st International School on Nano-Toolingnanotoolingschool.isasi.cnr.it/wp-content/uploads/2017/03/Nano... · 1st International School on Nano-Tooling Manipulating, Shaping and Functionalizing

1stInternationalSchoolonNano-ToolingManipulating,ShapingandFunctionalizingtheMatter

30-31March2017Pozzuoli(NA),Italy

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CNR-ISASIDirectorPietroFerraroDirectorsoftheSchoolCarmineGranataSimonettaGrilliDomenicoPaparoLuciaPettiClaudiaTortiglioneOrganizingCommitteeAntigoneMarinoBerardoRuggieroLogisticsupportAntoniod’OrazioPatrizioMignianoGianlucaCodaSecretaryValentinaFormicolaFlaviaCafiero

InCollaborationwith

TechnicalSponsor

Supportedby

SocietàItalianadiFisica

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INTRODUCTION“Nano-Tooling:Manipulating, Shaping and Functionalizing theMatter” is one of the five scientificpillars of the mission at CNR-ISASI (www.isasi.cnr.it). The unique competences and technologicalfacilitiesresidingatCNR-ISASIaffordsubstantialandinterdisciplinaryresearchskillsonseveralup-to-datetopicsinbiomedicaltechnologies,aerospace,energy,materialscience.Theavailableadvancedfacilitiesandtherelatedtechnologiespermittoprocessthematteratmicroandnanoscaleandcansupportdesignandrealizationofdevicesforanykindofapplication.The scopeofNano-Tooling School is toprovidea two-days full-immersion trainingon6advancedtechnologies:

1) HolographicLithography;2) E-BeamLithography;3) MagneticNanosensing;4) AdvancedInkjetPrinting&AdditiveManufacturingatNanoscale;5) FunctionalNanoparticlesforNanomedicine;6) FemtosecondLaserStructuringandPatterning.

TheNano-ToolingSchoolisaddressedmainlytoMScstudents,PhDstudentsandpost-docresearchers,butalsoresearchersfromanybranchofsciencewhowishtoincreasetheirknowledgeandawarenessaboutmicroandnanotechnologiesareverywelcome.TheobjectivesofNano-ToolingSchoolare

• Bringing to the attendees the concepts and the basic working principles of the above-mentionedNano-Tools

• AddressingcompleteunderstandingofhowtheNano-Toolshavebeenexploitedforachievingrecent significant results in groundbreaking research as well as in applied sciences by theinvestigatorsworkingatCNR-ISASI

• GivethechancetofollowguidedvisitsatCNR-ISASIfacilitieswiththelocalexpertsTheSchool isdirectedbyCNR-ISASIteamLeadersthatareresponsibleforthefacilitiesandfortherelatedresearchtopics.LecturesbyworldwideprominentscientistswillbegiveninstreamingoneachoneoftheaboveNano-Tools.

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ABOUTSCIENCEAPPTheInstituteofAppliedSciences&IntelligentSystems(ScienceApp)isoneamongthe106institutesoftheItalianNationalResearchCouncil(CNR).FormernameofScienceAppwasInstituteofCybernetics,thatwasstartedbythephysicistEduardoRenatoCaianielloin1968.ThemissionandthenameofInstituteofCyberneticswaschangedrecentlyaccordingtothenewstrategiclinesdrawnbythenewdirectorPietroFerrarothatonthe1stdayofNovember2014wasappointedas6thdirectorinthehistoryofInstituteofCybernetics.TheCNRofItalyisapublicorganization;itsdutyistocarryout,promote,spread,transferandimproveresearchactivitiesinthemainsectorsofknowledgegrowthandofitsapplicationsforthescientific,technological,economicandsocialdevelopmentoftheCountry.ScienceAppisoneof11institutesofthePhysicalSciencesandTechnologiesofMatter.TheInstituteheadquarterislocatedinPozzuoli(Napoli)c/oComprensorioOlivetti.ScienceAppisfocusedoninterdisciplinaryresearchandtheculturalbackgroundsofresearchstaffandfellowsisarealmixofdifferentexpertiseanddisciplines.ScienceAppisequippedwithrelevanttechnologicalFacilitiesandLabs.CurrentlyScienceAppstaffhasatotalof50Researchers,31amongPostDocResearchFellows,PhDstudentsandcollaborators.MoreovercontributetoresearchactivitiesofScienceAppabout23AssociateResearchersfromvariousuniversitiesandresearchcenters.

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08:50-09:00 WelcomebyISASIDirectorPietroFerraro

HolographicLithography(chairSimonettaGrilli)

09:00-09:40 VitoPagliarulo(ISASI,Pozzuoli,Italy)Introductiontoholographiclithography:fromfundamentalstoapplications

09:40-10:30 RobertoAlfioFallica(PaulScherrerInstitut,Villingen,Swiss)EnablingnextgenerationlithographyattheXILbeamline:fromsingle-digitresolutiontomaterialscharacterization.

10:30-11:00 CoffeeBreak

AdvancedInkjetPrinting&AdditiveManufacturingatNanoscale(chairSimonettaGrilli)

11:00-11:20 SaraCoppola(ISASI,Pozzuoli,Italy)Liquidnano-dispensingbypyro-electrohydrodynamics

11:20-11:40 OriellaGennari(ISASI,Pozzuoli,Italy)Pyroelectric-basedplatformsforbiologicalapplications

11:40-12:30 SerdarOnses(ErciyesUniversity,Turkey)Mechanisms,Capabilities,andApplicationsofHigh-ResolutionElectrohydrodynamicJetPrinting

12:30-14:00 LunchBreak

MagneticNanosensing(chairCarmineGranata)

14:00-14:45 CarmineGranata(ISASI,Pozzuoli,Italy)Magneticnanosensorbasedonquantuminterference:apowerfultoolfornanoscaleinvestigations

14:45-15:30 JohnGallop(NationalPhysicalLaboratory,Teddington,LondonUK)MagneticnanosensingwithSuperconductingQuantumSensor


E-BeamLithography(chairLuciaPetti)

16:00-16:30 LuciaPetti(ISASI,Pozzuoli,Italy)"Man-made"CuttingEdgeMaterialsforLightControlandManipulationattheNanoscale

16:30-17:00 MassimoRippa(ISASI,Pozzuoli,Italy)EngineeredPlasmonicPhotonicNanostructuresfor"Label-Free"Biosensing

17:00-17:30 JanLagerwall(UniversityofLuxembourg,Luxembourg)Combiningnanoscaleself-assemblyand3D-printingtomeettheconstructionchallengesofthefuture

17:30 Endoftheday

Thursday30March

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FunctionalNanoparticlesforNanomedicine(chairClaudiaTortiglione)

09:00-09:20 MariaMoros(ISASI,Pozzuoli,Italy)Synthesisandcharacterizationofinorganicnanoparticlesforbiomedicalapplication

09:20-09:40 ClaudiaTortiglione(ISASI,Pozzuoli,Italy)Asimplebiologicalmodelfornanomedicine

09:40-10:30 ValeriaGrazu(AragònMaterialScienceInstitute,Zaragoza,Spain)MovingNanobiotechnologyfromtheLabtotheMarket


FemtosecondLaserStructuringandPatterning(chairDomenicoPaparo)

11:00-11:30 SalvatoreAmoruso(UniversityofNaplesFedericoII,Naples,Italy)Femtosecondlasersurfacestructuring:principlesandapplications

11:30-12:00 DomenicoPaparo(ISASI,Pozzuoli,Italy)Femtosecondlasersurfacestructuringwithpolarization-shapedlight

12:00-12:30 EmmanuelI.Stratakis(UniversityofCrete,Hellas)Ultrashortpulsedlasersurfacestructuringformicrofluidicsandtissueengineering

12:30-14:00 LunchBreak

14:00-14:10 PhaserOSAStudentChapter

17:30 SchoolCertificateDelivery

Friday31March

14:10-17:30 LabVisit

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Introductiontoholographiclithography:fromfundamentalstoapplications

VitoPagliarulo

InstituteofAppliedSciencesandIntelligentSystemsoftheNationalCouncilofResearch(CNR-ISASI)ViaCampiFlegrei34,80078Pozzuoli(NA),Italy

E-mail:[email protected]

Starting from an introduction on nanolithography in general, this lesson is an overview on thefundamentalsofLaserInterferenceLithography.ItshowstwosimplesetupsthatareMach-ZehnderInterferometerandLloydmirroranddiscussestherelativeadvantagesanddisadvantagesintermsofefficiency,exposedareaandresolution.Differentexamplesregardingdifferentapplicationfields(i.e.aerospace, biomaterials, ferroelectricmaterials) are illustrated. Aerospace application regards thefabricationofHolographicOpticalElements to improve theefficiencyof solarpanels forsatellites.Biomaterialregardstheuseofazopolymerstocreatepatternedsurfacestoinvestigatevariousaspectsofcellbehaviour.Lastly,weshowsthefabricationofperiodicallypoledlithiumniobatesamplesbyelectricfieldpoling,afterpatterningbyinterferencelithography.

References[1] C.Riannaetal.Reversibleholographicpatternsonazopolymersforguidingcelladhesionand

orientationACSappliedmaterials&interfaces7,31(2015).[2] G.Biancoetal.Multiplexedholographic lenses:realizationandopticalcharacterizationIET3-3

(2015).[3] R.Rega,O.Gennari, L.Mecozzi,S.Grilli,V.Pagliarulo,P.Ferraro,AdvancedMaterials28,454

(2016).[4] S. Grilli et al. Surface nanoscale periodic structures in congruent lithium niobate by domain

reversalpatterninganddifferentialetchingApp.PhysLett.87,23(2005).

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EnablingnextgenerationlithographyattheXILbeamline:fromsingle-digitresolutiontomaterialscharacterization.

RobertoFallicaandYasinEkinci

PaulScherrerInstitute,5232VilligenPSI,Switzerland

Nextgenerationlithographyforthemassproductionofintegratedcircuitswillbebasedonextremeultraviolet(EUV)lightat13.5nm,whichisasignificantimprovementoverthecurrenttechnologybased on deep ultraviolet light at 193 nm. EUV lithography will enable higher resolution,simplificationofprocessandlowercost-per-waferincomparisontotheactualtechnology.However,the transition to EUV demands both the design of novel photosensitive materials and a solidunderstandingofthephysicochemicalprocessesoccurringinthisregime.

AttheXILbeamlineoftheSwissLightSource(SLS)wetestthepatterningperformanceofphotoresistsby use of the EUV interference lithography tool which is capable of unparalleled single-digit

resolutionpatterning1,2.TheschematicprincipleofoperationisshownintheFigure(top);scanningelectron imagesofhighresolutionpatternsarealsoshown(bottom).TheXIL isbeingextensivelyused for pre-screening of novel photoresists under development in academia and industry. As aresult,wehadtheopportunitytotestawiderangeofmaterials:fromthechemicallyamplifiedresistswithpolymerbackbone,tothephotocondensedtin-basedmetaloxides,tocarbon-basedmolecularcompounds. In thisoverview, theadvantageanddisadvantageofeachapproachand thevariousapplicationswillbepresented.Iwillalsopresentanddiscussthechallengesintermsoflithographicsensitivity,sidewallroughnessandresolutionneededtomeetthetargetspecificationrequiredbyadoptionofEUVlithographyatthe7nmtechnologicalnode.Besidesitsindustrialimportance,thestudyofphotoresistsopensnewpossibilitiesinpatterningschemesaswellasinsightforfundamentalresearch. In the last part of my talk, I will present a methodology to measure the absorptioncoefficientatEUVofphotoresistsandtoextractthereactionrateandkineticsduringexposurebyinsitutransmissionmeasurement.

References[1]N.Mojarad,J.Gobrecht,andY.Ekinci,MicroelectronicEngineering143,55(2015).[2]D.FanandY.Ekinci,JournalofMicro/Nanolithography,MEMSandMOEMS15(3),033505(2016).

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Liquidnano-dispensingbypyro-electrohydrodynamics

SaraCoppolaInstituteofAppliedSciencesandIntelligentSystemsoftheNationalCouncilofResearch(CNR-ISASI)ViaCampiFlegrei34,80078Pozzuoli(NA),Italy


Thepossibilityofshapingthesoftmatterintocomplexthree-dimensionalstructuresisbecomingveryimportantintherealmofnanotechnology.Microelectroniccomponents,flexibleelectroniccircuits,optical-waveguides,microlenses,3Dscaffoldfortissueengineering,biomaterialsandhighresolutionbiosensor are just few examples of possible applications of 3D components. Many differentapproaches have been developed and tested for materials manipulation and microfabricationpurposes.Veryrecentlytheink-jetprintingapproachhasopennewfrontiersfornon-contactprintingand high resolution dispensing. Here we report on thework and the experiments related to thedescriptionofanunconventionalapproachdevelopedforthemanipulationofliquidandpolymericmaterials.Thenovelproposedconcept,namedas“pyro-fluidicplatform”sharessimilaritieswiththeink-jetprintingapproachbutitismorepowerfulintermofsimplicityandflexibility.The“pyro-fluidicplatform”offerstheabilityofworkingonfluidicmultiphasematerialsbyexploitingthepyro-electriceffectactivatedontoaferroelectriccrystal.ThePyro-platformworksinanozzle-lessandcontact-freemodality and is probably very close to the industrial demand being independent to the kind ofreceivingsubstrateusedandmaterialprocessed,allowingalsoadirectprintingondevicesreadyforuse. Moreover working in stable condition the printing cone generated by the pyro-ElectroHydroDynamic(EHD)effectallowsthefreeformfabricationofdesired3Dstructures.

Examples of pyro-EHD printing of dots and lines

References[1]J.Ackenhusen,IEEEJ.QuantumElectron.,vol.15,no.9,1026,(1979).[2]T.-K.Shin,IEEEPhoton.Technol.Lett.,vol.16,no.9,2078—2080,(2004).[3]I.A.Grimaldietal.AppliedOptics52,7699-7705(2013).[4]FerraroPetal.NatureNanotechnology5(6),429-435(2010).[5]Coppolaetal.ChemistryofMaterials26(11),3357-3360(2014).[6]Coppolaetal.Opt.Lett.37,13,2460-2462(2012).[7]Vespinietal.LabonaChip-MiniaturisationforChemistryandBiology16(2),pp.326-333(2016).

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Pyroelectric-basedplatformsforbiologicalapplications

OriellaGennariInstituteofAppliedSciencesandIntelligentSystemsoftheNationalCouncilofResearch(CNR-ISASI)

ViaCampiFlegrei34,80078Pozzuoli(NA),ItalyE-mail:[email protected]

InthelastdecadethepyroelectriceffecthasbeenstudiedatCNR-ISASIfor innovativeapplicationswhere electric fields address the assembling of particles and polymers through electrode-freeprocedures.Thislecturefocusestheattentionontotherecentadvancementsregardingtheuseofapyroelectric-basedplatformforthemanipulationofbiologicalmatter.Apyro-electrohydrodynamicjetsystemhasbeendevelopedfordispensingfemto-litredropletsabletoconcentratelowabundantbiomoleculesfor ‘super-sensing’applications,butalsoforpatterningmultiscalebioinkpatternsforaddressingthecelladhesionmorphology.Thespontaneouspolarizationofferroelectricwafercrystalshasbeendemonstratedtobeabletoinfluencethearrangementofthecytoskeletonoflivecells(seethe Figure below as example). A pyro-electrodynamic spinning system has been developed forfabricating spiralling fibres able to modulate the cell adhesion morphology along curvilineargeometries.Webelievethatalloftheseresultswillbringthepyro-electrohydrodynamicplatformtothe development of a new tool for deep investigation of cell-material interaction and thus formanipulatingtherelatedmechanisms.

References[1] C.S.Chen,M.Mrksich,S.Huang,G.M.Whitesides,D.E.Ingber,Science276,1425(1997).[2] N.C. Carville, L. Collins,M.Manzo, K. Gallo, B.I. Lukasz, K.K.McKayed, J.C. Simpson, B.J. Rodriguez, J.

Biomed.Mater.Res.,PartA103,2540(2015).[3] R.Rega,O.Gennari,L.Mecozzi,S.Grilli,V.Pagliarulo,P.Ferraro,AdvancedMaterials28,454(2016).[4] S. Grilli, L. Miccio, O. Gennari, S. Coppola, V. Vespini, L. Battista, P. Orlando, P. Ferraro, Nature

Communications5,5314(2014).[5] L.Mecozzi,O.Gennari,R.Rega,S.Grilli,S.Bhowmick,M.A.Gioffre`,G.Coppola,P.Ferraro,SoftMatter

12,5542(2016).[6] V.Marchesano,O.Gennari,L.Mecozzi,S.Grilli,P.Ferraro,ACSAppliedMaterials&Interfaces7,18113

(2015).[7] O.Gennari,L.Battista,B.Silva,S.Grilli,L.Miccio,V.Vespini,S.Coppola,P.Orlando,L.Aprin,P.Slangen,P.

Ferraro,AppliedPhysicsLetters106,054103(2015).[8] L.Mecozzi,O.Gennari,R.Rega,L.Battista,P.Ferraro,S.Grilli,DOI:10.1002/mabi.201600307(2016).

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Mechanisms,Capabilities,andApplicationsofHigh-ResolutionElectrohydrodynamicJetPrinting

M.SerdarOnses

DepartmentofMaterialsScienceandEngineering,NanotechnologyResearchCenter(ERNAM)

ErciyesUniversity,Kayseri,38039,Turkey

We give here an overview of techniques used for high resolution jet printing that rely onelectrohydrodynamically induced flows. Such methods enable the direct, additive patterning ofmaterialswitharesolutionthatcanextendbelow100nmtoprovideuniqueopportunitiesnotonlyinscientific studies but also in a range of applications that includes printed electronics, tissueengineering,andphotonicandplasmonicdevices.Afterabriefhistoricalperspective,wereviewherethedescriptionsof theunderlyingprocesses involved in the formationof liquid cones and jets toestablishcriticalfactorsintheprintingprocess.Wedescribeheredifferentprintingsystemsthatsharesimilarprinciples,alongwithkeyadvancesthathavebeenmade inthe lastdecade.Capabilities intermsofprintablematerialsandlevelsofresolutionarereviewed,withastrongemphasisonareasofpotentialapplication.

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Magneticnanosensorbasedonquantuminterference: apowerfultoolfornanoscaleinvestigation

C.GranataandA.Vettoliere


The magnetic sensing at nanoscale level is a promising and interesting research topic of nanoscience [1]. Indeed,magnetic imaging isapowerful tool forprobingbiological,chemical andphysical systems. The study of small spin cluster, like magnetic molecules and nanoparticles,single electron, cold atomclouds, is oneof themost stimulating challengesof applied and basicresearch of the next years. In particular, the magnetic nanoparticle investigation plays afundamental role for the modern materialscienceand itsrelative technologicalapplicationslikeferrofluids, magnetic refrigeration and biomedical applications, including drug delivery, hyper-thermiacancertreatmentandmagneticresonanceimaging contrastagent.Actually,oneofthemostambitious goals of the high sensitivity magnetometry is the detection of elementary magneticmomentorspin.Inthisframework,severaleffortshavebeendevotedtothedevelopmentofahighsensitivitymagnetic nanosensor pushing sensing capability to the individual spin level. Among the differentmagnetic sensors, SuperconductingQUantum InterferenceDevices (SQUIDs) exhibit an ultra highsensitivityandarewidelyemployedinnumerousapplications[2,3]. Basically,a SQUID consists ofa superconducting ring (sensitive area) interrupted by two Josephson junctions.Intherecentyears,ithasbeenprovedthatthemagneticresponseofnano-objects canbeeffectivelymeasuredbyusingaSQUIDwithaverysmallsensitivearea(nanoSQUID). In fact,thesensornoise,expressed interms of the elementarymagneticmoment (spin or Bohrmagneton),islinearlydependentontheSQUIDloopsidelength.Forthisreason,SQUIDs have been progressivelyminiaturized in order toimprove the sensitivityup to fewspinper unit of bandwidth. With respect to other techniques,nanoSQUIDs offer the advantage of directmeasurement ofmagnetization changes in small spinsystems.Inthislecture,wewill focusonnanoSQUIDs,inparticular,wewilldiscussthemotivations,thetheoreticalaspects, thefabricationtechniquesandthedifferentnanoSQUIDs.References[1] D.Bader,Colloquium:“Opportunitiesinnanomagnetism”,Rev.ModernPhys,vol.78,pp1–15,

2006.[2] C.GranataandA.Vettoliere,NanoSuperconductingQuantumInterferencedevice: Apowerful

toolfornanoscaleinvestigations,PhysicsReports,614, pp1-69, 2016.[3] W.Wernsdorfer,“Frommicro-to-nano-SQUIDs:applicationstonanomagnetism” Supercond.

Sci.Technol.,vol.22,pp.0640131-13,2009.

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MagneticnanosensingwithSuperconducting QuantumSensors

J.GallopandL.Hao

NationalPhysicalLaboratory,HamptonRd.,TeddingtonTW110LW,LondonUKIn the recent years one of the most stimulating challenge for the Superconducting Quantum Interferencedevices(SQUIDs)isthedetectionofasingleorafewelectronicspinsofferingthe possibilitytoexplorenewstimulatingnanosciencetopicssuchasthestudyofsingleelectron, molecularmagnets,andthereversalmagnetizationofa singleor fewnanoparticles[1].The SQUID capability to detectmagneticmomentor spin isproportional to the size of its loop. Thankstocurrentnanotechnologytechniques, it is possible to fabricate SQUID having a loop radius less than 100 nm,obtaininganadequatesensitivitytodetectthemagneticresponseof smallspinpopulations.Oneof themost interestingapplication isthe investigationofsinglemagneticnanoparticle. In fact,although techniques for measuring the magnetic properties of large particles or collections ofnanoparticles are well-established, single nanoparticle measurements are less straightforwardandbecomeincreasinglychallengingastheparticledimensionsandmagnetic moments are reduced. Theinvestigationofnanoparticlesatnanoscale level couldbeof significancenotonlyfortheinformationtechnologyandthequantumcomputingbutalsofor futuremedicalandbiologicalapplications.Other interesting application are readout of a nanoscale electromechanical systems (NEMS) resonator and the single photon or macromolecule detector [2]. Thebasicprincipleofthefirst applicationliesonthecouplingbetweentheelectricallyconductingresonatorandtheSQUID loop.ThisproducesaSQUIDinductancevariationandaconsequentchangeoftheoutput signal.Asregardthesecondapplication,asuperconductivethinfilmpatch(radiation absorber) is placedwithin the loopof nanoSQUID andis maintained just below its critical temperature. The SQUID has a higher transition temperaturethan the absorber. When a photonhitstheabsorber, itstemperature increasesslightly,causingavariationof the inductanceoftheSQUIDduetothechangeoftheLondonpenetrationdepthoftheabsorber. Suchinductancevariationgivesrisetoavoltagepulse,theheightofwhichisproportionalto theabsorbedphotonenergy.Inthislecture,wewillfocusonnanoSQUIDapplicationsincludingnanomagnetism,detectorformotionofresonatorsmadefromNEMS,singlephotonormacromoleculedetection.References[1] C.GranataandA.Vettoliere,NanoSuperconductingQuantumInterferencedevice: Apowerfultool

fornanoscaleinvestigations,PhysicsReports,614, pp1-69, 2016.[2] L. Hao, J.C. Gallop, D.C. Cox, J. Chen, Fabrication and analogue applications of nanoSQUIDs

usingDayembridgejunctions,IEEEJ.Sel.Top.QuantumElectron,vol. 21,pp.9100108,2015.

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“Man-made"CuttingEdgeMaterialsforLightControlandManipulationattheNanoscale

M.Rippa,R.CastagnaandL.Petti

InstituteofAppliedScienceandIntelligentSystems,Pozzuoli(Na),Italy

Theadventofnanotechnologyhasallowedscientiststostudylight–matterinteractionsatthenanoscale.Controllinglightpropagationatthenanoscaleisafascinatingopportunityofferedbymodernphotonics,more thanachallenge to faceoff.Nanophotonicsprovidedapathwaytobothcontrolandmanipulateopticalsignalsbycouplingthemtomatter;this ledtothedevelopmentofatoolboxofsub-wavelengthphotonic components likemirrors, lenses, photonic crystals andwaveguides, capable ofmanipulatingphotonicsignals.Amongtheclassesofphotonicnanostructures,“PhotonicCrystals”and“PhotonicQuasi-Crystals”(PQCs)-orphotonicband-gapmaterials-exhibitaninclusionspacingthatisofthesameorderof lightwavelength.Theyareartificial lithographydefined structures, inwhich latticepatternsarenotnecessarily constrained to designs found in nature, a feature that could overcome the technologicalapplicabilityofnaturalstructures.Unlikeperiodicallyarrangedphotoniccrystals,PQCsarefascinatingnewphotonicmaterials inwhich the lack of a translational symmetry is compensated by a high rotationalsymmetry(suchasoctagonalordodecagonalin2D,oricosahedralin3D),notachievableinconventionalperiodiccrystals.ElectromagneticpropertiesofPCsandPQCscanbecontrolledbyproperlydesigningtheirgeometry:Almosteachsingleparameterofthesestructures,relatedtoperiodicityoraperiodicity,shape,material,etc.,canbemanagedtoachieveadesiredpropagationorextractionproperty.Thispresentationwill illustrate thenanofabricationprocessbyEBL technologyand someapplicationof suchengineeredphotonicnanostructures:

DevelopmentofNovelhybridorganic/inorganicphotoniccrystal(PC)andquasicrystals(PCs)forlightemittingdevices[1];

NanostructuredhighlyconductivePEDOT:PSSfilmswith2DphotoniccrystalsandquasicrystalsforefficientOLEDdevices[2];

PhotonicCrystals–DispersedLiquidCrystallineMetamaterialsforswitchingallopticalorelectro-opticaltransmissionoflight[3];

DevelopmentofChiralNLOmeta-moleculesforquantuminformationprocessing[4]

References[1] M. Rippa, R. Capasso, P. Mormile, S. De Nicola, M. Zanella, L. Manna, G. Nenna and L. Petti.

Nanoscale,2013,5,331.[2] L.Petti,M.Rippa,R.Capasso,G.Nenna,A.DeGirolamoDelMauro,G.Pandolfi,C.Minarini.ACS

AppliedMaterials&Interfaces5(11),pp.4777-4782(2013).[3] V.Caligiuri+,L.DeSio+,L.Petti+,R.Capasso,M.Rippa,M.G.Maglione,N.TabiryanandC.Umeton.

AdvancedOpticalMaterials,2:950–955(2014)[4] R.Kolkowski,L.Petti,M.Rippa,C.LafargueandJ.Zyss.ACSPhotonics2,899−906(2015).

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EngineeredPlasmonicPhotonicNanostructuresfor

“Label-Free”BiosensingM.Rippa,R.CastagnaandL.Petti

InstituteofAppliedSciencesandIntelligentSystemsoftheNationalCouncilofResearch(CNR-ISASI)


In the last decade thedevelopmentofnanosensorsbasedon theuniqueplasmonicpropertieshasattractedmuch attention for thedetection andmonitoring of biological andenvironmental agents[1].Withtheuseofplasmonicnanostructuresbasedonperiodicoraperiodic pattern, it is possibleto synthesize novel nanobiosensors characterized byselective responses,which, in turn,undergosignificantfrequencyshiftsinpresenceofanalytes. Among the variety of devices available, sensorsbasedonLocalizedSurfacePlasmon Resonance (LSPR) and Surface Enhanced Raman Spectroscopy(SERS) has gained increasing attention in view of its applications to the detection of analytes atextremelylowconcentrationswiththenotableadvantagesofalabel-freesensing.Inparticular,SERSisarapid,non-destructivevibrational spectroscopy technique capable toprovide to thefingerprint-like molecular information [2]. Compared to SERS, LSPR nanosensors allow torealize lowcostprototypeand canbe implementedby theuseofaneasy instrumental setup [3]. In both types ofsensorsitisofcrucialimportancetodevelopmetalnanostructureswithtailored plasmonicproperty,highly efficient and reproducible. Electron Beam Lythographytechnique allows to realize highlyreproducible nanostructures by the control withhighprecisionofsize,shape,butalsooftheinter-particle distanceand consequently to tune theplasmonic response in the visible andnear infraredrange.Theproposedresearchactivityisbasedontheapplicationofnanophotonicsforbiosensingbyunitingthelatestadvancesinplasmonics,nanofabricationandsurfacechemistry.Inthistalkweshallpresentsomeapplicationsof these sensors realizedby theNanoPhotonic Teamheaded by L. Pettiin the detection of analytes of biological interest as proteins (Bovine Serum Albumin), virus(bacteriophages)andbacteria(Brucella)andofenvironmentalinterestaspesticide(Thiram)[4].References[1]S.Zeng,D.Baillargeat,H.P.HoandK.T.Yong,Chem.Soc.Rev.,43,3426,(2014).[2]L.Petti,R.Capasso,M.Rippa,M.Pannico,P.LaManna,G.Peluso,A.Calarco,E.Bobeico,P.

Musto.VibrationalSpectroscopy,82,22-30(2016).[3] J.L.Hammond,N.Bhalla,S.D.RaffieandP.Estrela,Biosensors,4,172-188(2014).[4]M. Rippa, R. Castagna,M. Pannico, P. Musto,V. Tkachenko, J. Zhou and LuciaPetti,

Nanophotonics,DOI:10.1515/nanoph-2016-0146(2017).

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Combiningnanoscaleself-assemblyand3D-printingtomeettheconstructionchallengesofthefuture

JanP.F.Lagerwall

UniversityofLuxembourg,Physics&MaterialsScienceResearchUnit,LuxembourgE-mail:[email protected]

Additivemanufacturing,or3Dprinting,hasthepotentialtorevolutionizeconstruction,allowingon-demand production of complex structures in remote locations, with a minimum (or even no)infrastructure in place, potentially with zero waste production. However, as the ambition for 3D-printed objects is rising from home-printed plastic gadgets with little demands to large-scaleconstructionsthatmustsustainheavyloads,thelimitationsofcurrent 3D printing technology appearpainfully obvious [1]. Attempts to reproduce ourstandarddesignfor large-scaleconstructionsfore.g.housesandbridgeswithadditivemanufacturinghavefailed:itissimplynotrealisticto3D-printsteel-reinforcedconcrete.Iarguethatthegoaltomimicourtraditionalconstructionparadigmwith3Dprinting isthewrongwayforward.Arevolutionarynewconstructionmethodologylike3Dprintingcallsfor anequally revolutionary design solution. An ideal place to look for such a solution isNature,whichoffersextremelytoughmaterials,ofadesignverydifferentfromourcurrentbuilding constructions.The archetypal design theme for strong biological composites is a helical arrangement ofpolysaccharides, primarily chitin or cellulose, embedded in other organic and/or inorganiccomponents.Amongthetoughest compositesknownisthestomatopoddactylclub,whichowes itsextraordinary ability to dissipate impact and stopcrackpropagationtoanexquisitearrangementofchitin helices with smoothly varying pitchanddirection,mineralized inhydroxyapatiteandcalciumcarbonate[2].ChitinandcellulosearethemostabundantpolymersonEarth,prominent intheanimaland plant kingdoms, respectively. By a combination of mechanical and chemical treatment, it ispossibletoextractpurelycrystallinechitinorcellulosefromanaturalsource,asneedle-likenanorodssome 100nm in length and 5nm in diameter. After sulphuric acid hydrolysisthe nanorods can beeasily dispersed inwater thanks to the surface charge introduced bythe acid. Thanks to the rod-like shape and the chirality of the polymer, these suspensions form liquid crystal phases withspontaneoushelix formation if the concentration isbeyond2-4%. Chitin solutions, prepared fromseafood trash, have already been 3D-printed intolarge-scale complexdesigns [3].Bydevelopingthisapproach,takingthescienceofcolloidalliquid crystal formation into account, I believewe willbe able to achieve unprecedentedtoughbiomimeticmaterialsviachitinorcellulosenanocrystal3Dprinting.References [1] M.Rhodes, Wired on-line, 03.02.16, https://www.wired.com/2016/03/additive-

manufacturing-integrated-energy-structure/(2016)[2] J.C.Weaveretal.Science336,1275-1280(2012).[3] J.Duro-Royoetal.,Computer-AidedDesign69,p.143(2015)

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Synthesisandcharacterizationofinorganicnanoparticlesforbiomedicalapplication

MariaMorosInstituteofAppliedSciencesandIntelligentSystemsoftheNationalCouncilofResearch(CNR-ISASI)


Todatenanoparticles(NPs)arealreadyusedinnumerousproductsandapplications.OneofthefieldsthatcangreatlybenefitfromtheuseofNPsisnanomedicine,byimprovingdiagnosis,treatmentorpreventionofdisease.1 Interestingly, inorganicNPspresentuniquephysico-chemicalproperties,assize reduction is associated with new optic, electronic, magnetic and catalytic properties incomparisonwiththebulkmaterial.Forexample,goldandmagneticNPscanbeusedintumoralcellablation and/or remotely controlled drug release due to heat generation in response to lightirradiationorthepresenceofanalternatingmagneticfield.2,3Also,theycanbeusedasmultifunctionalplatformsindrugdelivery,imagingandbiosensing.4,5However,thesynthesisandfunctionalizationprocedureshavetobecarefullyselectedinordertoobtainstableandreproducibleNPs.

An overview of different techniques to synthetize some inorganic NPs, highlighting their possibleapplicationsinthenanomedicinefieldwillbepresented.

References[1] Moros,M.;Mitchell,S.;Grazu,V.;Fuente,J.M.de.Curr.Med.Chem.20,2759–2778(2013,).[2] Moros,M.;Ambrosone,A.;Stepien,G.;Fabozzi,F.;Marchesano,V.;Castaldi,A.;Tino,A.;dela

Fuente,J.;Tortiglione,C.Nanomedicine(Lond.)10,2167–2183,(2015)[3] Pérez-Hernández,M.;delPino,P.;Mitchell,S.G.;Moros,M.;Stepien,G.;Pelaz,B.;Parak,W.J.;

Gálvez,E.M.;Pardo,J.;delaFuente,J.M.ACSNano,9(1),52-61,(2015)[4] Moros,MandCasciaro,B.;Rivera-Fernández,S.;Bellelli,A.;delaFuente,J.M.;Mangoni,M.L.

ActaBiomater.,47,170–181(2017)[5] Moros,M.;Hernáez,B.;Garet,E.;Dias,J.;Sáez,B.;Grazu,V.;González-Fernández,A.;Alonso,C.;

delaFuente,J.ACSNano2012,6,1565–1577.

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AsimplebiologicalmodelfornanomedicineClaudiaTortiglione



TheremarkableamenabilityofaquaticinvertebratestolaboratorymanipulationhasalreadymadeafewspeciesbelongingtothephylumCnidariaasattractingsystemsforexploringanimaldevelopment.The proliferation of molecular and genomic tools, including the whole genomic sequence of thefreshwaterpolypHydravulgarisfurtherenhancesthepromiseofthisspeciestoinvestigatenotonlyonkeyaspectsofdevelopmentalbiology,butalsotootherresearchfields,suchasnanomedicineandnanotoxicology.Overthepastyears,ourgroupadoptedthismodeltotestbioactivityandfunctionalityof nanomaterials1, micro and nanodevices 2-4. Recently, the mechanism of photostimulation ofsemiconductingpolymernanoparticlesnormally employed inphotovoltaicswas investigatedusingHydra5confirmingthefeasibilitytotestchemicalandelectricalpropertiesofsmartfunctionaldevices.Moreover, the high sensitivity to heavy metals enabled development of multiple protocols fortoxicologicalassessmentofananostructuredmaterials6.AnoverviewofdifferentissuesfacedinHydrabyusingnanoparticleswillbepresented,highlightingfeaturesofthefasttime,costeffectiveinvivomodelforhigh-throughputevaluationofnanomaterialsimpactonenvironmentandhumanhealth,andtakingintoaccountethicalandeconomicissues.

References[1] CondeJ,AmbrosoneA,SanzV,HernandezY,MarchesanoV,TianF,ChildH,BerryCC,IbarraMR,

BaptistaPV,TortiglioneC,delaFuenteJM.ACSNano6(9),8316–8324(2012)[2] MorosM,AmbrosoneA,StepienG,FabozziF,MarchesanoV,CastaldiA,TinoA,delaFuenteJM,

TortiglioneC.Nanomedicine(UK).10(14):2167-83(2015).[3] AmbrosoneA.,MarchesanoV.,Carregal-RomeroS,IntartagliaD,ParakWJ,TortiglioneC.ACS

Nano2016,10,4828-4834(2016)[4] AmbrosoneA,delPinoP,MarchesanoV,ParakWJ,delaFuenteJMandTortiglioneC.

Nanomedicine(UK)2014,9(13):1913-22(2014)[5] C.Tortiglione,M.R.Antognazza,A.Tino,C.Bossio,V.Marchesano,A.Bauduin,M.Zangoli,S.V.

Morata,G.Lanzani.ScienceAdvances.3(1)e1601699(2017)[6] AmbrosoneA,RoopinM,PelazB,AbdelmonemAM,AckermannLM,MatteraL,AlloccaM,Tino

A,KlapperM,Parak,WJ,LevyO,TortiglioneC.Nanotoxicology.,11(2):289-303(2017)

19

MovingNanobiotechnologyfromtheLabtotheMarket

MªValeriaGrazú

AragónMaterialsScienceInstitute(ICMA)SpanishNationalResearchCouncil,UniversityofZaragoza(CSIC-UNIZAR)

E-mail:vgrazu@unizar.esInnovationandexcellencecanhelpaddressmajorsocietalchallenges,whichcouldpositivelyimpactonourlivesinverydifferentways.Toachievethisiscrucialtobridgethegapbetweengeneratingnewknowledge and turning it into new products and services. Transforming the results of scientificresearchintonewcommercialproductsishoweveracomplexprocessthatneedsastronginteractionbetweenpublicorganizationsandcompaniesinatypeofresearchknownastransdiciplinaryresearch.During this talk, several examples of a successful transference of knowledge generated at theNanotechnologyandApoptosisGroup(NAP)intoproductswillbediscussed.Theseexamplesincludefrom kits for an easy functionalization of nanoparticles with different biomolecules (enzymes,antibodies,etc)toadisruptivenovelbiosensingtechnologybasedontheuseofnanoprismsasthermallabels(HEATSENS).Inbothcasesalltheroadtothemarketwillbediscussedthatisfromthebirthoftheidea,theproofofconcept,thetransferenceoftheknowledgetoNanoimmunotech(NIT),andeventheworkthatNIThaddonetobridgethegapfromalowtechnologyreadinesslevel(TRL2or4)tothemarket.Asex-RDdirectorofNITandamemberofNAPgroup,DrValeriaGrazúwill givea globalperspectiveofbothmarketimplementationprocesses.

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Femtosecondlasersurfacestructuring:principlesandapplications

SalvatoreAmorusoDipartimentodiFisica“EttorePancini”,UniversitàdiNapoliFedericoII,Napoli,Italy

E-mail:[email protected];[email protected]

The interaction of ultrashort laser pulses (≈ 100 fs)with solid targets is largely exploited both infundamental research and scientific and technological applications. In particular, laser ablationinduced by ultrashort laser pulses is opening up several interesting opportunities in “materialprocessing” [1-3]. Among the various examples, the direct generation of nanoparticles and thecreation ofmicro- and nano-structured surfaces represent two cases of striking scientific interestwhichcanalsoleadtodiverseimportantapplications[2-4].

Thispresentationwill firstly illustrate thebasicmechanisms involved in laserablation triggeredbyintense,femtosecondlaserpulsesandthepeculiarcharacteristicsofthedecompositionprocessesoftheirradiatedmaterialoccurringattheearlystagesafterthepulsehitsthetarget.Then,theglancewill bemoved to the surface of the targetmaterial discussing the formationofmicro- andnano-structuredsurfacesby“directfemtosecondlasersurfaceprocessing”withbeamscharacterizedbyaGaussian spatial profile [2-5]. In particular, the peculiar morphologies of random and regularstructures produced on the surface of metallic and semiconductor targets will be addressed,illustratingsomeofthemainmechanismsinvolved.Phenomenonlikeincubation,formationofregularsubwavelengthripplesonmetalsandsemiconductorsandproductionofsupra-wavelengthgroovesonsemiconductorswillbepresentedanddiscussed[5,6].Finally,someofthepossibleapplicationsofthestructuredsurfacetogetherwiththeirnovelfunctionalitieswillbeaddressed[1-3].

References[1] K.C.Phillips,H.H.Gandhi,E.MazurandS.K.Sundaram,Adv.Opt.Phot.7,684(2015).[2] A.Y.VorobyevandC.Guo,LaserPhotonicsRev.7,385(2013).[3] J.Bonse,S.Höhm,S.V.Kirner,A.Rosenfeld,andJ.Krüger,IEEEJ.Sel.TopicsQuantumElectron.

23,9000615(2017).[4] N.Tsakiris,K.K.Anoop,G.Ausanio,M.Gill-Comeau,R.Bruzzese,S.Amoruso,andL.J.Lewis,J.

Appl.Phys.115,243301(2014).[5] S.He,J.JJNivas,A.Vecchione,M.Hu,andS.Amoruso,Opt.Express24,3238(2016).[6] S.He,J.JJNivas,K.K.Anoop,A.Vecchione,M.Hu,R.Bruzzese,S.Amoruso,Appl.Surf.Sci.353,

1214(2015).

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Femtosecondlasersurfacestructuringwithpolarization-shapedlightDomenicoPaparo


E-mail:[email protected];[email protected]

Termsasstructuredlight,tailoredlight,shapedlight,sculptedlight,refertothenowadayspossibilityofgeneratingcustomopticalfieldswithcomplexstructuresinbothtimeandspace.Inthelastdecadethistopichasattractedahugeinterestbecauseofthemyriadofpossibleapplicationsofstructuredlightinfieldsgoingfrommicromanipulationtoquantumtechnology[1].Inparticular,oneapplicationofstructuredlightthatisstillatitsinfancyresidesinthepossibilityofusinglightwithcomplexpolarizationpatternsforfabricatingcomplexsurfacestructuresinmaterialsthatrespondtothepolarizationoflight[2].

Inthisrespect,thispresentationisthenaturalcontinuationofthepresentationbyProf.Amoruso.TherefemtosecondlasersurfaceprocessingwithbeamscharacterizedbyaGaussianspatialprofileisconsidered;herewegoastepfurtherbyexploitingtheadditionalfeaturesofstructuredlightandinparticularfemtosecondvortexbeams.

Thispresentationisdividedintwomainparts.Inthefirstpartwewilldescribethetechniquesusedtogeneratevortexbeams.Inparticular,wewillfocusourattentiononasimpleandpracticalliquidcrystaldeviceinventedinourgroupandnamed‘q-plate’[3].

Inthesecondpartwewillreviewsomeapplicationsoffemtosecondvectorbeamsfordirectlyfabricatingmicrostructuresonmetalandsemiconductingsurfaces[4].Wewillshowhowdifferentstatesofthevortexbeammaybeusedtofabricatevariousregularsurfacepatternsandhowthespatialfeaturesofthesestructuresnicelycorrelatetothespecificspatiallyinhomogeneousstateofpolarizationofthesebeams.

References[1] H..Rubinsztein-Dunlopetal.,Roadmaponstructuredlight,J.Opt.19,013001(2017).[2] K.Louetal.,FemtosecondLaserProcessingbyUsingOpticalPatternedVectorOpticalFields,Sci.

Rep.3,2281(2013).[3] L. Marrucci, C. Manzo, D. Paparo, Optical Spin-to-Orbital Angular Momentum Conversion in

InhomogeneousAnisotropicMedia,Phys.Rev.Lett.96,163905(2006).[4] J. J. J. Nivas et al., Direct Femtosecond Laser Surface StructuringwithOptical Vortex Beams

Generatedbyaq-plate,Sci.Rep.7,42142(2017).

22

Ultrashortpulsedlasersurfacestructuringformicrofluidicsandtissueengineering

E.StratakisInstituteofElectronicStructureandLaser(IESL),FoundationforResearchandTechnology(FORTH),

GreeceMaterialScience&TechnologyDepartment,UniversityofCrete,Greece

Email:[email protected]

Thispresentationreviewsourworkontheapplicationofultrafastlasersforthe3-dimensionalbiomimeticmodificationofmaterials.Inparticular,itisshownthattheartificialsurfacesobtainedbyfemtosecondlasertexturingofsolidsurfacesexhibitdualscaleroughnessinthemicro-andnano-lengthscalesthatmimicsthemorphologyofnaturalsurfaces.Thebiomimeticmorphologyattainedgivesrisetonotablemultifunctionalpropertieswhencombinedwithmethodsoftailoringthesurfacechemistry.Dependingonthefunctionalcoatingdepositedonthelaserpatternedthreedimensionalstructureswecanachieveartificialsurfacesthatare:(a)ofextremelylowsurfaceenergy,thuswaterrepellentandself-cleanedand(b)responsive,i.eshowtheabilitytochangetheirsurfacepropertiesinresponsetodifferentexternalstimuli.Furthermore,theabilitytotailorthemorphologyandchemistryisanimportantadvantagefortheuseofsuchstructuresasmodelstostudythedependenceofgrowth,divisionanddifferentiationofneuroncellsontopographicalcuesandthesurfaceenergyofbiomimeticculturescaffoldsfortissueregeneration.Potentialmicrofluidicandneuraltissueengineeringapplicationsoflaserfabricatedbiomimeticmaterialsaredemonstratedanddiscussed.

Acknowledgement

ThefinancialsupportfromtheEU-fundedprojectLinaBiofluid(undertheH2020frameworkprogrammeforresearchandinnovationunderGrantAgreementNo.665337),isacknowledged.

23

[email protected]

http://nanotoolingschool.isasi.cnr.it

IstitutodiScienzeApplicateeSistemiIntelligenti"EduardoCaianiello"

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