Organic Thin Films for Photonic g s.or001 1 | http://pubs.ack-2010-1039.fw Applications 1b H on April 7, 200 | doi: 10.1021/ G1 R20 BU28, TTSpril V OF PIWeb): A NIe ( Uat y D d bon deati ac wnloPubli Do In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. g s.or001 1 | http://pubs.ack-2010-1039.fw 1b H on April 7, 200 | doi: 10.1021/ G1 R20 BU28, TTSpril V OF PIWeb): A NIe ( Uat y D d bon deati ac wnloPubli Do In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. 1039 ACS SYMPOSIUM SERIES Organic Thin Films for Photonic Applications Warren N. Herman, Editor g LaboratoryforPhysicalSciences,UniversityofMaryland s.or001 11 | http://pubs.acbk-2010-1039.fw OpticalScSiteSencpteehsveDeninviHsRio..nF,FNolauovmlagle,RrEe,sdeEiatdrocihrtoLraboratory H on April 7, 200 | doi: 10.1021/ SchoolofMaterialsScienceandEngineering,ClemsonUniversity G1 R20 BU28, TTSpril V OF PIWeb): A NIe ( Uat y D d bon deati ac wnloPubli Do Sponsored by the ACS Division of Polymer Chemistry AmericanChemicalSociety,Washington,DC In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. LibraryofCongressCataloging-in-PublicationData g 1 | http://pubs.acs.ork-2010-1039.fw001 OMS1IIr.tSnagectBTpaeplnhurNh.iiediaccnn9elmtss7fihH..8biln.-mI-i-.0bFfiH-lod(l8imAouee4vrglC1sgmir2cfeaSaoe-rpn2rssh;.,5ypisW26cmhpa.3oopal-tnOro3orrsesnpe(ofiinatuercolermNkeaed.lpn.esbppcIceyaIletri.prsictFoeehaasnlrteno)ii;odcmA1ndiC0,sneS3S/dv9t[eieeD)cxvde.ieisvtn.eis3dRi.ob.nIyOI]oIr.WgfFaPaonoruirlcelygntmheNrie,nr.SHfiCtelehmpremhsme.ain4ns.t,HrSyP.t.hIeVov.teoAnnRmic.esFr-i-lcoamn, 1b H on April 7, 200 | doi: 10.1021/ CT6h2Ke17m.38i67c-2a-l.dTSc52o52cOie6ty7.5D2i0v1is0ionofPolym2e0r1C0h0e1m29is0t5ry. G1 R20 BU28, V OF PITTSWeb): April TSAthNaenSdpIaaZrpde3r9fo.u4rs8eIndn1fi9on8rtm4h.iastipounbSlicciaetniocnesm—eePtesrmthaenmeninciemoufmPraepqeurirfeomr PenritnstoefdALmiberraircyanMNaatetiroianlasl, NIe ( Copyright©2010AmericanChemicalSociety Uat d by on D DistributedbyOxfordUniversityPress adecati AllRightsReserved. ReprographiccopyingbeyondthatpermittedbySections107or108 Downlo Publi o$f40th.2e5Up.Slu.sC$o0p.y7r5igphetrApacgtiesiasllpoawidedtofothreinCteorpnyarliguhsetConlelya,rapnroceviCdeednttehra,tIancp.e,r2-2c2haRpotesrefweoeoodf Drive,Danvers,MA01923,USA.Republicationorreproductionforsaleofpagesinthis bookispermittedonlyunderlicensefromACS.Directtheseandotherpermissionrequests toACSCopyrightOffice,PublicationsDivision,115516thStreet,N.W.,Washington,DC 20036. Thecitationoftradenamesand/ornamesofmanufacturersinthispublicationisnottobe construedasanendorsementorasapprovalbyACSofthecommercialproductsorservices referenced herein; nor should the mere reference herein to any drawing, specification, chemicalprocess, orotherdataberegardedasalicenseorasaconveyanceofanyright or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce,use,orsellanypatentedinventionorcopyrightedworkthatmayinanywaybe relatedthereto. Registerednames,trademarks,etc.,usedinthispublication,evenwithout specificindicationthereof,arenottobeconsideredunprotectedbylaw. PRINTEDINTHEUNITEDSTATESOFAMERICA In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare 1 | http://pubs.acs.org k-2010-1039.fw001 fdpkoeaervpeaneepBlroispneprmftoeeodparreeyrfsiaratbotgetemoreeatexnshicdynelmcgucodphtmeooedsmppitruaioesbhstblrpeiyesonthnstaeiasuvrodebfriooeecdocnoukcvbse,ey.trthahoegetehpbearoornopdokorf;gsooeardtnihnitezatreabsrtliemeosnotastfyocwbtohehneeatneadnudttdhesiedeisnttoocrepepv.irciSoeiovwsmiedodeef H on April 7, 2010 | doi: 10.1021/b caaodnmddempAdr.asenDhauersnacrsfurtisivlpeeot,nsfeocasnhrsela.ypptrWoeerrpshigaearinrneedaalppienrpeercrso-aeprmaerrviecairhteaew-,rpeeoadapvdepeyrrrsvifoioerarwnmtodaofitor.nraiingltiarncoacdleuprcettavonirecywecohrpaarpeptjeeerrcsstioaarrnee, RG201 included in the volumes. Verbatim reproductions of previous published papers BU28, arenotaccepted. TTSpril V OF PIWeb): A ACSBooksDepartment NIe ( Uat y D d bon deati ac wnloPubli Do In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. Preface Organics are an extraordinarily large class of materials with promising applicationsforphotonicsandelectronics. Thisvolumeisbasedonasymposium entitled“OrganicThinFilmsforPhotonicsApplications(OTF)”heldatthe236th Annual Meeting of the American Chemical Society in Philadelphia, PA August, 011 | http://pubs.acs.org 1/bk-2010-1039.pr001 oOa2oolf0prctge0ttiAaor8cnnTb.amiahelcTterese,rhisltigyhe1ecni9aonsam9yrld3emfipja.eolrtptmioiinnoncstgsegliyssufsbombiaornycrgwikagt,phaioptnesoplatitAthcitecamhedateil1eofrd5finriitocsrshamsptniilnnajCayoafishir,nseeeatelmcldnryoisidecgssanospluipootcStfiniohoctsnoacoaplireosidetcfdyaaottlpaahmmtnesiedcteoeapetrtlhotiainetgncegeognO.mstipiTnahmthliocTuesaiontmmlericdoSpeanaoeettctciioiottinhengoitesnysrf, 22 7, 10 have evolved to also include discussions of three dimensional photolithography n April doi: 10. ahnadvesporloarvipdoewdearugneiqnuereaotipopno.rtuOnviteyrftohrecyheeamrsi,ststh,emseateinritaelrsdisscciiepnltiinsatsry, pmhyeseitcinisgtss GH o010 | and engineers to gather to present and discuss new theoretical and experimental TTSBURpril 28, 2 rinesteurlTntsahtoeion1n5oatrlhglyasnyrimeccpothogisnniuizfimeldminsmccliuaetdneetridisat1lss8caionnvvdeirtpeihndogttaoalnkwisciaddneedvv2iac1reicseo.tyntorifbtuotpeidcpsaipnecrlusdfrinogm: OF PIeb): A Electro-opticpolymersforhighspeeddatamodulationandterahertzemissionand V W sensing; Third order nonlinear optical materials for all-optical signal processing NIe ( and optical limiting; Multiphoton absorption polymerization fabrication of Uat y D optical devices; Organic photovoltaics; Terahertz spectroscopy of organic ded bation semiconducting materials; Polymer based plasmonic devices; Photorefractive wnloaPublic paboslyomrbeinrsgamndatdeerivailcsesfofror3Dholoopgtriacpahlidcadtaispsltaoyrasg;eA;llE-pleocltyrmo-elurmlaisneerssc;eTnwtoc-oplhlooitdosn; o D and Conducting and semiconducting polymers for photovoltaic and transistor applications. Today, organic light emitting diodes for optical displays and polymer waveguidesdiscussedinseveraloftheearlyOTFmeetingshavebeendeveloped tothepointofhighlysuccessfulcommercialization. Thedevelopmentoforganic nonlinearopticalandoptoelectronicmaterialsforopticalcommunications,power generation, data storage, and other applications have not yet reached the same level of maturity but offer the similar levels of promise that the early OLED and polymer waveguides studies showed. This book describes recent research in materials development, characterization techniques, and device development relatedtoorganicthinfilmsforphotonicapplications. ix In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. Acknowledgments ThissymposiumwassponsoredbytheAmericanChemicalSocietyDivision ofPolymerChemistrywithadditionalgeneroussupportprovidedbytheU.S.Air ForceOfficeofScientificResearchandtheU.S.OfficeofNavalResearch. WarrenN.Herman Editor LaboratoryforPhysicalSciences,UniversityofMaryland g 011 | http://pubs.acs.or1/bk-2010-1039.pr001 SEOtdpeitvtioceranlRSc.iFenlocmesDivision,NavalResearchLaboratory 7, 2102 StephenH.Foulger n April doi: 10. Editor H o0 | SchoolofMaterialsScienceandEngineering,ClemsonUniversity G01 R2 BU28, TTSpril OF PIeb): A V W NIe ( Uat y D d bon deati ac wnloPubli o D x In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. Chapter 1 Introduction WarrenN.Herman,*,1StevenR.Flom,2andStephenH.Foulger3 1 | http://pubs.acs.org k-2010-1039.ch001 3CSecnh1toLeo2raOlbfopoof8trriM0acO5taoa0lprttSeGyirccrifaiaeeollenrsMncPSmeashcWteiyeDeaasrndiiiscvcahDaeilisslnriaoSiSgnvnctcdeo,ii,eenENnCn,nccaoDeegvlsCliaae,nlngeU2eRde0nrPe3Eiis7vnane5ergagrk,ris,nCciMthelyeeDLrmoiafns2bogM0on7Tra4Uear0ctynohliranvynoe,drlos,gitiye,s, 1b n April 7, 20doi: 10.1021/ *hCerlemmasno@n,lpSsC.u2m9d6.3e4du H o0 | G01 TTSBURpril 28, 2 tiTonhoekAucpghluaapsctteer2s0in0o8f.PhthiliTasdheeblyopohdkiaesacarrotibseetherferosaemnarncuahalspyrAmogCproSessisummienettithnhaget OF PIeb): A development of materials, characterization techniques, and V W devices related to organic thin films for photonic applications. NIe ( Thetopicscoveredcanbedividedintotwogeneralcategories: Uat ded by ation D itnhveolfivresst ionrvgoanlvicesseomrgiacnoincduncotnolrisnewarithopetmicpshaansids tohne osregcaonnidc ac wnloPubli owpittoherleeccotrrodninicgs-.sIenttcilnugdeedleacrteroth-oepdtiecveclooepfmficeinetnotsfcahnrdompoolpinhgoroesf o D thickpolymerslabs,demonstrationofplasmonicwaveguidesin electro-opticmaterials,fabricationofthelargestphotorefractive 3D display to date, new photosensitive polymeric systems for optical data storage, 3D photonic structures fabricated by multiphoton absorption polymerization, a practical technique for measuring the phase of the complex third-order nonlinear susceptibility without the need for a reference material, electroluminescent colloidal particles that can be designed to produce a wide range of emission colors, the creation of thin-film lasers through the coextrusion of multilayered polymeric films, issues related to improving the power conversion efficiency of organic solar cells, various organic semiconductor materials and the use of terahertz spectroscopy ©2010AmericanChemicalSociety In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0. techniques for determining carrier dynamics in organic semiconductors. In this introduction we provide some background information and a brief summary of the exciting developmentsreportedintheremainderofthebook. Organic Nonlinear Optical Materials and Devices Electro-OpticOrganicMaterialsandDevices Electro-optic materials are a special case of second-order nonlinear optical (NLO) materials (1). They possess the property than an applied electric-field g (generated by a voltage applied to electrodes) modifies the refractive index 1 | http://pubs.acs.ork-2010-1039.ch001 ompcaonfhomdodtthbtuoreilranaeptemfoprdarainctwaegtniri.vdtihaeTsl.wmhefeioftTcelleihchnctiisuensalgafrpordrerecolvoephicmeoctrlerptoosyog-fnoropaeprepnttrihtemcsilceiettchfsiofanemtftchoptmerrm(ouofvnaraitibdicPoreaointccciaokhstnetaiooslrsrgnaaeepgofpgeffleeicacnotnaep)tdrtiaiiosctdniaorislsenpal,wanlattdaeryavdesnentsgwaopubhotilehdretnees, n April 7, 201doi: 10.1021/b sienelecacontnreidcxopfiraednledsriEoenl.eTocoftrtithcheisrumdsaoccerdrpoetsirbciionlpitpiycoχwe(l2ee)rcastproipcfeEpaor,iltnahgriiszuaentxdiopenarntvhseieocntdoicrpaoPnleibnaeppwopwrroitextreismnoaftitohne H o0 | G01 R2 BU28, TTSpril whereε0isthepermittivityoffreespaceandthecoordinateindicestakethevalues OF PIeb): A 1v,e2c,t3orws,iththseuemvmena-toiordneorvseursrceeppetaibteidlitiinedsicmeussutnvdaenrsistohofdo.rBaemcaauteseriPalatnhdatEpaorsesepsosleasr V W a center of inversion. The macroscopic second-order optical nonlinearity in NIe ( Uat organic materials originates from chromophores, organic molecules that lack y D d bon inversion symmetry and exhibit optical nonlinearity on the microscopic scale deati (2). Macroscopic structures incorporating chromophores that are randomly ac ownlo Publi osyrimenmteedtrywiclalnpobsesersesmionvveedrsiboyncsryymstmalegtrryo,watnhd,cboynLseaqnugemnutliyr-aBzloedrogeχt(t2)d.eIpnovseirtsiioonn, D or by orientationally ordering the chromphores with an applied electric field, referredtoaselectricfieldpoling(3–5). Theexistenceofsecondorderopticalnonlinearitiesinorganicmoleculeshas been known since the late 1960s (6, 7). Experimental findings were primarily based on second-harmonic generation (SHG) in organic crystals or electric-field inducedSHGinliquidsuntilthefirstelectric-fieldpoledsecond-ordernonlinear polymericthinsolidfilmswerereportedin1982(8,9). Activeresearchthrough late 1970 and the 1980s led to a number of professional symposia resulting in numerous symposium books (10–13) on both second-order and third-order nonlinearopticalpropertiesoforganicthinfilms. In 1992, electro-optic polymeric materials garnered serious attention with the demonstration of a wideband 40 GHz Mach-Zehnder optical modulator using a methacrylate polymer with side chain groups containing 2 In Organic Thin Films for Photonic Applications; Herman, W., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 0.