Anisotropic Resonant X ‑ ray Di ff raction of a Conjugated Polymer at the Sulfur K ‑ Edge - Freychet et al. - 2021 - Unknown

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pubs.acs.org/JPCLLetterAnisotropicResonantX‑rayDiffractionofaConjugatedPolymerattheSulfurK‑EdgeGuillaumeFreychet,EliotGann,MikhailZhernenkov,andChristopherR.McNeill*CiteThis:J.Phys.Chem.Lett.2021,12,3762−3766ReadOnlineACCESSMetrics&MoreArticleRecommendations*sıSupportingInformationABSTRACT:Theplanar,aromaticnatureofthebackboneofconjugatedpolymersendowsthemwithanisotropicproperties.HereweshowthattheresonantX-raydiffractionofasulfur-containingsemicrystallineconjugatedpolymeratthesulfurK-edgeishighlyanisotropic,withstrongmodulationofdiffractedintensitydependingupontherelativeorientationofthepolarizationoftheincidentbeamwithrespecttothediffractingcrystalplanes.Throughdeterminationoftheanisotropicresonantscatteringfactors,wecanspectroscopicallyreproducetheobservedresonantanisotropicscatteringeffectsbasedonaproposedunitcellgeometryforthepolymer.onjugatedpolymershavebeenintenselystudiedovertheThechemicalstructureofthepolymerstudied,poly([N,N′-Cpastfewdecadesforapplicationinpolymersolarcells,bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-field-effecttransistors,light-emittingdiodes,andthermo-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)),P(NDI2OD-T2),isde-1pictedinFigure1a.P(NDI2OD-T2)isasemicrystallineelectrics.Theoptoelectronicpropertiesofconjugatedpolymers1electrontransportingpolymerwitharelativelyhighelectronderivefromtheplanarconjugatednatureofthebackbone.6,73,8Flexiblealkylside-chainsimpartsolubility,withmanymobilityandrelativelyhighcrystallinity.Likemany2,3conjugatedpolymers,itadoptsalamellarcrystalstructure,9conjugatedpolymersexhibitingasemicrystallinenature.Themolecularpackingofconjugatedpolymerchainsstronglywithlayersofextendedπ-stackedbackbonesseparatedbylayersinfluencestheopticalandelectronicpropertiesoftheseofalkylside-chains.Thealkyl-stackingdirectionisindexedasthematerials,andbeingabletoaccuratelycharacterizemoleculara-axisofthetriclinicunitcell,withtheπ−πstackingdirectionpackingiscriticalforestablishingstructure−functionrelation-indexedastheb-axisandthebackbonedirectionindexedastheships.4Whilemanyconjugatedpolymersaresemicrystalline,c-axis(seeFigure1b).P(NDI2OD-T2)hastwosulfuratomspertheyarealsoparacrystallinewithfewdiffractionpeaksrepeatunit,whichmakeitsuitableforresonantdiffractionobservablewithconventionalX-raydiffraction.RecentlyweexperimentsatthesulfurK-edge.DownloadedviaUNIVOFCALIFORNIASANTABARBARAonMay16,2021at11:36:32(UTC).Seehttps://pubs.acs.org/sharingguidelinesforoptionsonhowtolegitimatelysharepublishedarticles.reportedstrongresonantdiffractioneffectsatthesulfurK-edgeResonantX-raydiffractionwasperformedintransmissiononofawell-studiedconjugatedpolymer.5ThesulfurK-edgeisfilms630±30nmthicksupportedbysiliconnitridemembraneslocatedinthe“tender”X-rayregime,withanenergyof∼2500with100nmmembranethickness.EvenwiththisthickereVcorrespondingtoawavelengthof∼0.5nm.Thisenablessample,theX-raytransmissionisstill>98%throughthesulfurK-edge,(seeFigureS1intheSupportingInformation).Filmswerediffractionpeakscorrespondingtod-spacingsofdownto0.5nmspin-coatedfromchlorobenzene(30g/L,2000rpmspinspeed)tobeprobed;whilethisisinsufficienttodirectlyobserveπ−πontoglassslidescoatedwithawater-solublelayerofsodiumstackingpeaks,itissufficienttostudylamellarstackingpeakspolystyrenesulfonate(NaPSS).Filmswerethenannealedat210andbackbonestackingpeaksinconjugatedpolymers.The°Cfor20mininanitrogengloveboxandthensubsequentlyadditionalinformationprovidedbythemodulationindiffractedfloatedoffontodeionizedwaterandtransferredtosiliconnitrideintensitywithenergyenabledustodiscernbetweendifferentproposedunitcellpackinggeometries.AnisotropyintheobservedresonantdiffractionwasalsonotedbutwasnotReceived:February17,2021exploredinanydepthoradequatelyexplained.AidedbyAccepted:April2,2021improveddataqualityfromathickersampleandindependentPublished:April12,2021measurementoftheanisotropicatomicscatteringfactors,herewereportonandaccountforthespectroscopicsignatureofanisotropicscattering.©2021AmericanChemicalSocietyhttps://doi.org/10.1021/acs.jpclett.1c005323762J.Phys.Chem.Lett.2021,12,3762−3766

1TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterrayenergyismovedthroughthesulfurK-edge,theintensityofthesepeaksisstronglymodulated(seeVideoS1).ProminentdiffractionanisotropyisalsoobservedastheX-rayenergyismovedthroughthesulfurK-edge,withvariationsintherelativemagnitudeofdiffractionalongqx(i.e.,paralleltotheelectricfieldvector)andalongqz(i.e.,perpendiculartotheelectricfieldvector).Whilethereisnotmacroscopicin-planealignmentofthecrystallites,byobservingthescatteringpatternonatwo-dimensionaldetector,wecandiscriminatebetweencrystalliteswithbackbonesparallelandperpendiculartothepolarizationoftheincidentbeam.Forexample,theintensityofthe(001)peakobservedonthedetectoralongtheqxdirectiondirectlycorrespondstopolymercrystalliteswhosebackbonesarealignedwiththeqxdirectionandhenceareparalleltothebeampolarization.Conversely,theintensityofthe(001)peakintheqzdirectioncorrespondstopolymercrystalliteswhosebackbonesarealignedwiththeqzdirectionandhenceareperpendiculartothebeampolarization.Thus,bysamplingthediffractionintensityalongtheqxandqzdirections,wecanselectivelyanalyzecrystalliteswithbackbonealignmentparallelandperpendiculartothebeampolarization.Figure2aplotsthevariationintheradiallyaverageddiffractionintensityoftheFigure1.(a)ChemicalstructureofthepolymerP(NDI2OD-T2).(b)(100)peakalongwithvariationsintheparallel(alongqx)andSchematicoftheunitcellgeometryandproposedunitcellpackingofperpendicular(alongqz)diffractionintensitiesofthe(100)9P(NDI2OD-T2)withtheb-axisoutofplaneafterLemauretal.(c)peak.(DetailsofdatareductionandpeakfittingtoproducetheTransmissionX-rayscatteringpatternofaP(NDI2OD-T2)filmtakenatanenergyof2445eV.membranes.P(NDI2OD-T2)wassuppliedbyRaynergyTekInc.withamolarmassofMn=85.5kDaanddispersityofĐ=2.1.(Certainsuppliers,commercialequipment,instruments,ormaterialsareidentifiedinthispapertofosterunderstanding.SuchidentificationdoesnotimplyrecommendationorendorsementbytheNationalInstituteofStandardsandTechnology,nordoesitimplythatthematerialsorequipmentidentifiedarenecessarilythebestavailableforthepurpose.)ResonantdiffractionmeasurementswereperformedattheSoftMatterInterfaces(SMI)beamline(Beamline12-ID)atthe10NationalSynchrotronLightSourceII.Samplesweremeasuredwiththesiliconnitridemembranesnormaltotheincidentbeam.Experimentswereperformedinvacuumwithtwo-dimensionalscatteringpatternsrecordedonaPilatus300K-Wdetector.Scatteringpatternsweremeasuredasafunctionofenergybyvaryingthephotonenergybetween2445and2500eV,withstepsof0.25eVtakenthroughthesulfurK-edgebetween2470and2480eV.TheelectricfieldvectoroftheincidentpolarizedX-raybeamwasinthehorizontalplane,coincidingwiththex-axisoftheexperimentframe,withthey-axiscoincidingwiththebeamdirectionandthez-axisbeingdirectedintheverticaldirection.Furtherdetailsoftheexperimentanddatareduction5canbefoundinourpreviouspaperandintheSupportingInformation.Thetwo-dimensionaltransmissionX-rayscatteringpatternoftheP(NDI2OD-T2)filmtakenat2450eV(justbelowthesulfurK-edge)isshowninFigure1c.TheP(NDI2OD-T2)film8exhibitsa“face-on”texture,withgrazingincidencewide-angleX-rayscatteringdataprovidedinFigureS4.Thefirstpeakatq∼−1−1Figure2.Energydependenceofdiffractionintensityfor(a)the(100)0.25Åisthe(100)peak,whilethepeakatq∼0.5Åisa−1peakand(b)the(001)peak.Symbolsrepresentexperimentaldatacompositeofthe(001)peakat0.46Åandthe(200)peakatwhilesolidlinesrepresentcalculatedintensities.Blacksymbolsand0.49Å−18(seealsoFiguresS2andS3).Spin-coatedlinesrepresentradiallyaveragedintensity;redsymbolsandlinesP(NDI2OD-T2)filmslackanylong-rangein-planealignment,representintensityinthedirectionparalleltotheelectricfieldvectorofwiththenonresonantscatteringpatterntakenat2450eVthebeam;greensymbolsandlinesrepresentintensityinthedirectionshowingisotropicscatteringfeaturesintheqxzplane.AstheX-perpendiculartotheelectricfieldvectorofthebeam.3763https://doi.org/10.1021/acs.jpclett.1c00532J.Phys.Chem.Lett.2021,12,3762−3766

2TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterresultsofFigure2areprovidedintheSupportingInformation.)ijjfffuu′′′vuwyzzijjfffuu″″″vuwyzzFigure2bsimilarlyplotsthevariationsindiffractionintensityforjjzzjjzzjjzzjjzzthe(001)peak.Both(100)and(001)peaksexhibitstrongf′=jjjjfffuv′′′vvwzzzz,f″=jjjjfffuv″″″vvwzzzzmodulationindiffractionintensityastheX-raybeamismovedjjzzjjzzjjfff′′′zzjjfff″″″zzthroughthesulfuredge.Foreachpeak,therearealsostrikingkuwvww{kuwvww{(4)spectroscopicdifferencesbetweenthescatteringparallelandwheretheu-andw-axesareparalleltotheaandc*directionsperpendiculartothepolarizationoftheX-raybeam,reflecting12andthey-axisisorthogonaltouandw.ToexperimentallydifferentinteractionsofcrystalliteswiththeX-raybeamdeterminef′andf″,aminimumofsixX-rayabsorptionspectradependingontherelativeorientationsofthecrystalliteswithneedtobemeasuredwithdifferentorientationsoftheX-rayrespecttothebeampolarization.Forthe(100)peak,theparallelpolarizationrelativetotheunitcell.Tothisend,angle-resolvedscatteringintensityis∼1.8timestheperpendicularintensityatX-rayabsorptionmeasurementsatthesulfurK-edgehavebeen2476.25eV,withthisanisotropyreversingat2477.75eVwithperformedonalignedP(NDI2OD-T2)filmspreparedbybladetheperpendicularintensitythen∼2timesasintenseasthe14coating.TheseX-rayabsorptionmeasurementswerealsoparallelintensity.Forthe(001)peak,theparallelintensityisperformedattheSMIbeamlinebyusingthePilatusarea∼1.4timestheperpendicularintensityat2476.75eV,withthisdetectorasafluorescencedetector.Sevenspectrawereacquiredanisotropyreversingat2478eVwiththeperpendicularintensitywithdifferentrelativeorientationsoftheelectricfieldvectorthen∼2.4timesasintenseastheparallelintensity.withrespecttothealignmentdirection,withfurtherdetailsTounderstandtheoriginoftheobserveddiffractionprovidedintheSupportingInformation.Followingtheanisotropy,weturntothetheoryofresonantdiffraction.The12approachofBricogneetal.,thefullabsorptiontensorwasintensityofanobservedreflectionh=(h,k,l)isproportionaltocalculatedwiththecross-termsfoundtobenegligible.Basedonthemagnitudeofthestructurefactorsquared,thatistheabsorptionspectracorrespondingtothepolarizationaligned2alongthethreeprincipalaxes,theatomicscatteringfactorswereI()hh∝|F()|(1)calculated(seetheSupportingInformationformoredetails).ThestructurefactordependsuponthetypeandrelativepositionTheresultsareshowninFigure3,withfu′andfu″beingoftheatomsintheunitcell:atomsFf()hh=·∑exp(2πir)jjj(2)whereristhelocationofthejthatomintheunitcellandfisthejjenergydependentatomicscatteringfactorofthejthatom.Changesinscatteringintensityatresonancecomeaboutduetotheenergydependenceoftheatomicscatteringfactors.Theatomicscatteringfactorshavearealandimaginarycomponentswhichcanbeexpressedasf=+′ffi0+″f(3)followingtheconventionoftheproteincrystallography11community.TherealcomponentoftheatomicscatteringFigure3.Anisotropicresonantscatteringfactorsforthesulfuratomsinfactorissplitintoanenergy-independentcomponentf0whichP(NDI2OD-T2).canbeapproximatedbytheatomicnumberZaintheforwardscatteringlimitandanenergy-dependentcomponentf′.Theimaginarycomponentoftheatomicscatteringfactorf″isrelatedapplicablewhentheX-raypolarizationisparalleltothelamellartotheimaginarycomponentoftherefractiveindexandcanbestackingdirection,fv′andfv″beingapplicablewhentheX-rayexperimentallydeterminedfromabsorptionmeasurements,withpolarizationisparalleltotheπ−πstackingdirection,andfw′andtherealcomponentf′determinedviatheKramers−Kronigfw″beingapplicablewhentheX-raypolarizationisparalleltothe11relationship.Notethattheenergydependenceoftheatomicbackbonestackingdirection.Basedonpreviousobservationsscatteringfactorsisrelatedtothebondinginthematerial,andsoandcalculationsoftheX-rayabsorptionspectraofthiophene15−18theyarenotpurely“atomic”andneedtobemeasuredforeachandthiophene-containingmoleculesandpolymers,thedifferentpolymerstudiedastheywilleachhavedifferentlargepeakinthefw″spectrumcorrespondstothe1s→(S−chemistry.C)σ*peakwhosetransitiondipolemomentispredominantly19Foranisotropicmaterialssuchasconjugatedpolymers,thedirectedalongthebackbone.Thedominantpeakinthefv″atomicscatteringfactorsaretensors;aswellasbeingenergy-spectrumthatis∼1eVlowerinenergycorrespondstothe1s→dependent,f′andf″willtakedifferentvaluesdependingonthe(S−C)π*peakwhosetransitiondipolemomentisorientedorientationofthepolarizationoftheX-raybeamrelativetotheperpendiculartothethiopheneringandhenceperpendicularto12unitcell.WhiledichroismoftheX-rayabsorptionofthepolymerbackbone.Theseassignmentsarealsoconsistent13conjugatedpolymersiswell-known,anisotropicresonantwithangle-resolvedmeasurementsofthiophenemoleculeson20diffractioneffectshavenotbeenpreviouslydescribed,norhavemetalsurfaces.Thehigherenergypeakssuchasthosethataretheanisotropicatomicscatteringfactorsbeendetermined.Inprominentinthefw″spectrumarelikelyassociatedwith1s→general,foratriclinicunitcell,thetensorsf′andf″willhavesix(C−C)σ*transitions.Usingtheseanisotropicscatteringfactors,12independentelements:wearethenabletocalculatetheexpectedresonantdiffraction3764https://doi.org/10.1021/acs.jpclett.1c00532J.Phys.Chem.Lett.2021,12,3762−3766

3TheJournalofPhysicalChemistryLetterspubs.acs.org/JPCLLetterprofilesforthe(100)and(001)peaksforscatteringparallelandhttps://pubs.acs.org/10.1021/acs.jpclett.1c00532perpendiculartothepolarizationoftheincidentbeam.Thisisachievedbycomputing|F(h)|2accordingtoeqs1and2byusingNotesfw′andfw″forpolymerchainswhosebackbonesarealignedTheauthorsdeclarenocompetingfinancialinterest.paralleltopolarizationofthebeam(thatproducea(100)peakalongqzanda(001)peakalongqx),andfu′andfu″forpolymer■ACKNOWLEDGMENTSchainswhosebackbonesarealignedperpendiculartotheThisresearchusedtheSoftMatterInterfaces(SMI)beamlinepolarizationofthebeam(thatproducea(100)peakalongqxand(Beamline12-ID)oftheNationalSynchrotronLightSourceII,aa(001)peakalongqz).The“Anti(R,S)”unitcellfromLemaur9U.S.DepartmentofEnergy(DOE)OfficeofScienceUseretal.wasusedfortheatomicpositions,withfurtherdetailsof5FacilityoperatedfortheDOEOfficeofSciencebyBrookhaventhecalculationsprovidedinourpreviouspublication.NationalLaboratoryunderContractDE-SC0012704.TheThecalculatedanisotropicscatteringprofilesareshownasauthorsthankVincentLemaur(U.Mons)forprovidingthesolidlinesinFigure2.ExcellentagreementisfoundbetweenthecrystallographicinformationfileoftheAnti(R,S)unitcellofexperimentalprofilesandthesimulatedprofiles,withall9P(NDI2OD-T2).spectroscopicfeaturesreproduced.Thedeviationsfromtheradiallyaveragedprofilesareallaccuratelypredictedalongwith■theobservedrelativeintensitiesofthespectralfeatures.First-REFERENCESprinciplescalculationsofX-rayabsorption21,22atthesulfurK-(1)Heeger,A.J.Semiconductingpolymers:theThirdGeneration.edgeareproposedwhichwillhelpprovidefurtherphysicalChem.Soc.Rev.2010,39(7),2354−2371.insightintothespectralfeaturesobservedandtoconnectthe(2)Sirringhaus,H.;Brown,P.J.;Friend,R.H.;Nielsen,M.M.;Bechgaard,K.;Langeveld-Voss,B.M.W.;Spiering,A.J.H.;Janssen,R.resonantdiffractioneffectstomolecularanisotropy.A.J.;Meijer,E.W.;Herwig,P.;deLeeuw,D.M.Two-dimensionalInsummary,wehavereportedforthefirsttimethechargetransportinself-organized,high-mobilityconjugatedpolymers.spectroscopicsignatureofanisotropicresonantdiffractionofaNature1999,401(6754),685−688.conjugatedpolymeratthesulfurK-edge.Bydeterminingthe(3)Takacs,C.J.;Treat,N.D.;Krämer,S.;Chen,Z.;Facchetti,A.;anisotropicscatteringfactorsfrommeasurementoftheproper-Chabinyc,M.L.;Heeger,A.J.RemarkableOrderofaHigh-tiesofalignedfilms,wehavealsobeenabletotheoreticallyPerformancePolymer.NanoLett.2013,13(6),2522−2527.reproducetheobservedanisotropicresonantdiffraction(4)Rivnay,J.;Mannsfeld,S.C.B.;Miller,C.E.;Salleo,A.;Toney,M.features,demonstratingthedirectcorrespondencebetweenF.QuantitativeDeterminationofOrganicSemiconductorMicro-theanisotropicX-rayopticalpropertiesofthesematerialsandstructurefromtheMoleculartoDeviceScale.Chem.Rev.2012,112theiranisotropicdiffraction.Understandingofanisotropic(10),5488−5519.(5)Freychet,G.;Gann,E.;Thomsen,L.;Jiao,X.;McNeill,C.R.resonantdiffractionisanimportantstepinthedevelopmentResonantTenderX-rayDiffractionforDisclosingtheMolecularofresonanttenderX-raydiffractiontoprobemolecularPackingofParacrystallineConjugatedPolymerFilms.J.Am.Chem.Soc.conformationswithintheunitcellofconjugatedpolymers.2021,143(3),1409−1415.(6)Yan,H.;Chen,Z.;Zheng,Y.;Newman,C.;Quinn,J.R.;Dötz,F.;■ASSOCIATEDCONTENTKastler,M.;Facchetti,A.Ahigh-mobilityelectron-transporting*sıSupportingInformationpolymerforprintedtransistors.Nature2009,457,679−687.TheSupportingInformationisavailablefreeofchargeat(7)Bucella,S.;Luzio,A.;Gann,E.;Thomsen,L.;McNeill,C.R.;Pace,G.;Perinot,A.;Chen,Z.;Facchetti,A.;Caironi,M.Macroscopicandhttps://pubs.acs.org/doi/10.1021/acs.jpclett.1c00532.high-throughputprintingofalignednanostructuredpolymersemi-CalculatedX-raytransmissionvaluesandfurtherconductorsforMHzlarge-areaelectronics.Nat.Commun.2015,6,experimentaldetailsincludingdetailsofpeakfittingand8394.determinationoftheabsorptiontensor(PDF)(8)Rivnay,J.;Toney,M.F.;Zheng,Y.;Kauvar,I.V.;Chen,Z.;VideoS1showingtheevolutionofscatteringpatternsWagner,V.;Facchetti,A.;Salleo,A.UnconventionalFace-OnTextureandExceptionalIn-PlaneOrderofaHighMobilityn-TypePolymer.withX-rayenergy(MP4)Adv.Mater.2010,22(39),4359−4363.(9)Lemaur,V.;Muccioli,L.;Zannoni,C.;Beljonne,D.;Lazzaroni,R.;■AUTHORINFORMATIONCornil,J.;Olivier,Y.OntheSupramolecularPackingofHighElectronCorrespondingAuthorMobilityNaphthaleneDiimideCopolymers:ThePerfectRegistryofAsymmetricBranchedAlkylSideChains.Macromolecules2013,46ChristopherR.McNeill−DepartmentofMaterialsScienceand(20),8171−8178.Engineering,MonashUniversity,Clayton,Victoria3800,(10)Zhernenkov,M.;Canestrari,N.;Chubar,O.;DiMasi,E.SoftAustralia;orcid.org/0000-0001-5221-878X;matterinterfacesbeamlineatNSLS-II:geometricalray-tracingvs.Email:christopher.mcneill@monash.eduwavefrontpropagationsimulations.Proc.SPIE2014,9209,92090G.(11)Hendrickson,W.A.DeterminationofMacromolecularAuthorsStructuresfromAnomalousDiffractionofSynchrotronRadiationGuillaumeFreychet−NSLS-II,BrookhavenNationalfromAnomalousDiffractionofSynchrotronRadiation.Science1991,Laboratory,Upton,NewYork11973,UnitedStates254(5028),51.EliotGann−MaterialsMeasurementScienceDivision,(12)Bricogne,G.;Capelli,S.C.;Evans,G.;Mitschler,A.;Pattison,P.;MaterialsMeasurementLaboratory,NationalInstituteofRoversi,P.;Schiltz,M.X-rayabsorption,refractionandresonantStandardsandTechnology,Gaithersburg,Maryland20899,scatteringtensorsinselenatedproteincrystals:implicationsfordataUnitedStates;orcid.org/0000-0001-5570-8880collectionstrategiesinmacromolecularcrystallography.J.Appl.MikhailZhernenkov−NSLS-II,BrookhavenNationalCrystallogr.2005,38(1),168−182.Laboratory,Upton,NewYork11973,UnitedStates;(13)Nahid,M.M.;Gann,E.;Thomsen,L.;McNeill,C.R.NEXAFSspectroscopyofconjugatedpolymers.Eur.Polym.J.2016,81,532−554.orcid.org/0000-0003-3604-0672(14)Trefz,D.;Gross,Y.M.;Dingler,C.;Tkachov,R.;Hamidi-Sakr,Completecontactinformationisavailableat:A.;Kiriy,A.;McNeill,C.R.;Brinkmann,M.;Ludwigs,S.Tuning3765https://doi.org/10.1021/acs.jpclett.1c00532J.Phys.Chem.Lett.2021,12,3762−3766

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