Springer Theses Recognizing Outstanding Ph.D. Research Jill Guyonnet Ferroelectric Domain Walls Statics, Dynamics, and Functionalities Revealed by Atomic Force Microscopy Springer Theses Recognizing Outstanding Ph.D. Research For furthervolumes: http://www.springer.com/series/8790 Aims and Scope The series ‘‘Springer Theses’’ brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected for its scientific excellence and the high impact of its contents for the pertinent fieldofresearch.Forgreateraccessibilitytonon-specialists,thepublishedversions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explaining the special relevance of the work for the field. 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Jill Guyonnet Ferroelectric Domain Walls Statics, Dynamics, and Functionalities Revealed by Atomic Force Microscopy Doctoral Thesis accepted by the University of Geneva, Switzerland 123 Author Supervisor Dr. JillGuyonnet Prof.Patrycja Paruch DPMC-MaNEP DPMC-MaNEP Universityof Geneva Universityof Geneva Geneva Geneva Switzerland Switzerland ISSN 2190-5053 ISSN 2190-5061 (electronic) ISBN 978-3-319-05749-1 ISBN 978-3-319-05750-7 (eBook) DOI 10.1007/978-3-319-05750-7 Springer ChamHeidelberg New YorkDordrecht London LibraryofCongressControlNumber:2014935277 (cid:2)SpringerInternationalPublishingSwitzerland2014 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodology now known or hereafter developed. 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While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Every wall is a door —R. W. Emerson Supervisor’s Foreword Ferroelectricmaterials,initiallyseenasmerelyacuriosityupontheirdiscoveryin 1920 by Valasek, have become an important feature of the modern technological landscape. Named in analogy to ferromagnets, although often containing no iron whatsoever, ferroelectrics are characterised by a non-volatile electric dipole moment,orpolarisation,whosedirectioncanbeswitchedunderanappliedelectric field. Like their ferromagnetic counterparts, ferroelectric samples generally com- prise many regions or domains with different orientation of the polarisation, separated by interfaces known as domain walls. They also present associated pyroelectric, piezoelectric and electro-optic properties, allowing their widespread integration as electromechanical transducers in radar and ultrasound applications, for second harmonic and sum frequency generation in nonlinear optics, and as transistor elements in ferroelectric random access memories. The domain walls, essentially extended topological defects in their parent ferroelectricphaseinwhichthepolarisationislocallyminimised,werehistorically perceived as something of a nuisance, contributing to fatigue (a gradual decrease of the switching response in devices) and, at increasing density in ever-thinner films, diminishing the total volume of actually ferroelectric material. More recently,however,itisthedomainwallsthathavebecomeamajorresearchfocus. Attheseintrinsicallynanoscaleinterfaces,symmetrybreaking,variationsinstrain, defect segregation, and more complex electronic or structural reconstruction can lead to radically different physical properties from those presented by the parent phase. More generally, the energy cost associated with the formation offerroelectric domain walls, and their pinning by many different defects inherently present in thin films, including oxygen vacancies, dislocations, or grain boundaries, allow them to be described as disordered elastic manifolds. This statistical physics approach provides a general framework in which the behaviour of systems as diverse as propagating fractures, wetting lines, burning fronts or surface growth canbeunderstood.Insuchsystems,thecompetitionbetweenelasticityandpinning in a fluctuation potential energy landscape gives rise to characteristic roughening and a complex dynamic response to applied forces. Ferroelectric domain walls provide ausefulexperimental model system with precise control over the applied electric field, temperature, and strain, and the ability to influence the type and vii viii Supervisor’sForeword densityofdefectspresentinthesample.Conversely,abetterunderstandingofthis fundamentalphysicsallowskeyparameterscontrollingdomainswitching,growth, and stability to be determined, and used to improve the performance of ferro- electric materials in memory, optics, sensor, and actuator applications. JillGuyonnet’sthesisexploresboththemorefundamentalaspectsofroughness scaling offerroelectric domain walls within the disordered elastic system frame- work, and their localised novel functional behaviour, motivated by potential nanoelectronic applications, using the relatively simple tetragonal ferroelectric solid solution of Pb(Zr,Ti)O , widely integrated in modern ferroelectrics tech- 3 nologies, and exploiting the nanoscale resolution of scanned probe microscopy techniques. During her doctoral research, Jill identified a novel piezoelectric response at domain walls, forbidden by symmetry in the parent phase, and which could be useful in surface acoustic wave transducers based on ferroelectric domain struc- tures. She also demonstrated domain-wall-specific electrical conduction in this otherwide insulating material, the first such observation beyond the discovery of this unexpected phenomenon in the much more complex multiferroic BiFeO , 3 showing its very general nature. Analysing the roughening of such domain walls withinafullmultiscalingapproach,Jillalsofoundthatstronglocaldefectsleadto abreakdownofthesimple,monoaffineroughnessscalingwhichhadbeenassumed inallpreviousstudiesofthesesystems.Finally,comparingdomainroughnessand switching dynamics in both ambient conditions and under ultrahigh vacuum, she was able to elucidate the complex interplay between screening by surface water, andthepinningbysampledefects,whichtogethercontrolthegrowthrates,aswell as the final shape and stability of the domains. The results of this thesis are not only exciting and topical, but should also appeal to a broad range of interests, from (multi)ferroic studies in condensed matterphysicstofractureanalysisandsurfacegrowthinstatisticalphysics.Atthe sametime,thethesisprovidesaclearandeasilyaccessibleintroductiontotherich and interesting physics offerroelectric domain walls—which we hope you’ll find as fascinating and as fun as we do. Geneva, January 2014 Prof. Patrycja Paruch Acknowledgments I first wish to express my infinite gratitude to Prof. Patrycja Paruch for accepting me in her group, back in its early days. Her kindness, availability, keenness, and supportwereaconstantsourceofmotivation,andIdaresayIamnotexaggerating when saying I could not have hoped for a more amazing advisor. Thank you, Patrycja,forenablingmetoworkonsuch excitingresearch topics with such cool ‘‘toys’’, for allowing me to participate to nearly 20 conferences and workshops during my Ph.D. years, for helping me to considerably hone my communication skills, but first and foremost for your trust and humanity. IsincerelythankProf.Jean-MarcTriscone,who mightverywellbethereason why I have carried on with my studies after my Bachelor degree. When I was a third year undergrad student, I approached Jean-Marc for information about his researchforaseminarpresentation.Hisenthusiasmandkindnesslaterledmetoa summer internship in his group, which in turn led to a Master, and eventually a Ph.D. thesis under his co-supervision. Thank you, Jean-Marc, for all you generosity! Many special thanks to Prof. Thierry Giamarchi, who in addition to being our theorywellofwisdomhadtoendurealltheexperimentalandtechnicalaspectsof my thesis. His optimism and insight have been invaluable throughout our efforts to disentangle some mysteries of disordered elastic systems. Disentangling the mysteriesbehindhismagicperformances,ontheotherhand,willprobablycontinue toeludeus. I warmly thank Prof. Gustau Catalan, not only for accepting to be part of the jury but also for many fruitful interactions during the course of my thesis and his general keenness, which I find inspiring. I am very grateful to Dr. Stéphane Santucci, who was our connection with the world of fracture physics, thus demonstrating the significant benefits of interdis- ciplinary exchanges. In this respect, I especially thank him for reading through a thesis manuscript only partly and loosely related to his area of expertise. IwishtoaddressveryspecialthankstoElisabethAgoritsas,whoseesinterfaces everywhere,incoffeestains,inScottishshorelines,inpavementcracks,inclouds, in bruised apples, and even in domain walls. I have occasionally traded some of hertimeandwisdomforchocolate,butsheusuallyrefusedtobepaid.Tobeable to work not only with such an intelligent and patient person but also with one’s closest friends is a rare gift. ix x Acknowledgments I am extremely grateful to Dr. Sebastián Bustingorry, who gave me my first contactwithdisorderedelasticsystemswhenIwasstillaMasterstudent,andlater became one of our key collaborators when we started to incorporate numerical simulations in our studies. His kindness and impressive enthusiasm have largely fueled these successful collaborations, and I am truly thankful for everything he taughtme.IamalsoverygratefulfortheamazingtimespentinBariloche,oneof my most enriching experiences outside of Geneva. ¡Muchas gracias, Sebastián! A really big and hearty thank to Iaroslav Gaponenko, for taking some happy first steps in ophidology with me. Also for the continued taming of our UHV-VT AFM system, our ‘‘Omicron’’, the machine from heaven with a devilish temper. And tea. Lots and lots of tea. Mygratitudeevidentlyextendstoallcurrentandpastmembersofthegroupsof Patrycja Paruch and Jean-Marc Triscone, nearly all of them having helped me at some point, and certainly all of them being wonderful people: Benedikt Ziegler, Yuliya Lisunova, Cédric Blaser, Gijsbert Rispens, Christophe Caillier, Céline Lichtensteiger, Stefano Gariglio, Pavlo Zubko, Claudia Cancellieri, Alessia Sambri, Nicolas Reyren, Nicolas Stucki, Andrea Caviglia, Almudena Torres, Stéphanie Fernandez, Daniela Stornaiuolo, Raoul Scherwitzl, Alexandre Fête, Denver Li, and Sara Catalano. My thesis would not be what it is were it not for exceptional technical support of Sébastien Muller and Marco Lopes, whom I thank most sincerely for their kindness and help. I also extend my gratitude to Gregory Manfrini, Patrick Magnin, and Sandro d’Aleo. I wish to address particular and most sincere thanks to Prof. Michel Decroux, whom I had the genuine pleasure of assisting in his general physics course for medical students. That these students have come to enjoy physics and consider it useful knowledge is a testament to the care he has instilled in his course, which I find truly inspiring. Michel has also played a significant part in the advancement forwomenprogram,whichhascertainlyhelpedmotivatemydecisiontoundertake a Ph.D. thesis. Thank you, Michel, for your extraordinary commitment. I kindly thank Lidia Favre-Quattropani for her nice support and advices throughout the years, the good mood in the office, as well as for the nice work I had the opportunity to do with her on outreach projects. I wish to express my sincerest gratitude towards our administrative collabora- tors, Fabienne Hartmeier, Denise Borjon, Esther Schwarz, Nathalie Chaduiron, and Marianne Gervais, whose help to navigate the treacherous waters of admin- istration has been essential for survival. IalsogratefullyacknowledgefinancialsupportfromtheSwissNationalScience Fundation under MaNEP and Division II, and the financial and academic support of the University of Geneva. IthankofcoursealltheGuyonnetclan.GenevièveGuyonnet,whoistheearliest reasonwhyIcametolovescience.JacquesGuyonnet,whofirsttaughtmetofly,and has always demonstrated supportand pride during mystudies. Sylvère Guyonnet, always present and probably wiser than me. Adasol Alsonso-Guyonnet, ¡muchas