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Functional Dielectrics for Electronics: Fundamentals of Conversion Properties (Woodhead Publishing Series in Electronic and Optical Materials) PDF

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Preview Functional Dielectrics for Electronics: Fundamentals of Conversion Properties (Woodhead Publishing Series in Electronic and Optical Materials)

Functional Dielectrics for Electronics Woodhead Publishing Series in Electronic and Optical Materials Functional Dielectrics for Electronics Fundamentals of Conversion Properties Yuriy Poplavko Yuriy Yakymenko An imprint of Elsevier WoodheadPublishingisanimprintofElsevier TheOfficers’MessBusinessCentre,RoystonRoad,Duxford,CB224QH,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates TheBoulevard,LangfordLane,Kidlington,OX51GB,UnitedKingdom ©2020ElsevierLtd.Allrightsreserved. Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans,electronic ormechanical,includingphotocopying,recording,oranyinformationstorageandretrievalsystem, withoutpermissioninwritingfromthepublisher.Detailsonhowtoseekpermission,further informationaboutthePublisher’spermissionspoliciesandourarrangementswithorganizationssuch astheCopyrightClearanceCenterandtheCopyrightLicensingAgency,canbefoundatourwebsite: www.elsevier.com/permissions. Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythe Publisher(otherthanasmaybenotedherein). Notices Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperience broadenourunderstanding,changesinresearchmethods,professionalpractices,ormedicaltreatment maybecomenecessary. Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgeinevaluating andusinganyinformation,methods,compounds,orexperimentsdescribedherein.Inusingsuch informationormethodstheyshouldbemindfuloftheirownsafetyandthesafetyofothers,including partiesforwhomtheyhaveaprofessionalresponsibility. Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors,assume anyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproductsliability, negligenceorotherwise,orfromanyuseoroperationofanymethods,products,instructions, orideascontainedinthematerialherein. LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress BritishLibraryCataloguing-in-PublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN:978-0-12-818835-4(print) ISBN:978-0-12-818836-1(online) ForinformationonallWoodheadpublications visitourwebsiteathttps://www.elsevier.com/books-and-journals Publisher:MatthewDeans AcquisitionEditor:KaylaDosSantos EditorialProjectManager:PeterAdamson ProductionProjectManager:SojanP.Pazhayattil CoverDesigner:VictoriaPearson TypesetbySPiGlobal,India Preface The authors of this book represent the microelectronics department of National Technical University of Ukraine (Kiev Polytechnic Institute), founded 120years agoandnamedafterIgorSikorsky,whotrainedatthisinstitute.Functionaldielectrics havebeenstudied,elaborated,andtaughtinthemicroelectronicsdepartmentformany years, and the authors have published hundreds of articles and several books in this area. Thetaskofthisbookistoprovideengineersspecializinginmaterialsscienceappli- cation and research in electronics and information technology with up-to-date and clearideasaboutthenatureofelectricalpolarization,dielectricnonlinearity,electrical chargetransfermechanisms,thermalproperties,andthenatureofthermalstableper- mittivityinlow-lossmicrowavedielectricsandotherfunctionaldielectrics.Thebook describes in detail the intrinsic mechanisms of electrical polarization and energy transformationsinnoncentrosymmetriccrystals,whichareresponsibleforconverting thermal, mechanical, optical, and other actions into electrical signals. In order to extend the use of functional dielectrics into the field of nanoelectronics, this book contains a versatile and comprehensive presentation of the main physical processes thatprovidetheelectrical,mechanoelectrical,thermoelectrical,andotherconversion phenomena in polarcrystals. Moredetaileddescriptionsaregiventoelectricalmanifestationsofpolarsensitivity incrystals;interactionofpolarizationwithconductivityisdescribed,aswellasanom- alies in thermal expansion coefficient and the main peculiarities of heat transfer in polar-sensitive crystals. Some applications of polarity theory to pyroelectrics and piezoelectrics are described. Microwave dielectrics are also of great importance in modernelectronics,becausetheyarewidelyusedincommunicationdevices.Inthem, smalldielectriclossescanbeachievedinsingle-phasecompositions,basedon“hard” paraelectric material that resists polar structure formation. The thermal stability of permittivity can be obtained when paraelectricity is suppressed by paramagnetism. Nonlineardielectricsprovideanimportantopportunityforrapidcontrolbypermittiv- ity, used in microwave phase shifters. Other frequency-agile devices are also described: tunable dielectric resonators and phase shifters consisting of microwave dielectricscoupledwithcontrolbyapiezoelectricairgapthatavoidsinsertedlosses. The authors express their deep gratitude to their colleagues from “Igor Sikorsky Kiev Polytechnic Institute” for their interest in this work and for their valuable comments. The authors are also grateful to their students who pointed out hard- to-understand concepts and asked us for clarification. The responsibility for any remaining errors orshortcomings is, ofcourse,ours. viii Preface WewanttogivespecialthankstoProf.Dr.Sci.YuriyProkopenko,Ass.Prof.Dr. VictorKazmirenko,Ass.Prof.Dr.DmitriyTatarchuk,andDr.YuriyDidenkofortheir usefulcollaboration. Finally, we are deeply grateful to the staff of Elsevier: to Kayla Dos Santos and PeterAdamsonfortheirpatienceineliminatingtheshortcomingsofthemanuscript. Dr. Phys.-Mat. Sci. Prof.Yuriy Poplavko Academician of UAS, First Vice Rector, Dr. Sci.Prof. Yuriy Yakymenko Introduction The dielectrics intended for use inelectrical and electronic devices must have good electrical insulating properties, including very low electrical conductivity and high electrical strength. At the same time, in present-day electronics technology, other properties of dielectrics have gained special importance, namely those that allow for conversion of energy or information; these dielectrics may be considered functional materials. Thefunctional(oractive,oradaptive,orcontrolled,orsmart)dielectricsactively reacttochangesoftemperature,pressure,mechanicalstress,electricalandmagnetic fields, light illumination, and even smell. Functional dielectrics can be classified as pyroelectrics, ferroelectrics, piezoelectrics, electrets, quantum-electronics materials, microwave dielectrics with tunable permittivity, etc. Active dielectrics perform different functions. For example, the piezoelectrics convert mechanical energy into electrical energy (and vice versa) that is used in piezoelectric filters, ultrasound emitters, piezoelectric transformers, piezoelectric motors, etc. Pyroelectrics convert heat into electricity and are applied as sensitive detectorsofradiation,thermal-visiondevices,etc.Thenonlinearpropertiesofferro- electricsandparaelectricsandtheconstantelectricalfieldproducedbyelectretsallow use of these functional dielectrics for modulation, detection, amplification, register- ing, storing, displaying, and other types of electrical conversion of signals carrying information. It is also necessary to mention the use of functional dielectrics in multifunctionalelectronicdevices,alongwiththeactivesearchfornewtechnological solutionstochallengesregardingapplicationofthesedielectricsinthefieldofinfor- mationtechnology. Themainpropertyofanydielectricisitselectricalpolarization,i.e.,theeffectof separation of electrical charges that remain bonded in spite of their shifting. As a result,anelectricalmomentappears(asaproductofchargemagnitudeanddisplace- ment);thevolumetricdensityofthismomentispolarizationP.Oneunusualfeatureof functionaldielectricsisthattheirelectricalpolarizationcanbeinducednotonlybyan electrical field, but also by other causes. A comparison of conventional (nonpolar) dielectricsandtwocategoriesofpolardielectricsareshowninTableI.1.Theessential distinctionbetweenactive(functional)dielectricsandordinarydielectricsisobvious. In many applications of functional dielectrics (such as sensors, actuators, filters, transformers,motors,etc.),theyaresubjectedtoexternalthermal,electrical,mechan- ical,andotherinfluences—scalar,vector,ortensortypes.TableI.1showsthatacon- ventional dielectric electrically reacts only to electrical field action: E)P, while polar piezoelectrics and pyroelectrics, besides the E)P response, are capable of electrical response to other actions: mechanical X)P and thermal dT)dP. x Introduction TableI.1 ElectricalpolarizationPasaresponsetovariousactions. Nonpolar Actions crystals Piezoelectrics Pyroelectrics Scalaraction: TemperaturedT – – Pyroelectriceffect: Pressuredp – – dP¼γdT Volumepiezoelectric effect:dP¼ζdT Vectoraction: ElectricalfieldE P¼ε εE P¼ε χE P¼ε χE+(e2/c)E 0 0 0 +(e2/c)E +(γ2Т)E/(ε C) 0 Tensoraction: Mechanical – P¼dX P¼d0X stressX Note:Parameterγispyroelectriccoefficient;ζisvolumetricpiezoelectricmodulus;dispiezoelectricmodulus;cis elasticstiffness;Cisspecificheat.Thistabledoesnottakeintoaccount: (1) flexoelectricitypossibleinalldielectricsundernonhomogeneousmechanicalaction; (2) actinoelectricitythatoccursinpiezoelectricsunderthegradTaction; (3) photopolarizationeffectinpolar(noncentrosymmetric)dielectrics. Atthesametime,piezoelectricsrespondtoelectricalactionnotbyordinarypolariza- tiononly,ofP¼ε χE,butalsoproduceanelectromechanicalresponseP0¼(e2/c)E, 0 whilepyroelectrics,inaddition,alsoproduceanelectrothermalresponseP00 ¼(γ2Т) E/(ε C). 0 Inviewofpossibleapplicationsofdielectricsasfunctional(converting)elements inelectronics, oneshouldidentifyand describetheir properties notonly interms of theirexclusivelyelectricalcharacteristicsbutalsotheircapabilitytomanifestvarious electrical,mechanical,andthermalproperties.Thesematerialsareimportantalsofor miniaturizationofmicrowaveandtelecommunicationsequipment.Inthiscase,adeci- sive role is played by the value of permittivity (ε), since the planar dimensions of microwavedevicesarereducedexactlybythefactorε.Insomefunctionaldielectrics (paraelectrics),alargevalueofεcanbeobtainedtogetherwithlowdielectriclosses, whichhasimportanttechnicalapplicationinhigh-frequencydevices.Somefunctional dielectrics allow electrical control by permittivity that can be used for electrically controlled microwave devices. For all the reasons mentioned, interest in ferroelectrics, paraelectrics, piezoelec- trics,andpyroelectricshasrecentlygrowninthefieldofelectronicsmaterialsscience, preciselybecauseoftheirnewapplicationsininstrumentationengineeringandelec- tronics, and also owing to significant progress in modern microelectronic and nanoelectronic technologies. Functionalmaterialsareparticularlyrelevanttomodernandfutureinstrumentation basedonmicromachining.Inthistrend,microelectronicgrouptechnologyisusedina varietyoftechnicalfields.Usingmodernequipment,micromachiningisorganically Introduction xi connectedwithmicroelectronicsandnanoelectronics.Amongcontemporaryapplica- tionsoffunctionaldielectrics,oneshouldnotethefollowingmainareasofparticular relevance: ferroelectric and paraelectric thin films integrated with semiconductors; microsystems combining sensors, processors, and actuators; microwave micro- electronics, based on functional dielectric components; nanodielectrics, which are prospective technologies for sensors, computer memories, and electrical power generation. Engineers specializing in the application of materials science to electronics and informationtechnologiesneedtoaccessthelatestknowledgeonthenatureofelectri- cal polarization, electrical charge transfer mechanisms, thermal properties of func- tional dielectrics, mechanisms of dielectric losses, as well as intrinsic mechanisms ofpolarizationinnoncentrosymmetriccrystals,whichareresponsibleforconverting thermal, mechanical, optical, and other actions into electrical signals. In order to extendtheuseoffunctionaldielectricsintothefieldofnanoelectronics,itisnecessary for designers and technologists to have a thorough and deep understanding of the physical processes that provide electrical, mechanoelectrical, thermoelectrical, pho- toelectrical andotherconversion phenomena inpolarcrystals. Itmightbethatthemoststrikingfeaturesofpolardielectricsare,first,themutual influenceofmechanical,electrical,andthermalpropertiesoneachotherand,second, thedependenceofthesepropertiesontheconditionsinwhichpolarcrystalsarestud- iedorapplied.Todemonstratethisinterdependence,thebasicmechanical,electrical, andthermallineareffectsinthenonpolarandpolardielectricsaresymbolicallycom- paredinFig.I.1.Itisseenthatintheordinarydielectricsthesepropertiesareindepen- dent,but inthe polarcrystals they are connected by quite complex interactions. Fig.I.1Asymbolicallyshowsthattheelasticmechanicaldeformationx(strain)ina solid dielectric is proportional to the applied mechanical stress x¼s(cid:2)X, where s is elasticcompliance.Notethatthislinearrelationshipcanalsobewritteninthereverse direction,X¼c(cid:2)x,asHooke’slaw,whereciselasticstiffness.Similarly,inadielec- tric,electricallyinducedpolarizationPisproportionaltothemagnitudeoftheapplied electricalfield,P¼ε χ(cid:2)E,whereχisdielectricsusceptibilitywhileε istheelectrical 0 0 constantinSIunits.Ifelectricalpolarizationisinducednonelectrically,thenanother recording of this linear connection will be more convenient: Е¼ε(cid:3)1ξ(cid:2)P where 0 Fig.I.1 Linkingdiagramformechanical,electrical,andthermaleffects:(A)Innonpolar dielectric;(B)inpolardielectric. xii Introduction ξ¼χ(cid:3)1isdielectricimpermeability.Finally,thermalpropertiesaredescribedbythe proportionalityoftheamountofheatδQinacrystalappearingduetoambienttem- perature change: δQ¼C(cid:2)δT whereCisspecific heat. In polar crystals, the mechanical, electrical, and thermal properties are interdependent,soapossiblediagramoftheirinteractionlooksliketwosquarescon- nectedbyoneside(Fig.I.1B).Thisschemeshowshowcomplicatedthedescriptionof noncentrosymmetric (polar) crystal properties can be. PiezoelectricityissymbolicallydescribedbytheleftsquareinFig.I.1B.Twohor- izontalandtwocrossed-connectinglineswitharrowspresenteightlinearpiezoelectric effectsthatmaybeobservedinpolarcrystalsunderdifferentconditions.Thenumber ofpiezoelectriceffectsis8,sincethiseffectcanbedirectorconverse(2),thecrystal canbeelectricallyopen-circuitedorshort-circuited(2),andthecrystalmechanically canbefreeorclamped(2),so2(cid:4)2(cid:4)2¼8.Theseeffectsaredescribedbyfourpie- zoelectric coefficients-moduli (d, e, g, h); further, simplified equations of the direct effects are P¼d(cid:2)X, P¼e(cid:2)х, E¼(cid:3)g(cid:2)x, E ¼(cid:3)h(cid:2)X, and for the converse effect the j equations are х¼d(cid:2)Е, X¼e(cid:2)E, х¼g(cid:2)P, X¼h(cid:2)P. However, all four moduli men- tioned can be calculated through each other and through known elastic constants, for example, in simplified form: d ¼ε ε(cid:2)g¼e(cid:2)s¼ε ε(cid:2)h(cid:2)s, and so on. As can be in 0 0 seen,thedescriptionofelectromechanicaleffectsinpolarcrystals(eveninthelinear case)isnot aneasy task. Inpolar-sensitivecrystals,thedescriptionofelectrothermaleffectsisalsonotsim- ple.Thepyroelectriceffectoccurswhenthedisturbancefactoristhethermalactionon acrystalwhile theresponse hasanelectricalnature. The electrocaloriceffectisthe converseeffect:itariseswhentheelectricalfieldactsonthepyroelectric,whilethe result is heating or cooling of the polar crystal. Both these effects are symbolically presented inthe rightsquare inFig. I.1B. First,two horizontallines and twocrossed-connectedlineswith arrows symboli- cally characterize four options in the pyroelectric effect implementation: the polar crystalcanbeelectricallyopen-circuitedorshort-circuited;inaddition,thepyroelec- triceffectcanoccurintwodifferentthermalconditions:adiabaticwithδQ¼0oriso- thermalwithδТ ¼0.Sothepyroelectriceffectmightbedescribedbyfourequations: Р¼γ(cid:2)δТ, P ¼γ0(cid:2)δQ, E¼γ00(cid:2)δТ, and Е¼γ000(cid:2)δQ, in which different pyroelectric i coefficients correspond to various boundary conditions. Second,fourlineswitharrows,shownintherightpartofFig.I.1B,areusedherefor symbolicdescriptionoftheelectrocaloriceffect.Asapyroelectriceffect,thiseffect may be described by four different linear relationships (depending on thermal and electricalboundaryconditions).However,thiseffectundernormalconditions(attem- perature(cid:5)300K)isratherweakandisnotconsideredhereinmoredetail.(However, in Chapter 4, a large electrocaloric effect will be discussed, arising when an anti- ferroelectricisswitchingelectricallyintoaferroelectricphase,whichcanbeconsid- ered asa possible basis for an electrocaloric refrigerator.) Animportantconsequenceoftheserelationshipsisthedependenceofthecrystal fundamental parameters on thermal, electrical, or mechanical processes passing in polarcrystalsatdifferentboundaryconditions.Forexample,dielectricsusceptibility ofafreecrystalχX(whichmeansthestressX¼0)andofaclampedcrystalχx(that

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