1

MARIE SKLODOWSKA-CURIE ACTIONS

Co-funding of regional, national and international programmes (COFUND)

DOC2AMU THESIS PROJECT 2018 CALL FOR APPLICATIONS

OVERDOSE

1. GENERAL INFORMATION

Call 2018-4

Topic Climate change, Nano-health

Keywords Optical sensor, VOC, adsorption/desorption, sol-gel

2. THESIS DIRECTOR(S), RESEARCH UNITS AND DOCTORAL SCHOOLS

Thesis director David GROSSO

Research Unit Institut Matériaux Microélectronique Nanosciences de Provence

Doctoral school ED 352 - Physique et Sciences de la Matière

Thesis co-director Philip LLEWELLYN

Research Unit Matériaux Divisés, Interfaces, Réactivité, Électrochimie (MADIREL)

Doctoral school ED 250 - Sciences Chimiques

1

MARIESKLODOWSKA-CURIEACTIONS

Co-fundingofregional,nationalandinternationalprogrammes(COFUND)

DOC2AMUTHESISPROJECT2018CALLFORAPPLICATIONS

(OVERDOSE)

2

1. DESCRIPTIONOFTHEPHDTHESISPROJECT

1.1OBJECTIVESOFTHEPROJECTBASEDONTHECURRENTSTATEOFTHEARTInteractionofvolatilecompoundscontainedinairwithman-customisedmaterialsisanoldbutstillintensefieldof research in domains of atmospheric pollutant detection and capture but also for medical diagnosis. Theobjective of the OVERDOSE project is to design simple and cost-effective optical sensors allowingmolecularselective detection of volatile species in gaseous state, relying on the controlled elaboration of specificallysensitivenanostructuredlayers,coupledtoanoptimisedopticaltransduction,fornon-invasivemedicaldiagnosisandairpollutionanalysis.OVERDOSEwilladdressissuesmanlyrelatedtothe“Nano-Health”researchtopic,butalsoinalesserextendto“Climatechange”,and“Networks”,sinceout-comesmayleadtosensorsthatcouldbeintegratedingridsofwirelessdistributednodesforairpollutionspatialvariationanalysisinurbanorindustrialenvironments.

Sinceseveraldecades,theincreasingofmeansforhumanlivessafetyhavecreatedgreatinterestsinresearchfieldofchemicalcompoundsemissionanddetectioninhumanbody.Forinstance,literaturereportsuptoseveralhundredVOCsandothergasesthatarepresentinbreathorthatcanbeemittedthroughthehumanskin.Theseincludemoleculessuchasammonia,tolueneoracetone,whichareidentifiedasdiseasebiomarkers[1]andmaybedetectedbynon-invasivemethods.Furthermore,ambientairpollutionwithvolatilespeciessuchasO3,NOX,CO, formaldehydes and many other VOCs (Volatile Organic Compounds), resulting from emission of diversepollutants fromvarioussources,areknowncausesofhumandiseasesandconsiderableeffortsareconductedtodaytomonitorspatiotemporallytheircompositionandlevelinconfinedspaces(vehicleinteriors)orinopen-space(atmosphericair)[2].Forsuchapplications, long-life, low-cost,stable,andreliableselectivesensorsarestrongly needed [3]. For both types of sensor, a high sensitivity down to ppm levels is required since targetmoleculesarefoundintraceamounts.Moreimportantly,thesemoleculesco-existmoreorlesssimultaneouslywithpotentiallyinterferingotherswhichmakestheirdetectionchallengingduetoco-adsorption/reactiononthesensitive materials. This issue of chemical selectivity is always present in gas sensors and maybe solved bycombiningresponsesobtainedwithdifferenttransductionsand/orsensitivematerials(artificialnoses).Amongstthe potentially interferingmolecules, H2O is certainly the most critical, especially as it can interact throughdispersiveandstronghydrogenbondingwithmostsurfaces.Furthermore,itexistsinmuchhigherconcentrations(around1to2104ppm)intheair,breath,andsweat,thanotherpollutants.Finally,humiditystronglyfluctuateswithday-timeandclimatechanges.Inthiscontext,sensorssolvingtheabove-mentionedsensitivityandselectivityissues, aswell asmeeting the requirements for long-life operation in fluctuating conditions is not yet in themarketplace.Regardlessofthetransductionprinciple,mostgassensorsrelyontheadsorption/diffusionofthemoleculeswithinahigh-surface-areaporousmaterial[4].Therefore,thedesignofnewmicroporousmaterialswithhighresistance,well-controlledporosity(1nm<poresize<2nm),andespeciallywithwell-definedsurfacefunctionalisation isamajor fieldof improvement.Recent reviewsofprogresses inusingMOF (MetalOrganicFrameworks)asVOCsensitive systemsshow interesting resultsbut concluded that improvements in stability,selectivity, and especially processability as thin layers is still required to achieve the maturation for realapplications [5]. Sol-gel chemistry and processing, on the other hand, provide simple, reliable and low-environmental-impactmethods to elaborate solid functional optical coatingswith tailored porous structures.Diffusion of gases in microporous xerogels has been well documented in domains of separation but barelyinvestigatedinthinopticallayers.Duetorandomformationofporeorganisation,thecontrolovertheporosityisnotasaccuratethanwithMOFs,butmicroporoushybridxerogelscoatingscanbepreparedwithpreciselytunedcharacteristics and properties and have recently proven to be highly sensitive and relatively selective in gassensing.Furthermore,theyarecomposedofsilicabackbonesthatinsuretheresistanceandlong-termconstantefficiency.Couplingthesesensitivelayerswithanoptimaltransductionbasedondirectreflectivity,andcombiningthe responses obtainedwith two layers of different chemical affinities and structures (see Fig. 1) allows forinstancethedetectionofdownto10ppmethanolinahighlyhumidenvironmentandfordifferenttemperatures.Thecostofsuchsensoris lessthan5€andits longevityhasbeenconfirmedover1yearsofar.Italsohasthe

3

advantage of self-regeneratingin less than a minute, which isnecessary for real timemonitoring. This finding fromthe IM2NP was the subject oftwo patents in 2017 [6] and isnow regarded as a seriouslyalternative to existing ethanolbreathalysers by NANOZ, theSME partner of the presentproject.Thegoodselectivityofthelatterxerogellayertoethanol,eveninsaturatedhumidity,isduetoaprecisetuningoftheporosityandthesurfacefunctionalityofthesilicanetwork,whichcanbeachievedonlywithahighcontrol over the sol-gel chemistry, the xerogel layer processing conditions by dip-coating, and the thermaltreatmentconditions.Otherxerogellayers,differinginfunctionalityandporosity,werethenelaboratedwithsuchan approach, and their affinity to other VOCwas investigated. They revealed extremely different interactionbehaviorswitheachtargetmolecule(seeFig.2),whichisastrongindicationthatthesematerialsarepromisingcandidatestoaddresstheselectivityissue.TheOVERDOSEprojectaimsthusatexploringthecouplingofthelatteroptimisedopticaltransductionandthetailor-madexerogelsforselectivegassensing.Besides,theprojectwillprovideadditionalfundamentalunderstandingandnewinsightsingasadsorptionbyfinitethinxerogellayers.

1.2METHODOLOGYDevelopingaselectivegassensorbasedontheabove-mentionedapproachrequiresseveraltasks.First,itisofutmostimportancetoperfectlyunderstandthebehaviours(adsorption/diffusion/desorption)ofdifferenttypesofmodel adsorbatemoleculeswithin the nanoporous adsorbentmaterialswith respect to their porosity andsurfacefunctionality.Thestructuralandchemicalcharacteristicsofthesensitiveadsorbentmaterialscanthenbeoptimised to favourably interact with a specific molecule, or family of molecules, as driven by the dynamicequilibrium between molecules adsorbed in the materials and those free in the surrounding volume. Bothadsorptionatequilibriumandoutofequilibrium(time-resolved)willbestudiedtodetermine,thermodynamicconstants and diffusionmodes (Knudsen, viscous, surface) [7], fromwhich the best signal treatmentwill beconstructed.Isothermsfrom0tosaturation(0<P/P0<1)butalsointherangeofoperation(0<gasconcentrationin air < 100ppm) will be investigated using specific gas generation systems and direct optical response(ellipsometry). The xerogel layer thickness and the conditions of optical transduction (reflexion angle, signaltreatment,dynamicresponsetimeperiod,…)willhavetobeadaptedtotheopticalconstantofthelayerandtotheirexpectedvariationunderoperatingconditions.Aftertheselectionoftargetmoleculesof interest forthementioned applications, their detection will be investigated in various conditions (humidity, temperature,presence of interfering gas) toassessthelimitofsensitivityandthe selectivity efficiency, usingthe adapted patented methodsthat allows a correction oftemperature and humidity asdescribedabove.As a starting material, Fig. 2displays the preliminary resultsobtained when submittingdifferent newly customisedxerogels to different VOCs. Onthe leftdiagram, it is clear thatselected molecules interact

0

0,005

0,01

0,015

0,02

0,025

0,03

0,035

0 5000 10000 15000 20000

RIvariatio

n

Conc.Air(ppm)

Refractiveindexvariation

Toluene H2O

Ethanol Acetone

Influenceoforganicmoietiesandporosity.

0

0,005

0,01

0,015

0,02

0,025

0,03

0,035

0,04

0 200 400 600 800 1000

RIvariatio

n

Time/s

XetogelaffinitywithToluene

XerogelJ13

XerogelRef

XerogelS21

Fig. 2 Left: adsorption isotherm (equilibrium state) of different vapors withinxerogel J13 plotted as Refractive Index (RI) variation (in-situ ellipsometrymeasurement).RightRIvariationmeasuredduringadsorptionanddesorption(outofequilibriumregimes)oftoluenewithin3differentxerogels(arrowsindicatethetimeatwhichthezero-relativepressureintolueneisapplied).

!" !#

$%&%'&()*',-./%0 SiSubstrate

Hybrid orref- layer

SOURCE DETECTOR

! =$%&'(

)* = +)°-./01/23/4

-5'254/'3

Potential(75)

9:352;1<;==5/=

-0,2

0,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

0 50 100 150

Norm

alise

dSignal

C(EtOH)ppm1(2*-3&0%-&.%*&

40%*',3%2-3-3'),)33(.(&

Fig.1Schemesandperformancesofthepatentedethanolsensors.

4

differentlywiththesamexerogelatequilibrium,showingLangmuir-typebehavioursfortheorganicsandquasi-linearbehaviour(Henry’slawisotherm)forwater.Besides,theleftdiagramrevealsthatthesamemoleculecanadsorbanddesorbatverydifferentratesindifferentxerogels.Suchexperimentalresultscanbeusedtodefineaffinity constants, in addition to thermodynamic and kinetic constants associated to a specificadsorbate/adsorbentpair.However,understandingtheseinteractionsatthemolecularlevelispossibleonlyifthestructureandsurfacechemistryofthexerogeliswell-known.ThesewillbeassessedbyXPS,FTIR,micro-raman,microcalorimetry and various adsorption/desorption techniques including the use of gas mixtures. All thesetechniquesareavailableintheworkingenvironment,thatwillbecomposedofthreeacademicteamsandoneSME.(i)TheNOVAteam(IM2NP)willbeinchargeofthesensitivexerogellayerssynthesis,characterisation,andoptimisation.Theiropticalcharacteristicsandresponsetothefullrangeofgaspressurewillbestudiedusingin-situtime-resolvedEnvironmentalEllipsometryandotherappropriatedspectroscopicmethods(attheIM2NP).(ii)TheMicroSensorand Instrumentation(MCI) team(IM2NP)areexpert ingassensingtechnologyandwillhelpintegrating the layer/transduction with temperature control and signal treatment periphery, to constructprototypesensors.Theyalsodisposeofstate-of-the-artgas(EtOH,Aceton,BTEX,Isobutylene,O3,NO2,NH3,CO,CO2) generators and dilution systems to test the sensors in very low concentration (down to ppb levels) insimulatedoperatingconditions(0<T<100°C;0<RH%<80%;0.1<F<0,5L/min).(iii)Finally,the‘EnergyandAdsorption’group(EnAP,MADIREL),willcharacterisethexerogellayerporosity,achallengingtaskformaterialswithdisorderedmicroporosityundercoatingforms,andtoevaluatetheadsorptionthermodynamicandkineticconstants and relative selectivity of the latter adsorbents. The industrial partner (NANOZ) develop andcommercialise innovative sensors andwill advise on the economic and technical viability of the sensorswithrespecttothedirectiontakeninthecourseoftheproject.

1.3WORKPLANStartingfromthelatterpreliminaryresults,otherhybridxerogellayerswithdifferentmicroporosity(porevolume,poresizedistribution)andsurfacefunctionalisationwithorganicmoietiesofdifferentchemicalcharacteristics(polarity,polarizability,hydrophilicity,degreeofunsaturation,acidity,…)willbepreparedusingsol-gelchemistrycoupledtotemperatureandenvironmentallycontrolleddip-coating.Thislatterprocessiscrucialsincethetuningoftheporosityandpositioningoftheorganicgroupscanbekineticallycontrolledthroughthecompositionoftheatmosphereduringevaporation[8].As-preparedcoatingsneedtoundergoastabilisationstepbythermalcuringatmoderate temperature tomaintain theorganic function integrity,whichalsogoverns theevolutionof theporosity.Bothprocesseswillbecontrolledtoadjustthefinalcoatingcharacteristics.Targetedmodelgaseswillbeselectedwithrespecttotheirchemicalcharacteristicsanddynamicradius.Gasup-takeintothesensitivelayersdepend on non-specific and specific interactions (field-dipole interactions) and on the effective diffusioncoefficient. Isotherms, adsorption and desorption kinetics, on the full ranges of vapour pressurewill first beinvestigated using ellipsometry and sorption techniques. Selectivity to specific types of molecules will bedeterminedandfundamentalaspectsof the involvedadsorptionphenomenawillbestudiedbasedonthefullcharacterisationoftheporosity.Moreselectivecoatingswillthenbetestedinmoredilutedconditionsoftargetedgas and also in simulated real operating conditions (various humidity, concentrations in interfering gas,temperature).Forthislatterpart,thecorrectedopticaltransductionmethoddescribedinFig.1willbeused.Themathematicaltreatmentofthephoto-diodeelectricalsignals,proportionaltothereflected light intensity,willhavetobeadaptedtothe interactioncontrastandit is likelythat, inviewofthepreliminaryresults inFig.2,treatmentsofthedynamic(time-resolved)adsorption/desorptionsignalswillprovidebetterresponsesintermofselectivity.Onceoptimaldetectionconditionswillbeidentifiedforspecificgasofinterest/xerogelpairs,prototypesensors will be constructed andefficiencywillbe testedoveravailableperiod of times. In the case of theopticaltransductionnotgivingthegoalsensitivity,xerogelsmaybeappliedonsemi-conducting WO3-based sensors

Masteringxerogel coating

Fundamentalunderstanding ofgas/xerogel interactionsAssessselectivityparameters

Testsinrealconditions Prototype

Years--------------------------1---------------------------2 ---------------------------3

GANTT

5

developedintheMicro-sensorteam.Evenifmorecomplextoimplement,thelattersystemswillcombinethehighsensitivityoftheelectricaltransductionandtheselectivityofthexerogelmembrane,andwillbeinvestigatedascontingencyplan.[1]P.Mochalski,etal.,“Emissionratesofselectedvolatileorganiccompoundsfromskinofhealthyvolunteers”,J.Chromatogr.B2014,959,62–70.[2]S.Moltchanovetal.,“Onthefeasibilityofmeasuringurbanairpollutionbywirelessdistributedsensorsnetworks”Sc.oftheEnvironment2015,502,537-547.[3]P.Kumaretal.,“Theriseoflow-costsensingformanagingairpollutionincities”,EnvironmentInternational2015,75,199-205.[4]T.Wagneretal.“Mesoporousmaterialsasgassensors”,Chem.Soc.Rev.2013,42,4036-4053.[5]W.P.Lustigetal.“Metal–organicframeworks:functionalluminescentandphotonicmaterialsforsensingapplications”Chem.Soc.Rev.2017,46,3242-3285.[6] Grosso, Abbarchi, Alvarez, FR1754533(Dispositif optique de détection et de quantification de composés. Grosso, Boudot, FaustiniFR1655699(Dispositifdedétectiond'untauxalcoolémie).[7]H.M.Alsyourietal.«GasDiffusionandMicrostructuralPropertiesofOrderedMesoporousSilicaFibers”J.Phys.Chem.B2005,109,13623-13629;R.S.A.deLangeetal.«Analysisandtheoryofgastransportinmicroporoussol-gelderivedceramicmembranes”J.Memb.Sc.1995,104,81-100.[8]D.Grosso“Howtoexploitthefullpotentialofthedip-coatingprocesstobettercontrolfilmformation”JournalofMaterialsChemistry2011, 21, 17033 ;M. Faustini et al. “ From chemical solutions to inorganic nanostructuredmaterials: a journey into evaporation-drivenprocesses.”Chem.Mater.(25thyearsanniversary,specialissue)2014,26,709-723.

1.4 SUPERVISORSANDRESEARCHGROUPSDESCRIPTION

Partner IM2NP: Prof. D. Grosso (main supervisor, 185 publications (h=55), 25 patents) leader of the“Nanotechnologyandadvancedmaterials”(NOVA)team,isexpertinsol-gelchemistryandprocessing.Mostofhisachievementsconcernnanostructuredthinfilmsforvariousapplications.Hecurrentlyhasprojectstodeveloporiginal patterned surfaces by combining bottom-up (sol-gel) and top-down (soft-imprint) approaches forphotonics and other optical applications, including optical transduction for gas sensing. Besides, the teamincludes senior scientists, experts innanostructured semi-conductorsand inoptical spectroscopy, thatwill beinvolvedintheproject.Theprojectwillbenefitfromtherecentfully-equippedsol-gelprocessingchemicallabandfromtheNOVAteamcleanroomfacilitiesNanoTecMat(http://www.im2np.fr/recherche/plateformes.html).Thisexpertise iscompletedbythe implicationoftheMicroSensors& Instrumentationteam(MCI)headedbyMarcBendahan,thatiscomposedof15seniorscientiststhathaveastrongexpertiseintheconceptionandrealizationof gasand vapormicro-sensors for indoorandoutdoorair quality applications, but also fornoninvasiveandcontinuousmonitoring of biomedical parameters. A state-of-the-art automated test benches to characterizesensorsinthepresenceofgases,vaporsormixturesinconcentrationsrangingfromafewppbtoseveralhundredppmundercontrolledenvironment(T°andHumidity)willbeavailablefortheproject.

PartnerMADIREL:PhilipLLEWELLYN(co-supervisor,>200publications,>20000citations,h=64,3patents)isaResearchDirectorwiththeCNRSandheadsthe‘EnergyandAdsorption’group(EnAP)attheMADIRELlaboratory.Theexpertiseofthegroupliesinthecharacterizationofadsorbents,adsorptionphenomenaandtheevaluationofporousmaterialsforapplicationsincludinggasrecoveryandstorageaswellasmaterialsforenergyuses.Thegroup boasts an impressive array of experimental approaches to answer questions posed during thesecharacterizationandevaluationstudies.Originalin-housemethodologiesincludethedirectmeasurementoftheinteractionenergiesviamicrocalorimetry,aswellnovelhighthroughputmethodsfortheevaluationofmaterialsformolecularseparations.ThecharacterizationofporoussolidsbyadsorptionisastrongpointofthegroupwhichhasproducedoneofthereferencebooksonthesubjectanddispensesyearlyCNRS-Industrycoursesontheuseofnumerous characterizationmethods. The characterisation of the xerogel layer porosity is a challenge as thequantitiesavailablearerelativelysmall.However,surfacearea,poresizeandsurfaceenergymaybedeterminedusingsomerecentlyacquiredequipmentbasedoninversegaschromatography.Inthisaspect,EmilyBloch(IE,CNRS)willassistinthemethodology/protocoldevelopment.

6

2.3IDIMENSIONSANDOTHERASPECTSOFTHEPROJECT

2.1 INTERDISCIPLINARYDIMENSION

IM2NP(InstituteofMaterials,MicroelectronicandNanosciencesofProvence) isanInstituteofphysics that iscomposed of around 200 senior scientists working in different fields of nanotechnologies including energy,environmentandmicroelectronics.Prof.DavidGrosso,asNOVAteamleaderandmainsupervisor,will invest33%ofhistimetocoordinatetheprojectandinsureefficientcommunicationandprogressesatallstagesdefinedintheworkplan.Hewillinsurethatanoptimalenvironmentissetforthestudenttosucceedinhisformationandin his scientific production. Scientifically speaking, his personal input will concern sol-gel chemistry (hybridmaterials,nanostructuration,nanocomposite,self-assembly…),layerprocessing,ellipsometrycharacterisations(environmental,time-resolved),methodsforopticaltransduction.HewillbeassistedintheformationbyMarcoAbbarchi(NOVA),aphysicistexertsinopticsandspectroscopy,andMarcBendahan,expertinsensingtechnology.

MADIREL(DividedMaterials,Interfaces,Electrochemistry)isamixedCNRS-AMUlaboratorywhoseexpertiseliesintheuseofchemistryandphysicalchemistrydevotedtothecomprehensionofvariousinterfacialphenomena.Notabletothisprojectistheuseofadsorptionandrelatedmethodstocharacterizetheincreasedsurfaceareainduced by the introduction of porosity into the silica xerogel. Indeed, the porosity and particular surfacechemistryofthethinlayermaterialswillrequirespecificcharacterizationmethodsavailableattheEnAPteam.Itwillthenbepossibletodevelopstructure–propertyrelationsincombinationwiththetestingobtainedattheIN2NP.

2.2INTERSECTORALDIMENSION:

NANOZ(regionalSEM).NANOZ,the industrialpartner,willhelpselectingrelevantsystemstofurtherdevelop,with respect to themarket needs. Hewill also have the role to educate the Ph.D. student on thematter oftransferringanacademicdiscoverytoindustryinthedomainofsensors.Theobjectiveistocompletehis(her)competenceinpurescientificresearchwithaspectsrelatedtoinnovation,valorisation,market,societal,juridical,andeconomicconstraintsexistinginindustriesandalsoinproblemsgenerallyencounteredduringtechnologicaltransfer.ThePh.D.studentwillbespendingatotalof2monthstothepartner.

TheprojectdoesnotaddressdirectlyanobjectiveoftheSRI-S3butmayleadtothedevelopmentofnon-invasive“new methods of medical diagnosis” and may provide cost-effective atmospheric sensors necessary in the“reductionofatmosphericpollution”objectivementionedintheSRI-S3.

2.2 INTERNATIONALDIMENSION:

ArecentcollaborationhasbeeninitiatedwithProf.MichaelTiemannandhisgroupinPaderborn(Germany),thatdevelopelaborationmethodsofporousmetaloxidesmaterialsandrelateddevicesforchemicalsensinginliquidandvapourphasesusingopticalandelectricaltransductions.Inthecourseoftheproject,thePh.D.studentwillbesendforaperiodof2-3monthsintheresearchgroupofM.Tiemann(letterofintentionavailableonrequest)tocompletehiseducationwithinanenvironmentthatoffersdifferentproblematicsassociatedtosensinganddifferentscientificapproaches.

Inaddition,andasithasalwaysbeenthecasewithallformalstudents,everythingwillbedoneforthestudenttoparticipateanddeliveroralpresentationsonhis results inat leastone internationalconferenceduringtheprojectperiod.

7

3.RECENTPUBLICATIONS

(IM2NP)Moreinformationonhttp://davidgrosso.wixsite.com/scientist-site

(1)T.Bottein,T.Wood,D.Thomas,J.B.Claude,L.Favre,I.Berbezier,A.Ronda,M.Abbarchi,andD.Grosso*.“Black"Titaniacoatingscomposedofsol-gelImprintedMieresonatorsarrays.”Adv.Funct.Mater.2017,DOI:10.1002/adfm.201604924.(2)M.Boudot,D.Ceratti,M.Faustini,C;Boissière,D.Grosso*.Alcohol-AssistedWaterCondensationandStabilizationintoHydrophobicMesoporosityEtOH/H2Oadsorption,J.Phys.Chem.C.2014,118,41,23907-23917.(3)T.Bottein,J.Loizillon,D.Grosso*,“AFullInvestigationofAngleDependenceinDip-CoatingSol-GelFilms"J.Phys.Chem.C.2017DOI:10.1021/acs.jpcb.7b04122.(4)M.Boudot,H.Elettro,D.Grosso*.ConvertingWaterAdsorptionandCapillaryCondensationinUseableForceswithSimplePorousInorganicThinFilms.ACSNano2016,10(11),10031–10040.(5)Highlightedinwww.materialsviews.comasgame-changermethod.D.Ceratti,B.Louis,X.Paquez,M.Faustini,D.Grosso*.ANewDipCoatingMethodtoObtainLargeSurfaceCoatingswithaMinimumofSolution.Adv.Mater.2015,27,4958-4962.2patentshavebeendepositedontheconceptofethanolsensorsusingxerogellayers,andapublicationisabouttobesubmitted.(6)M.Acuautla,S.Bernardini,L.Gallais,T.Fiorido,L.Patout,M.Bendahan.;OzoneflexiblesensorsfabricatedbyphotolithographyandlaserablationprocessbasedonZnOnanoparticles.SensorsandActuatorsB,203,602–611,2014DOI:10.1016/j.snb.2014.07.010(7)V.Martini-Laithier,I.Graur,S.Bernardini,,K.Aguir,P.Perrier,M.Bendahan,;AmmoniadetectionbyanovelPyrex microsystem based on thermal creep phenomenon ; Sensors and Actuators B, 192, p 714-719, 2014DOI:10.1016/j.snb.2013.10.120(8)M.D.Dankoco,G.Y.Tesfay,E.Benevent,M.Bendahan;TemperatureSensorrealizedbyinkjetprintingprocesson flexible substrate; Materials Science & Engineering B, 205 (2016) pp. 1–5http://dx.doi.org/10.1016/j.mseb.2015.11.003(9)M.ACUAUTLA,S.BERNARDINI,E.PIETRI,M.Bendahan;Nozzle-lessUltrasonicSprayDepositionforFlexibleAmmoniaandOzoneGasSensors;Sensors&Transducersjournal(ISSN:2306-8515,e-ISSN1726-5479),Vol.201,June2016,pp.59-64(10)B.Lawson,V.Laithier,T.Fiorido,F.Annanouch,S.Burtey,C.Cassé-Perrot,Ch.Audebert,M.Bendahan,R.Bouchakour, O. Blin, K. Aguir; Transdermal alcohol measurements using MOX sensors in clinical trials;Proceeding2017,vol1,pp431:www.mdpi.com/2504-3900/1/4/431;doi:10.3390/proceedings1040431(11)E.Bènevent,M.D.Dankoco,M.Bendahan;Inkjet-printedON/OFFforcesensoronflexiblesubstrateforultra-low power applications; Proceeding 2017, vol 1, pp 620: www.mdpi.com/2504-3900/1/4/620;doi:10.3390/proceedings1040620

Moreinformationat:http://madirel.univ-amu.fr/pages_web_LLEWELLYN_PHILIP/infos

Adsorptioninducedstructuralphasetransformationinnanopores,B.Kuchta,E.Dundar,F.Firmalik,P.L.Llewellyn&L.Firlej,AngewandteChemieInt.Ed.,2017,online(DOI.10.1002/ange.201708993)Screeningtheeffectofwatervapourongasadsorptionperformance:ApplicationtoCO2capturefromfluegasinMOFs,N.Chanut,S.Bourrelly,B.Kuchta,C.Serre, J.-S.Chang,P.A.Wright,P.L.Llewellyn,ChemSusChem,2017,10(7),1543–1553MIL-91(Ti),asmallporeMetal-OrganicFrameworkwhich fulfills severalcriteria:anupscaledgreensynthesis,excellentwaterstability,highCO2selectivityandfastCO2transport,V.Benoit,R.S.Pillai,A.Orsi,P.Normand,H.Jobic,F.Nouar,P.Billemont,E.Bloch,S.Bourrelly,T.Devic,P.A.Wright,G.deWeireld,C.Serre,G.Maurin&P.L.Llewellyn,J.Mater.Chem.A.,2016,4,1383-1389.

8

Methane storage in flexible metal-organic frameworks with intrinsic thermal management, J. A. Mason, J.Oktawiec,M.K.Taylor,M.R.Hudson,J.Rodriguez,J.E.Bachman,M.Gonzalez,A.Guagliardi,C.M.Brown,P.L.Llewellyn,N.Masciocchi,J.R.Long,Nature,2015,527,357–361.

4.EXPECTEDPROFILEOFTHECANDIDATE

ThefuturePh.D.studentwillhavetofeelconcernedabouthumanhealthcare,sincetheprojectobjectiveisthedevelopmentoforiginalsystemsfortheselectivedetectionofgasformedicaldiagnosisandatmosphericpollutionevaluation.ThePh.D.candidatewillhaveaneducationin(nano)materialsciences.He(she)willideallybeskilledin inorganic chemistry to elaborate tailored materials (nucleation, growth, sintering, processing) and incharacterisationofporousmaterials(sorptionmethods).Abackgroundinphysical-chemistrywillbeappreciated.Becauseofthemultidisciplinarycharacteroftheproject(chemistry,materials,thinlayers,optics,spectroscopy,sorption phenomena, device conception, physical measurement methods) candidates showing interests inacquiringadditionalskillsindisciplinesunrelatedtohis(her)owneducationwillbeanadvantage.TheprojectmayinvolvebasictrainingintheLabVIEWplatformanddevelopmentenvironment.

5.SUPERVISORS’PROFILES

IM2NPLastName,FirstName:Grosso,David Homepage:http://davidgrosso.wix.com/scientist-site

Birthdate:30thJanuary1970(Age:47)Nationality:FrenchCurrentposition:FullProfessor-ChairofExcellenceAMIDEX(awardedtohighlevelprofessorscontributingtothe emergence of world class research teams at Aix-Marseille University). Leader of the team NOVA(Nanotechnology and Advanced Materials) at the Institut Matériaux Microélectronique Nanosciences deProvence.POSITIONSHELDEDUCATION2015-today Professor(exceptionalclass),IM2NP,AixMarseillesUniversity,France2014-2015 CNRSDelegation,Lab.dePhotoniqueetdeNanostructures(LPN)Marcoussis,France2007-2014 Fullprofessor,LCMCP,UniversityPierreandMarieCurie,Paris,France2006 HDR:Accreditationtosuperviseresearch,UniversityPierreandMarieCurie,Paris,France2000-2007 AssociateprofessorLCMCP,UniversityPierreandMarieCurie,Paris,France1999-2000 PostDoctoralpositionatPhilipsResearchLaboratory-Eindhoven,Netherlands1996-1999 Ph.D.AtomicWeaponsEstablishment(AWE)andUniversityofSurrey-UKCAREERPROJECT Asasol-gelchemist,Ihavealwaysbeeninterestedinmaterialsprocessing.Itisthereforenotsurprisingthat,afterthe important achievementsmade in elaboration of coatings, as a group leader inmyprevious laboratory, Idecidedtomoveontoadaptingtheseversatilematerialstothemoresophisticatedmorphologiesofsupportednanopatternsandcoatings.ThesearethemainreasonswhyIdecidedtomovetoMarseille,toaninstitutewhereclean room facilitiesandmicro-(nano-)fabrication technologieswereavailable,andwhere I could leadanewteam within which materials chemists, physicists of optics, experts in nanofabrication, electronic deviceconceptionandsensingcouldworkinsynergy.Ihavethusdedicatedthelasttwoyearstosettlingabrand-newsol-gellaboratoryattachedtoacleanroom,the“Nanotechmat”platformoftheinstitute,andtostartingnewprojectswithinmy newNOVA team. The settlement has however significantly contributed to a less efficientscientificproduction(16articlesin2014against4articlesin2016).Ontheotherhand,thesefirsttwoyearsspent

9

inmynewenvironment,andthepreliminaryachievements,fuelledbythecollaborationsIhavedeveloped,ledto7acceptedarticles(+3submitted)in2017and6grantedpatentsfrom2016.TwoofthesepatentsconcernVOCsensing,whichhavethusmotivatedthesubmissionofOVERDOSE.CAREERSUMMARY

TEACHINGACTIVITIESFrom2000tonow:192h/year:Basicchemistry,InorganicChemistry,ExperimentalChemistry,Ceramics,ProcessingMaterials,NanotechnologiesandNanomaterials,CoatingsandThinFilms,Introductiontotop-downmethods.From2009to2014:66%teachingdischargeduetoexcellenceinresearch(IUFstatute).2010–2013:Incharge(pedagogy)“ChemistryandPhysicsofMaterials”Bachelorcourses.2010–2015:Incharge(administration,pedagogy)“Coatingsandsupportednanomaterials”MastercoursesTheUniversityofAixMarseillewillassign66%teachingdischargetothePIiffundedbytheERC.BECOMINGOFFORMALPHDSTUDENTSANDPDFELLOW.AllPh.D.studentstrainedundermysupervisiondefendedtheirthesisintimeandwithsuccess.Mostoftheirworkswerepublishedinhighlycitedjournalswithbetween3to12articlesperstudent.Mostofthemwereco-authorsofapatent.Besides,manypostdoctoralworkersandPh.D.studentsofmygrouphavesincegoneontopursuetheircareerasPostDoc(1intheUSA,1inKorea,1inJapan),asprincipalinvestigatorsinacademy(9inFrance,2inSpain),seniorscientistsinindustry(1inUK,3inFrance,1inSwitzerland,1inJapan,1inUSA,1inGermany),orasstart-upfounders(1inFrance,1inUSA).In2018,2ofmyactualPh.D.studentswillbedefendingandathirdonewillbeinhissecondyear.MADIRELLastName,FirstName:Llewellyn,Philip

Homepage:http://madirel.univ-amu.fr/pages_web_LLEWELLYN_PHILIP/infos

Birthdate:29thMay1967(Age:50)Nationality:UK&France

- Trackrecord 188Peer-reviewedarticles 26Patents 36Invitedconferences(25international) 3Invitedbookchapters 14Invitationsinforeigninstitutes

-Supervision 18PhDstudents(13asdirector) 18Postdoctoralfellows 13Mastertheses-Distinctions: 2006InternationalSol-GelSociety(ISGS)award

2009-2014MemberofIUF(Frenchservicethatdistinguishesprofessorsfortheirresearchexcellenceandinternationalrecognition.Only2%ofFrenchuniversityprofessorshavebeencurrentlydistinguishedbyIUF)

2009AnnualAwardoftheFrenchChemicalSociety(SFC) 2015ChairofExcellenceAMIDEX

-FundedProjects 7regional;7national,14industrials,2FP7(FAME,TERRAMAGSTORE)-Organisationofevents 7internationalconferences,1internationalschool,1nationalconference-Teaching Inorganicchemistry,materials,processing,ceramics,nanotechnology (fromfinalyearbachelor’stomaster’s)+variousresponsibilities.-Miscellaneous Co-founderof2start-ups(2008-2015“Coligro”and2013-now“Solgelway”) MemberoftheScientificAdvisoryBoardof“ChemistryofMaterials”(ACS) Consulting(SOPRA,Photowatt,SaintGobain,AREVA,DSM).

Thomson Reuther Indicators h-index: 56

Av. Nb. Citations /art.: 60 Total citations: 1100

Amongst the 82 most cited French scientists (2014)

70th “World top scientist in Materials Science” (2011)

10

Currentposition:ResearchDirectorCNRS.LeaderoftheEnAPteam(EnergyandAdsorption)atMADIREL.POSITIONSHELDEDUCATION2009-today ResearchDirector,MADIREL,AixMarseillesUniversity,France1993-2009 ResearchAssistant,CTM-CNRS&MADIREL,France2000 VisitingScientistatNorthCarolinaStateUniversity,USA1992-1993 Post-DoctoralResearchFellowship,MainzUniversity,Germany1999 HDR:Accreditationtosuperviseresearch,ProvenceUniversity,France1989-1992 Ph.D.BrunelUniversityUK&CTM/CNRS,France Supervision of Graduate Students and Post-doctoral fellows Icurrentlydirectlymanagearesearchteamofaround5permanentstaff including1Professor,2Lecturers,1CNRSresearcherand1Engineer.Ihavesupervisedaround18PhDstudentswhichequates toanaverageofonePhDdefenceperyearsince IreceivedmyHDRin1999.Ihaveequallysupervised7Post-Doctoralstudentsand3ResearchEngineersontopofanumerousquantityofMastersandUndergraduateStudentprojects.Ofthegraduateandpost-doctoralfellowsthatIhavesupervised,aroundhalfhaveremainedinacademiaandtheotherhalfworkintheindustrialsector.IcurrentlyCo-supervise4PhDstudents. Organization of Scientific Meetings IamcloselyinvolvedeitherintheorganizationcommitteeorscientificcommitteeforseveralconferenceseriesincludingEuroMOF,FundamentalsofAdsorptionandtheCharacterizationofPorousSolids(COPS)series.Ihavebeenchairmanofseveralinternationalconferencesoverthelastfewyears,tabulatedbelow.Date Name Role Typeofevent Noparticipants CountryMay2017 COPS-XI Chairman International 200 FranceSept.2010 MOF2010 Chairman International 350 FranceMay2009 APMCA Co-chair International 50 CzechRepublicMay2005 COPS-VII Chairman International 230 France

Teaching activities IgiveayearlycourseconcerningtheCharacterizationofPorousSolidsviathe‘CNRS-Formationenterprises’(CNRSTrainingCompanies)structure(https://cnrsformation.cnrs.fr/).IteachattherecentlystartedMasterscourseonChemicalNano-Engineering(MasterMundus).CAREERSUMMARY(todo)

- Trackrecord 288Peer-reviewedarticles,books andbookchapters 3 Patents 3 Films >20Invitedinternationalconferences since2000

-Supervision 18PhDstudentsasdirector 7Postdoctoralfellows-Distinctions: 2000.1stAFCAT-SetaramPrize,‘Youngresearcherincalorimetryandthermalanalysis’ -FundedProjects 5regional;7national(2ascoordinator),11EU(4ascoordinator)-Organisationofevents 4InternationalconferencesasChairman,6inOrganizingCommittee,1

nationalconferenceChair -Teaching Adsorption,thermalanalysis,chemicalnano-engineeringat Master’slevel.-MiscellaneousAssociateEditor:‘JournalofExperimentalNanoscience’and‘Adsorption’ AdvisoryBoard:RSCChemicalSocietyReviews(ImpactFactor38.6) Consulting(Bird&Bird).

Google scholar Indicators h-index: 64

Av. Nb. Citations /art.: 70 Total citations: 20088

11