Heterogeneous Ferroelectric Solid Solutions: Phases and Domain States

167 Pages·2012·3.198 MB·English

by  Vitaly Topolov (auth.)

SpringerSeriesin
materials science
151
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SpringerSeriesin
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Editors: R.Hull C.Jagadish R.M.Osgood,Jr. J.Parisi Z.Wang
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Vitaly Yu. Topolov
Heterogeneous
Ferroelectric
Solid Solutions
Phases and Domain States
With 39 Figures
123
ProfessorVitalyYu. Topolov
SouthernFederalUniversity,DepartmentofPhysics
ZorgeSt.5,Rostov-on-Don
Russia
[email protected]
SeriesEditors:
ProfessorRobertHull ProfessorJu¨rgenParisi
UniversityofVirginia Universita¨tOldenburg,FachbereichPhysik
Dept.ofMaterialsScienceandEngineering Abt.Energie-undHalbleiterforschung
ThorntonHall Carl-von-Ossietzky-Straße9–11
Charlottesville,VA22903-2442,USA 26129Oldenburg,Germany
ProfessorChennupatiJagadish Dr.ZhimingWang
AustralianNationalUniversity UniversityofArkansas
ResearchSchoolofPhysicsandEngineering DepartmentofPhysics
J4-22,CarverBuilding 835W.DicknsonSt.
CanberraACT0200,Australia Fayetteville,AR72701,USA
ProfessorR.M.Osgood,Jr.
MicroelectronicsScienceLaboratory
DepartmentofElectricalEngineering
ColumbiaUniversity
SeeleyW.MuddBui•lding
NewYork,NY10027,USA
SpringerSeriesinMaterialsScience ISSN0933-033X
ISBN978-3-642-22482-9 e-ISBN978-3-642-22483-6
DOI10.1007/978-3-642-22483-6
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Preface
Asolid-solutionseriesisthecontinuoussequenceofsubstanceswithcompositions
intermediatebetweentwodistinctmineralphases,calledendmembers.Inasolid-
solution series, the componentsmay be thoughtto substitute for one another on a
molecularlevel in the crystal structure; the intermediatemembershave properties
that vary continuously with composition from those of one end member to those
of another. Solid-solution series are said to be complete if examples of complete
variationexistinnatureorhavebeensynthesizedinthelaboratory...
... onlythe appearanceof the computerprovideda qualitativejumpand made
itpossibletoperformeffectivestudyofreallycomplexsystemsinvariousareasof
knowledge.Actually,theconcerniswith coarsequalitativecriteria,differentiating
simple systems from complex; if the structure and behaviour of a system can be
studied by a single man in a reasonable time, the system is called simple. If the
effortsofmanypersonsandtheuseofspecialtechnicalequipment(computers)are
requiredtodrawthewholepicture,thesystemiscalledcomplex.
EncyclopaediaBritannicaUltimateReferenceSuite
Inthelast10–15years,crystallographicandcompositionalengineeringhasbecome
animportanttoolinthedevelopingfunctionalmaterialsandinenhancingtheirphys-
icalproperties.Ferroelectricsrepresentavastclassofmodernfunctionalmaterials
that find applications from medical equipment to aeronautics. Intricate domain,
twin and heterophase structures, sequences of structuralphase transitions (mainly
thefirst-orderphasetransitions),complexsystemsofsolidsolutionswithdifferent
structural and polar orderings, and outstanding electromechanical properties in
the poled state make ferroelectric materials attractive for basic research within
the frameworkof the well-knowndependencytriangleof ‘composition–structure–
properties’. As is known from numerous experimental studies, the first-order
phase transitions in ferroelectrics are characterized by jumps of the spontaneous
polarization,unit-cellparameters,byheterophasestatesconcernedwithaninternal
mechanical field, etc. The present book is intended to discuss recent experimen-
tal and theoretical results on heterophase states and to provide crystallographic
v
vi Preface
interpretations of heterophase structures in the ferroelectric solid solutions, espe-
ciallyinthepresenceofheavilytwinnedphases.
The most studied group of ferroelectric solid solutions is characterized by
the perovskite-typestructure (from the mineral perovskite,CaTiO3/. Components
of these solid solutions are perovskite oxides with a composition ABO3, where
A and B are cation elements or mixtures of two or more such elements, or
vacancies. The importance of ferroelectric perovskite-type materials is concerned
withthealmostunlimitedisomorphismoftheircrystalstructure.Asaconsequence,
a continuous change in the composition, structural characteristics, and physical
propertiesis achievedby substitution of differentelementsat equivalentpositions
(A and/or B). The isomorphism favours the formation of the ferroelectric solid
solutions with properties that can be varied within a wide range. It should be
addedthatmanyoftheferroelectricperovskite-typesolidsolutionsexhibitexcellent
piezoelectric properties. Experimental data on these solid solutions show that
the heterophase states in them are observed in certain ranges of temperature,
composition,and electric field strength, where volume densities of free energyof
the coexisting phases approximately equal. Recent studies on the representative
perovskite-type solid solutions (for instance, ferroelectric Pb(Zr1(cid:2)xTix/O3 and
relaxor-ferroelectric(1(cid:2)x)Pb(A1=3Nb2=3/O3–xPbTiO3withADMgorZn)show
thattheheterophasestatesthereinareofparticularinterestbecauseofthepresence
ofintermediatephasesandtheirconsiderableinfluenceonthe physicalproperties,
phasecoexistence,andstressreliefnearthemorphotropicphaseboundary.Thethree
aforementionedsolidsolutionsare themainsubjectsofresearch,comparison,and
discussioninthepresentbook.
Thisbookhasbeenwrittenonthebasisoftheauthor’sresearchresultsobtained
mainly at the Rostov State University (Russia, until December 2006), Southern
FederalUniversity(Russia,sinceDecember2006),andKarlsruheResearchCentre
(Germany, 2003–2004). The academic style of presentation of the results and
the discussion about them indicate that the book would be useful to researchers,
engineers,postgraduatestudents,andlecturersworkinginthefieldofferroelectrics,
ferroelastics, multiferroics, and other modern functional materials. The present
book fills a gap in materials science, crystallographyof ferroelectrics and related
materials,and in physicsof heterogeneousferroelectricsand,therefore,will beof
benefit to all specialists trying to understandbehaviourand physicalpropertiesof
modern heterogeneous materials suitable for various applications. Some chapters
and sections of the book could serve as a basis for a university course devoted to
ferroelectricsolidsolutions.
Rostov-on-Don VitalyYu.Topolov
Russia
Acknowledgements
TheauthorisgratefultoProf.Dr.A.V.Turik,Prof.Dr.V.G.Gavrilyachenko,Prof.
Dr.A.E.Panich,Prof.Dr.O.E.Fesenko,Dr.V.V.Eremkin,Dr.A.F.Semenchev,
Dr.V.G.SmotrakovandDr.V.A.Shuvaeva(SouthernFederalUniversity,Russia),
Prof. Dr. O. Kraft and Prof. Dr. M. Kamlah (Karlsruhe Institute of Technol-
ogy, Germany), Prof. Dr. H. Schmid (University of Geneva, Switzerland), Prof.
Dr. Z.-G. Ye and Dr. A. A. Bokov (Simon Fraser University, Canada), Prof.
Dr.B.Noheda(UniversityofGroningen,TheNetherlands),Prof.Dr.A.M.Glazer
(University of Oxford, UK), Prof. Dr. C. R. Bowen and Prof. Dr. R. Stevens
(University of Bath, UK), Prof. Dr. E. K. H. Salje (University of Cambridge,
UK), Prof. Dr. D. Pandey (Banaras Hindu University, India), Prof. Dr. A. S.
Sidorkin and Prof. Dr. B. M. Darinsky (Voronezh State University, Russia), Prof.
Dr. L. N. Korotkov (Voronezh State Technical University, Russia), and Prof.
Dr. D. ViehlandandDr. H. Cao (VirginiaTech,VA, USA) fortheirinterestin the
researchproblemsandfortheirimportantpapersthathavebeencitedinthepresent
book.
TheauthorsincerelythanksProf.Dr.C.AscheronandMrs.E.Sauer(Springer-
Verlag, Heidelberg, Germany) for their effective and timely cooperation in the
field of editing the manuscript and producing the book. The author is also
grateful to Prof. Dr. C. R. Bowen and Mr. R. W. C. Lewis (University of Bath,
UK) for their careful reading of the manuscript at the final stage. Copyright
permissionsobtainedfromIOPPublishing(http://www.iop.org),AmericanInstitute
of Physics (http://www.aip.org),American Physical Society (http://www.aps.org),
Taylor and Francis (http://www.informaworld.com), and Pleiades Publishing
(http://www.maik.ru)areacknowledgedwithdueattentionandgratitude.
Financial support that promoted the fruitful research collaboration and writing
thisbookis also acknowledgedwith thanks.Hereupongratefullyandproudly,the
author would like to mention the timely and effective supportfrom the Karlsruhe
Research Centre (now Karlsruhe Institute of Technology, Germany), Helmholtz
Society(Germany),andRostovStateUniversity(nowSouthernFederalUniversity,
Russia).
vii
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Contents
1 CrystallographicAspectsofInterfacesinFerroelectrics
andRelatedMaterials ...................................................... 1
1.1 DomainStructuresandInterfaces
BetweenPolydomainRegions......................................... 2
1.1.1 FormationofDomainStructuresinFerroelectric
SingleCrystals ................................................. 2
1.1.2 Elastic-MatchingConceptandItsApplication
toDomainBoundaries......................................... 4
1.1.3 Classification of Domain Boundaries
inFerroelectricSingleCrystals................................ 8
1.1.4 CrystallographicInterpretationofInterfaces
intheCaseofComplicatedDomainStructures............... 8
1.2 PhaseCoexistenceatFirst-OrderPhaseTransitions.................. 12
1.2.1 ElasticMatchingofPhasesandZero-Net-StrainPlanes..... 12
1.2.2 StressReliefandConicalInterphaseBoundaries............. 16
1.3 Polydomain/HeterophaseFerroelectrics............................... 18
References..................................................................... 19
2 Two-PhaseStates............................................................. 23
2.1 ElasticMatchingofMorphotropicPhasesinPb.Zr1(cid:2)xTix/O3....... 25
2.1.1 Tetragonal–rhombohedralPhaseCoexistence
andCrystallographicInterpretation ........................... 25
2.1.2 ElasticMatchingandStressReliefinthePresence
oftheIntermediateMonoclinicPhase......................... 28
2.2 Phase Coexistencein .1(cid:2)x/Pb(Mg1=3Nb2=3)O3 (cid:2)
xPbTiO3NeartheMorphotropicPhaseBoundary ................... 32
2.2.1 PhaseCoexistenceWithouttheMonoclinicPhase ........... 32
2.2.2 PhaseCoexistenceinthePresenceoftheMonoclinic
Phases .......................................................... 36
2.2.3 EffectofNon-180ıDomainsonPhaseCoexistence ......... 39
2.2.4 DifferentScenariosofStressRelief........................... 44
ix
x Contents
2.3 Model of Interpenetrating Phases: Application
to .1 (cid:2)x/Pb(Mg1=3Nb2=3)O3(cid:2)xPbTiO3 Near
theMorphotropicPhaseBoundary .................................... 49
2.4 Domain and Heterophase States
in .1 (cid:2) x/Pb.Zn1=3Nb2=3/O3–xPbTiO3 Near
theMorphotropicPhaseBoundary .................................... 53
2.4.1 PhaseTransitionsandIntermediatePhases................... 53
2.4.2 CrystallographicStudyofElastic Matching
ofMorphotropicPhases........................................ 55
2.4.3 Interpenetrating Phases
in 0.90Pb(Zn1=3Nb2=3)O3–0.10PbTiO3
SingleCrystals ................................................. 57
References..................................................................... 60
3 PhaseCoexistenceUnderElectricField................................... 65
3.1 HeterophasePb.Mg1=3Nb2=3/O3attheInducedPhaseTransition... 65
3.2 DomainState:InterfaceRelationshipsatElectric
FieldEjj[001].......................................................... 68
3.2.1 Heterophase.1(cid:2)x/Pb(Mg1=3Nb2=3)O3(cid:2)xPbTiO3 .......... 68
3.2.2 Heterophase.1(cid:2)x/Pb(Zn1=3Nb2=3)O3(cid:2)xPbTiO3........... 79
3.3 DomainState:InterfaceRelationshipsatElectric
FieldEjj[110].......................................................... 83
3.4 DomainState:InterfaceRelationshipsatElectric
FieldEjj[111].......................................................... 87
3.5 RoleofIntermediatePhasesinHeterophaseStates................... 92
References..................................................................... 93
4 Three-PhaseStates........................................................... 97
4.1 ModelofThree-PhaseSingleCrystal ................................. 97
4.2 Application of Model Concepts to PbZrO3
andPb.Zr1(cid:2)xTix/O3.x (cid:3)0:22/....................................... 100
4.2.1 PhaseCoexistenceinPbZrO3SingleCrystals................ 100
4.2.2 PhaseCoexistenceinPb.Zr1(cid:2)xTix/O3 Single
Crystals.x (cid:3)0:22/............................................ 101
4.3 Application of Model Concepts
to.1(cid:2)x/Pb.Mg1=3Nb2=3/O3(cid:2)xPbTiO3.............................. 102
4.4 Three-PhaseCoexistenceandCompleteStressRelief
in.1(cid:2)x/Pb.Zn1=3Nb2=3/O3(cid:2)xPbTiO3............................... 103
4.5 ThermodynamicDescriptionof Three-PhaseStates
inFerroelectricSolidSolutions........................................ 108
4.6 Crystallographic and Thermodynamic Studies
ofThree-PhaseStates .................................................. 114
References..................................................................... 115