Lead Magnesium Niobate (PMN) System sor rears comps ent poses re We i Se Nopsiceaine Limp ange Se Cn i ee Aoi ete Steet longtime Ceres a teh ie-z0M0 ks estan waa Normal Lon Range Aelasn bemetec Ferland tere le asta, Pike) FG ata Noh | EPR M Gs, SPST) Ce | PMS Nhat | NCPR Sh 0 WiPREO Con | Pmt Bia lieLead Magnesium Niobate (PMN) System Important Perovskite End Members for Relaxors Complex perovakites T,(°C) Behavior’ Simple Perovakites T,(°C) Behavior be Nb, 10 ‘RFE PbTiC 190 FE TNO. ‘es 40 RFR pee 230 AFE : 120 RFE BaTiO; 130 FE Py ei 2ND, 10 FE SYTIO; = PE. Pb¢FenaWin)Os, 35 RFE (MB) gW12)03 38 ‘AFB BoB ais 4 Ae ee eed Important Relaxors Based on MPB Compositions ‘System:* Example: Antiferoelectrc: proper ferroelectric PbZrO, : Pt Relaxor : poms erecta (Zn yyNb; ‘ nado range order): proper feroelectic Me NB, 5 ee eae POTIO, Relaxor : antiferroel )O, : PbZrO Rel oe ng 90s : Pb{Sc) NI fuer nd) "ina amtiomsicticegiemeast) nerdy sb, Palace Relaxor =} cae FL crest Ma Ns a Os Senta & Gaace, we oe rowerLead Magnesium Niobate (PMN) System Relaxor-Based Compositions for MLC TA wpecteation _ Manulcurer Pats me . Us Pe aH, ee Bae US Pe conse a Nec Us Pe sortos ww Nec Us pe aaieoue * TDK Us Peaaisi08 sy TDK Us Pea ass.sce ¥ De Us be aie wv TDK US bea aea7s bu BE Us pe aaiees zu Hits Us reasons Bu Mow US pease ioe _ z 250, vsv nee Us. pe.4.29.9 (sen Bu Nec US be aseaao 54 Rv ie US Pe sane 9 20 = Ue Pe SEA ato Bu me Ux Pe: 2aiae rst Zu Matta ‘pe 39995 (Oke 2 Masia pen Pa $6 200759 ise sv Nema pee S601 (9 ¥ ‘Toate zu UnienCurile US. 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MamitaLead Magnesium Niobate (PMN) System Areas of Applications for Relaxors Ferroelectrics and Solid Solutions Application Example Pyroclectries Pb(Sey; Tay2)05 (Bag 6g S949) TIOy Capacitors/dielectries Ph(Mgy,Nby)03 Electrostriction/actuators Ph(MgyNb2,3)05 Pb(Zn,,Nby3)O, Pb[(MgysNby)1Ti,]O Medical ultrasound/high Pb[(Zn,sNby3)1..Ti]O, efficiency transducers Pb[(Se,.Nb.,),.TI.JO5 Piezoelectries Pb(Zr, ,Ti,)O5 Pb[(ZnysNbya)y.,Ti1O, Pb[(Se,,Nby)1..TH1O5 Electrooptics (Phy sLar)(Zr1yTI)OyLead Magnesium Niobate (PMN) System Relaxor igh a Pb(B,B,)O, (B, ~ lower valency cation : Mg*, Zn, N2*, Fe**) (B, ~ higher valency cation : Nb°*, Ta*, +) u PMN © Pb(Mg,,,Nb,,;)O; u Important Relaxor Ferroelectric with T, ~ -10 C Broad diffused and dispersive phase transition on cooling below T, Very high room temperature dielectric constant Strong frequency-dependent dielectric properties t Nano-scaled compositional inhomogeniety Y Chemically order-disorder hehavior observed by TEM study Y B-site 1:2 order formula with 1:1 order arrangement in the structure (Most have rhombohedral symmetry due to slight lattice distortion)Lead Magnesium Niobate (PMN) System 00 =e -40 -20 0 «+2 OCOSCTO Diclectrie properties of Pb(Mg,;Nb,,,)O; showing diffused phase transition and relaxor characteristics (Tyygy (at 1 KHz) ~ -10 C with &, sya, ~ 20,000)Lead Ma: esium jobate (PMN) System Property Normal Ferroelectrics Relaxor Ferroelectrics Permittivity temperature dependence Permittivity frequency dependence Permittivity behavior in Paraelectric range Remnant polarization (P,) Scattering of light X-Ray diffraction Sharp 1* or 2"4 order transition about T, Weak frequency dependence Follow Curie-Weiss Relation above T, Strong remnant polarization Strong anisotropy (birefringent) Line splitting (eubie to tetragonal) Broad-diffused phase transition about Tax Strong frequency dependence Follow Curie-Weiss Square Relation above T, Weak remnant polarization Very weak anisotropy to light (pseudo-cubie) No line splitting (pseudo-cubie structure) Comparison of normal and relaxor ferroelectricsLead Magnesium Niobate (PMN) System Inverse Permittivity, Ve Li Inverse Permittivity, ee Polarization, P Temperature Polarization, P ‘Temperature First-Order Phase Transition | Second-Order Phase Transition | Spontaneous polarization (P,) => A discontinuity in the first-order phase transition = => A continuous change in the second-order phase transition <= Relaxor ferroelectric <> P, decays continuously with temperature, but does not follow the parabolic temperature dependence as in the second-order phase transition Permittivity, ¢Polarization, P Lead Magnesium Niobate (PMN) System Regime IIT Regime Regime T a i iP i & 1 i g " 5 i oe 3 |i 2 i + a i ‘Temperature s = ‘Temperature Normal Ferroelectrics = Dielectric Behavior > Relaxor Ferroelectrics Normal ferroelectrics => the onset of spontaneous polarization occurs simultaneously with the maximum in the paraelectric to ferroelectric phase transition. No P, above the transition temperature with a valid Curie-Weiss Law Relaxor ferroelectrics => Three regimes : Regime I Above dielectric maximum temperature, Regime II Between T, (depolarization temperature) and T,,,, (dielectric transition temperature), and Regime II Below T,Lead Magnesium Niobate (PMN) System Regime HL Regime I Regime I Regime I : Electrostrictive region with existence of chemically ordered region with no macro-scale ferroelectric domian —> little or no hysteresis Regime Il: Freezing-out of macro-domain region in which with decreasing temperature the polar regions grow and cluster —> hysteresis is observed and becomes more pronounced with decreasing temperature Regime III ; Macro-domain region becomes more stable which results to a large spontaneous polarization and piezoelectric effects with large remnant strainLead Magnesium Niobate (PMN) System Cable ionnaiype \, igay *y Disordcied Aninealen ELOidcrd ealialoubled), f Ox cies Ox eruw eo Ordered and Disordered Perovskite StructuresLead Magnesium Niobate (PMN) System @ Asisicn © Bisiteion O BY siteion X Oanion Ordered and Disordered Perovskite Structures Fully disorder of the cations in the B-sites occupation u “Normal” ferroelectric materials (such as PZT) Nano-scale order of the cations in the B-sites occupation u “Relaxor” ferroelectric materials (such as PMN)Lead Magnesium Niobate (PMN) System je ao f @9094@0. / dqea agions diserderad mates Nano-scale ordered region in disordered matrix Pb(MEiqND23)0s Nano-scale ordered region with Mg:Nb = 1:1 (like in NaCl structure) Non-stoichiometric short range chemical heterogeneity Different ferroelectric oe temperature regions u Diffused/broad dielectric behaviorLead Magnesium Niobate (PMN) System PbSe,,Tay.0; PbMg);Nb2,;03 Harmer and Bhalla Randall et al. Dark field TEM images showing nano-scale ordered region in disordered matrixLead Magnesium Niobate (PMN) System ef oa “ = Yee iets Ee Sah bs = : Sil a : “Temperance °C) Temeratare CC} Polarization ae R ‘ee em) Hysteresis Birefringence Features for Ordered and Disordered FerroelectricsLead Magnesium Niobate (PMN) System sie Structural Transition AaGehes Ferroelectric properties decay with increasing T> Features for Ordered and Disordered FerroelectricsLead Magnesium Niobate (PMN) System Relaxor gprs | PMNS PMB sNb2n)Os Strong frequency-dependent dielectric properties (Tynax Shifts to higher temperature with increasing frequency) (Dielectric losses are at the highest just below T,,,,,) + Dynamical thermal re-orientation of polar regions with frequency (As frequency increases, the polar regions cannot keep up —> ¢, + and loss T) Dielectric relaxation similar to ee (follows a Vogel-Fulcher model) However, no certain explanation for relaxor ferroelectrics Freezing of micro-region and chemical fluctuation @ Ordered-disordered region # @ Spin-glass model ¢Lead Magnesium Niobate (PMN) System One of the difficulties in processing PMN ceramics 4 Pyrochlore (General formula RNb,O, where R is a mixture of divalent ions) u Pb, y3Nby 7)Mgq 290,39 © formed at 700-850 C u Paraelectric with room temperature e, of 130 u Strong reduction in ¢, if present as inter-granular region in high ¢, PMN region (Not very significant if only disrete particles disperse in PMN matrix) Pure Phase PMN with “Columbite Precursor Method” (MgO + Nb,O; > MgNb,O, => MgNb,O, + PbO > PMN) Example of Pyrochlore PhaseLead Magnesium Niobate-Lead Titanate (PMN-PT) System Most widely studied relaxor materials <> PMN-PT Solid Solutions High-strain (0.1%) electrostrictive actuators High dielectric constant (¢, > 25,000) capacitorsLead Magnesium Niobate-Lead Titanate (PMN-PT) System Curie Point (°C) Mole % PT 0.65 PMN - 0.35 PT <> MPB Compositions with normal ferroelectric properties High dielectric constant capacitors <> 0.90 PMN - 0.1 PT <> Relaxor (with T,,., near room temperature with large dielectric constant) (large “electrost ” strain)Lead Magnesium Niobate-Lead Titanate (PMN-PT) System 18000 {3000 11000) 9 7000) 5000520 “4060 80100 TEMPERATURE (C) OIELECTRIC CONSTANT Dielectric Behavior of 0.9PMN-0.1PT Relaxor FerroelectricsLead Magnesium Niobate-Lead Titanate (PMN-PT) System STRAIN io yior4 ‘0.9 PMN-O.1PT d33~ 1S00p; AT 3.7 kv/em 1 0 id ELECTRIC “FIELD (kV/cm) 7 Strain-Field Relation of 0.9PMN-0.1PT Relaxor FerroelectricsLead Magnesium Niobate-Lead Titanate (PMN-PT) System Electrostriction in Ferroelectric Materials U Basis of electromechanical coupling in all insulators x = ME? and x = QP? (As compared to x ~ E ton piezoelectric effects) Large in ee just above T. due to electrical unstabability of ferroelectrics (PMN, PZN, and PLZT) (because of their diffused transition and possible field-activated coalescence of micropolar region to ss crosons aa of the parent ferroelectric ) “Field-Biased Piezoelectric Mode” DC Bias Field = Induced Ferroelectric Polarization => Normal Piezoelectric dy; = 2Q,,P2€33 ds, = 2Q,.Pr€33Lead Magnesium Niobate-Lead Titanate (PMN-PT) System Advantages of Electrostriction u #Minimal or negligible strain-field dependence hysteresis # (in selected temperature range) More stale realizable deformation than observed in piezo-ceramics # @No poling is required u Longitudinal strain 0.1% in PMN 0.3% in PLZT (La/Zr/Ti = 9/65/35) Disadvantages of Electrostriction u ¢Limited usable temperature range # (due to a strong temperature dependence) @ Small deformation at low electric field (as a result of a quadratic nature of electrostriction)P PT and PZN-PT Single Crystal: 1-x PMN — x PT Single Crystals x = 35 for MPB compositions = Large piezoelectric strain > 1% = High electromechanical coupling factor (kj; > 90%) => Relaxor-based crystals for next transducers piezoelectric generation 1-x PZN — x PT Single Crystals x= 9 for MPB compositions => Large piezoelectric strain ~ 1.7% = High electromechanical coupling factor (kj, = 92%) => Relaxor-based _ piezoelectric crystals for atuators high _ performancePMN-PT and PZN-PT Single Crystals Electric Field (kV/cm) Comparison of field-induced strain for various ceramics and single crystalsStrain (%) PMN-PT and PZN-PT Single Crystals ‘Comparison of Strain-Field Behavior for Crystals and Ceramics Field (kV/em) Field (kV/em)PisPePey ‘on swithing to high fies phase Pephe (PecP_on svntching back) Fi Engineered Domain States ¢Initially the domains are aligned as close as possible to the field direction ¢ Increased polarization in rhombohedral structure ¢ As the field is increased to certain values, the domains collapse to the <001> direction, as a result of rhombohedral-to-tetragonal phase transition ¢ Large increase in polarization, hence piezoelectric properties