaboratoireInternationalAssociéCNRS,France-Japon(LIA-IM-LED)

v THzpolarizationmodulationofvisiblelightbyTHzpulses

Abstract:Overthelastdecade,ultrafastTerahertzspectroscopyhasgainedtremendousattention thanks to the development of high-power ultrafast laser systems, whichallowed generating intense single-cycle picosecond pulses of electric field at THzfrequencies.Theirrelativelylongopticalcycleperiod(1psfor1THz)andhighelectricfield (from hundred of kV/cm to few MV/cm) provide a new tool for studyingfundamentalaspectsoflight-matterinteractions.Field-resolveddetectionofultra-shortTHzpulsesiswellknownsincemanyyearsandthemostcommontechniqueisbasedon

free-space electro-optic sampling. This leads to the polarization change of an opticalpulse,whichisdetectedbythepolarizationsensitivescheme,andtothefield-resolveddetection of a THz pulse. Herewe evidenced efficient non-resonant and noncollinearχ(2)-type type light-matter interaction in femtoseconds polarization sensitive time-resolved opticalmeasurements. Such nonlinear optical interaction of visible light andultra-short THz pulses leads to THz modulation of visible light polarization in bulkLiNbO3crystal.Theoreticalsimulationsbasedonthewavepropagationequationcapturethephysicalprocessesunderlyingthisnonlineareffect[1].

Left: A femtosecond optical pulse and a THz pulse, delayed in time respect to each other, areoverlapping in a LiNbO3 crystal. Right: Non-resonant and noncollinear χ(2)-type light-matterinteractionleadstoarotationΔθoftheopticalpulsepolarizationatTHzfrequencies.

Projets : Région Pays de la Loire (Pari Scientifique NanoPlasmag 2018-2021), ANRSANTA2018-2021.Publication(s),bookchapter(s),patent(s)[1]V.Juvé,G.Vaudel,Z.Ollmann,J.Hebling,V.Temnov,V.GusevandT.Pezeril,OpticsLetters43(2018)

v Ultrafast THz emission by spin to charge current conversion (ferroicmaterialsandtopologicalinsulators)

Abstract:Topologicalinsulators(Bi2Se3,Bi2Te3etc…)areanewclassofmaterial,whichisstatedtobeatthecoreofthenextgenerationofelectronicsdevices.Theirstructureconsistsofabulksmallbandgap insulator togetherwithspinpolarizedsurfacestates,whichcanleadtosurfacespincurrent.Studyingandcontrollingthesurfacespincurrentisofinterestforthescientificcommunity.UsingultrafastTHzspectroscopy,withphotonenergy smaller than the band gap, one can try to have access to the surface statesdynamics and, thus, to the spin dynamics. High quality samples, which are wellcharacterizedofBi2Te3,areprovidedbytheUniversityofSilesiainPoland[1].

Left:Simplifiedbandstructureoftopologicalinsulators,whichconsistsofacombinationofasmallband gap together with spin-polarized Dirac cones. Right: Relative change of the transmissioninducedbyaTHzpulse(2meVphotonenergy)measuredwitha3.1eVphotonenergyforaBi2Te3sampleof15nmthickness.

We also have started to investigate the emerging field related to spin-to-charegconversion (vice-versa). spin bursts can be produced by direct excitation of hotelectrons in a ferromagnetic layer triggered by a femtosecond laser pulse. During therelaxationprocessesthediffusionlifetimeandmobilitydifferformajorityandminorityspin carriers, resulting in the emission of angular momentum on a timescale ofpicoseconds. This effect, combined with Inverse Spin Hall Effect in an adjacent non-magnetic layer (Pt), was recently used to make efficient THz generation devices [2].Based on this principle, we have already carried out preliminary measurement withCoFeBonPt by shining femtosecond laserpulses to inject spin current bursts.As thedirectionofspincurrentisdeterminedbythemagnetizationoftheFerromagnetic,themechanismprovidesaneasyandefficientwayofcontrollingthedirectionofspintorquewithasmallmagnetic field.Thisproject ispartof theSantaANR(2018-2021) leadbyMichelViret(CEA/SPEC)withinwhichIMMMisinvolved(startingOct2018).

Left:PrincipleofthespintochargecurrentconversionleadingtoTHzemission(takenfromSeifertetalNat.Phot.2016).Right:UltrafastTHzemissionmeasuredbyelectro-opticsamplingafterultrafastphotoexcitationinaFeCoB(5nm)/Pt(3nm)sample.ReversingtheexternalmagneticfieldleadstoachangeofsignoftheTHzelectricfield.

Projets : Région Pays de la Loire (Pari Scientifique NanoPlasmag 2018-2021), ANRSANTA2018-2021.

Publication(s),bookchapter(s),patent(s):[1]V.Juvéetal,inpreparation[2]T.S.Seifert,N.M.Tran,O.Gueckstock,S.M.Rouzegar,L.Nadvornik,S.Jaiswal,G.Jakob,V.V.Temnov,M.Münzenberg,M.Wolf,M.KläuiandT.Kampfrath.J.Phys.DAppl.Phys.(2018)4-UltrafastAcousticsResearchers:R.Busselez,T.Pezeril,G.Vaudel,V.Juvé,G.Brotons,N.Delorme,P.Ruello.Coll. H. Piombini, P. Belleville CEA LeRipault, V. Gusev, S. Raetz, N. Chigrev LAUMLeMansUniv(LmacProject).K.Nelson,C.Klieber(MIT,USA)

❖ Vibrationalpropertiesofliquidsandinterfacialliquids

Abstract:AtSolid-Liquidinterface,adropofliquidfilmthicknesstowardsnanoscaleinducesdeepmodificationsofthe liquidpropertiessuchasheatorparticletransport, fluidrheologyandlubrication.Amongtheproperties impactedbythefluidsizereductionandliquid-solidinterface,theimportanceofthemodificationsinvibrationalpropertiesareactuallyscrutinized and debated. Despite this interest in interfacial liquids, experimentalmeasuresarenoteasilyaccessibleatexceptionsofSurfaceForceApparatusandAtomicForce Microscopy techniques. We recently develop a home-built Time DependantBrillouinScatteringpermittingtoreachtheGHzdynamicsrangeforliquidsofthicknesscomprises between few microns to tenth of nanometers permitting to access toviscoelasticpropertiesfromthebulkliquidstothinfilmsandmayshedanewlightonthecomprehensionofinterfacialfluidproperties.TDBS measurements are also supported by molecular dynamics simulations whichpermitstobridgeagapbetweenthelengthandtimescalesofbothtechniquesandmayrelate modifications of macroscopic values such as viscoelastic properties tomicroscopicaspects.

Figure 6: Left: TDBS spectra of glycerol at different temperatures. Right: Velocity of longitudinal andtransverse sound as a function of frequency obtained with molecular dynamics simulation of glycerol atdifferenttemperatures

Projects:ANRPlusDilRelatedpapers:

[1]I.Chaban,H.D.Shin,C.Klieber,R.Busselez,V.E.Gusev,K.A.NelsonandT.Pezeril,Time-domainBrillouin scattering for thedeterminationof laser-induced temperaturegradientsinliquids,ReviewofScientificInstruments,2017,88,074904.[2]R. Busselez, T. Pezeril and V. E. Gusev, Structural heterogeneities at the origin ofacoustic and transport anomalies in glycerol glass-former, The Journal of ChemicalPhysics,2014,140,234505.

v ProbingelasticityatthenanoscaleAbstract: The ability to generate and to detect with femtosecond lasers coherentacousticphononswithveryhighfrequency(10-100sGHz)offersanuniquepossibilitytodirectly measure the propagation speed of these acoustic phonons in nanostructuresand then to investigate the elasticity [1]. Within this context, we have applied ourmethod to probe the elasticity of different systems. First of all, we have studiedassemblies of silica nanoparticles (10nm). These are the central element in advancedcoating of many lenses in the French project Laser MégaJoule of CEA-DAM. Therealization of coatingwith NPs assemblies permits to remove the coating quite oftenaftereachLaserMegaJouleImpactandtorenewthenthelenses.However,noadvancedinvestigationsof themechanicalpropertiesof thesecoatingwereachievedup tonow.This was our task. In this study, we have been able then to reveal the nature of thecontact between nanoparticles (Van der Waals or Hydrogen, Covalent) directly byevaluatinghowfastthecoherentacousticphononpropagatewithinathinfilmmadeofthisnanoparticle(seefigurebelow).Thetransformationofsuchbond(calledhardeningprocess) was realized by chemists of CEA. We have been then able to extract thecharacteristicelasticmodulusoffilmsasthinas70nm(butthetechniquecanbeappliedto thinner system) [2].This researchhasbeen selectedbyCEADAMasoneof the25moreimportantresultsin2017ofresearchatCEADAM.Wehavealsorecentlyappliedthismethodtodetectaphasetransition inthin filmsofthe multiferroic compound BiFeO3. In particular, we are able to distinguish thetransition from the rhombhedral to tetragonal phase by analyzing the values of thesoundvelocitymeasuredinsub-micrometricfilms[3].

Left:principalofapump-probemethodonathinfilmmadeofanassemblyofnanoparticles.Thepump laser can induced mechanical resonances of the film that in turn induce some periodicmodulation in time on the optical reflectivity. The latter one ismeasuredwith the probe beamTypicallmechanicaloscillationsareshownontherightwherethechangeoffrequencyofthetwofirsteigenmodeclearlyindicatethemodificationofthenanoscontactstrength.

Projets:ContratCEA(2015-2018)avecBoursecofinancéCEA-RégionPaysdelaLoire.Publication(s),bookchapter(s),patent(s):[1] Advances in applications of time-domain Brillouin scattering for nanoscale imaging, VEGusev,PRuello,AppliedPhysicsReviews5(3),031101(2018)[2]Controlling theNanocontactNatureand theMechanicalPropertiesof a SilicaNanoparticleAssembly, J Avice, C Boscher,G Vaudel, G Brotons, V Juvé, M Edely, CMéthivier, Vitalyi EGusev,PhilippeBelleville,HervePiombini,Pascal Ruello The JournalofPhysicalChemistryC121(42),23769-23776(2017)[3]Evaluationof the structuralphase transition inmultiferroic (Bi1-xPrx)(Fe0.95Mn0.05)O3thinfilmsbyamulti-techniqueapproachincludingpicosecondlaserultrasonics,SamuelRaetz,Alexey Lomonosov, Sergey Avanesyan, Nikolay Chigarev, Elton de Lima Savi, Alain Bulou,NicolasDelorme,ZhengWen,QiaoJin,MajuKuriakose,AnthonyRousseau,GwenaëlleVaudel,PascalRuello,DiWu,VitalyiGusev,inrevisioninAppliedSciences.5-Simulationofultrafastphenomena Researchers:B.Arnaud,F.Calvayrac

❖ ElectronandphonondynamicsinphotoexcitedsolidsAbstract:Pump probe experiments like optical pump probe experiments, time resolved X-raydiffraction, or time resolved photoemission experiments are currently used to studyelectron and phonon dynamics in nanostructures on time scales ranging from a fewfemtoseconds to a few picoseconds. Among the aforementioned techniques, opticalpumpprobeexperimentsallowtostudythecoherentphonongenerationmechanismsor

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eventhepossibility todemagnetizeasamplewithanultrashort laserpulse. It isoftendifficult to interpret experimental results without resorting to models whoseparameters can be inferred from ab-initio calculations. There are few calculationsbecause of the need to describe non-equilibrium phenomenon occurring on differenttimescalesandlengthscales.Nonetheless,ab-initiocalculationscombinedwithmodelsalready shed new light on ultrafast physics, especially on the coherent phonongeneration, on the non thermalmelting processes or on the energy transfer from theelectronicdegreesoffreedomtothethevibrationaldegreesoffreedoms.

Figure 7: Schematic view of relaxationprocessesinphotoexcitedsilicon

RelatedPapers:IsabelGonzálezVallejo,GeoffreyGallé,BriceArnaud,ShelleyA.Scott,MaxG.Lagally,DavideBoschetto,Pierre-Eugene Coulon, Giancarlo Rizza, Florent Houdellier, David Le Bolloc’h, and Jerome Faure,“Observationoflargemultiplescatteringeffectsinultrafastelectrondiffraction”,Phys.Rev.B97,054302(2018).

❖ TDDFTapproachestocomputeexcitedstatesoffinitesystemsAbstract:ThePW-TELEMANprojectaimsatdevelopinganopensource(underGPL3)andeasyaccessiblepackageofreal-timeTDDFTlibrariesandcodes,basedonprogramsdevelopedoverthepast20yearsinaToulouse-ErlangencollaborationwhichspreadtoLe Mans and China via former students. At the time being no available code trulyaccountsforacompletenon-adiabaticelectron-ionscouplingallowingafullfollow-upofawholedynamical scenario fromearly excitation (fs or sub-fs) to long time response(ps) of a givenphysical system.To the best of our knowledge, theToulouse-Erlangen

packageisoneofthesingleonesallowingsuchaninvestigationinafullytime-resolvedmanner.Stillthispackagerequiresastrongeffortofstandardizationanddocumentationandinordertomakeitmoreefficientandusablebyexternalgroups.Moreoptimizationishighlydesirable toexploit the latest computer technologysuchasGPGPUandso toaccessthemuchmoredemandingtasksinorganicmolecules.Itisthegoaloftheprojecttosucceedinthesetwocomplementingdirections.The variety of potential applications is obvious. We mention in particular the verypracticalaspectsconcerningirradiationofbiologicalmoleculesandradiationdamageinmaterials. The plan is to develop our project in two complementing directions: first,implementation and tests of formal developments such as approximations toTDSIC/OEP methods, coupled with an exploration of various dynamical scenarios ofincreasing complexity (requiring ongoing optimization), starting with free moleculesandclusters, turningtosystemssuchasachromophoreclusterembeddedinamatrix,endingwithacoupledquantummechanics/molecularmechanicshierarchicalmodelingof a biophysical problem made possible due to the expected increase in numericalperformanceandontheotherhandstandardization,documentation,andpublicationofatoolboxofroutineswhichwillbeeasilyusablebyothergroups.

Figure 8: Benchmark of PW-Teleman code, Efficiency versus core number for differents architectureoptimisation

Projects:ANRTelemanRelatedPapers:F.Calvayrac,Kullback-Leiblerdivergenceasanestimateofreproducibilityofnumericalresults,in:IEEE,2015:pp.1–5.doi:10.1109/NTMS.2015.7266501.