Ferroelectrics. Disordered Ferroelectrics Relaxors.
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1 Ferroelectrics. Disordered Ferroelectrics Relaxors. 1
2 Ferroelctricity Main properties History. Discovery. Materials Relaxors Applications 2
3 Ferroelectric Materials. A ferroelectric material is a material that exhibits, over some range of temperature, a spontaneous electric polarization that can be reversed or reoriented by application of an electric field. An American National Standard IEEE Standard Definitions of Primary Ferroelectric Terms 3
4 Ferroelectricity: Two classes of ferroelectrics Displacement type Order-Disorder disorder O Ba P N Ti O O order BaTiO 3 P NaNO 2 4
5 Ferroelectricity: Polarization reversible. (P-E hysteresis) PLZST ceramics 4 Sn:Ti =.24: P ( C/cm 2 ) E DC (kv/cm) 5
6 Ferroelectricity: Domains + - Single domain state Multi domain state P net ~ 9 o domains Courtesy of Igor Lukyanchuk 18 o domain pattern Y Lu et al. Science 1997;276:
7 Ferroelectricity: Domains PMN-PT4% BaTiO 3 Courtesy of Benjamin Vega-Westhoff and Scott Scharfenberg, P43, Fall29 KH 2 PO 4 Courtesy of Allison Pohl, P43, Fall29 PMN-PT3% BaTiO 3 191K KD 2 PO 4 Crystal from Forschungsinstitut für mineralische und metallische Werkstoffe -Edelsteine/Edelmetalle 7
8 Ferroelectricity: Landau-Ginzburg phenomenological theory Free energy F P Order parameter (polarization) ap bp cp... EP F P the equilibrium solution Ignoring higher terms we can get the linear solution: Electric field Vitaly Ginzburg Lev Landau F ap E P P 1 E a Assuming linear dependence of a on temperature we will have: 1 ( T T c ) and finally we will have Curie-Weiss law C C ( T T ) c 8
9 Ferroelectricity: Landau-Ginzburg phenomenological theory 8 In case of b>) (C> also) We will have the solution for second order phase transition with two equilibrium points p and p. Both these states are equivalent F (a.u.) E= T>T c T=T c T<T c p P (a.u.) p 9
10 Ferroelectricity: Landau-Ginzburg phenomenological theory PLZST ceramics Ps Sn:Ti =.24: F (a.u.) Ps P (a.u.) P ( C/cm 2 ) Pr F (a.u.) P (a.u.) Ps F P Including EP term can illustrate the P-E hysteretic behavior ap bp cp E DC (kv/cm) EP F (a.u.) P (a.u.) Pr 1
11 Ferroelectricity: Susceptibility P E (1 ) D E P E E E E For ferroelectrics >>1 and BaTiO 3 '/1 9 6 C=1.9*1 5 ; T C =385.2K Curie-Weiss law: C ( T ) T CW T (K) 11
12 Rochelle Salt KNaC 4 H 4 O 6 *4H 2 O Potassium sodium tartrate discovered (in about 1675) by an apothecary, Pierre Seignette Elie Seignette Rochelle Salt originates from French city of La Rochelle where it was produced by Pierre Seignette another name of this material is Seignette salt Rochelle Salt was used in medicine and food industry 12
13 Rochelle Salt KNaC 4 H 4 O 6 *4H 2 O Paul-Jacques Curie Pierre Curie Brothers Curie discovered and investigated the piezoelectric effect I several materials including Rochelle salt 13
14 Joseph Valasek ( ) University of Minnesota Fig3. Piezoelectric response as a function of temperature [2] Fig.1. The first published hysteresis loop [1] 1. J. Valasek, Phys. Rev. 17, 475 (1921) 2. J. Valasek, Phys. Rev. 19, 478 (1922) Rochelle Salt KNaC 4 H 4 O 6 *4H 2 O 14
15 Ferroelectricity. Terminology. ferrum (Lat) gave the name of the broad class of magnetic materials ferromagnetics Fe has no relation to the phenomenon of ferroelctricity but because of a lot of common features of ferroelectric phase transition to ferromagnetic the new class of dielectrics was named as ferroelectrics. There is another name for this class of materials - Seignette-electrics named after the alternative name of the Rochelle salt 15
16 KDP (KH 2 PO 4 ) - potassium dihidrophosphate 1935 G. Busch and P. Scherrer, Naturwiss. 23, 737 (1935). Eine neue Seignetteelektrische Substanz. T c ~123K Georg Busch Paul Scherrer
17 KDP (KH 2 PO 4 ) - potassium dihidrophosphate T c ~123K heating KDP (sample 4) c-cut T>T c 3 1kHz '/1 2 T c ~121.5 K 1 T<T c KDP project (2): Graph6 T (K) Courtesy of Tim S. Thorp, Zhangji Zhao, Physics 43, Spring 213 Courtesy of Alison Pohl, Physics 43, Spring 29 17
18 1943 material with high (>12) value of the dielectric constant (Wainer, Solomon (USA); Wul, Goldman (USSR)) 1945 discovered the ferroelectric properties of BaTiO3 A. von Hippel (USA); Wul, Goldman (USSR)) T c ~4K Arthur R. von Hippel A. Von Hippel, Rev. Mod. Phys. 22,221,
19 P ( C/cm 2 ) rhombohedral orthorhombic tetragonal P P P Walter J. Merz, Phys. Rev. 76, 1221,
20 Physics 43 Lab, August 211 John A. Hooton, Walter J. Merz, Phys. Rev. 98, 49,1955 2
21 9 cooling heating 1Hz K 395K 6 1 '/ K 395K P ( C/cm 2 ) T (K) E (kv/cm) Courtesy of Liu M. & Lopez P, Physics 43, Spring
22 Ferroelectricity: Typical ferroelectric materials T C (K) Ps ( C/cm 2 ) KDP type KH 2 PO KD 2 PO RbH 2 PO Perovskites BaTiO KNbO PbTiO >5 LiTiO LiNbO ABO 3 Number of publications concerning ferroelectricity. From Jan Fousek Joseph Valasek and the Discovery of Ferroelectricity Springer Handbook of Condensed Matter and Materials Data 22
23 New Perovskite Materials - Relaxors B-site complex Lead magnesium niobate (PMN) Lead scandium tantalate (PST) PbMg l/3 Nb 2/3 3 PbSc 1/2 Ta 1/2 3 Lead zinc niobate (PZN) PbZn l/2 Nb 1/2 3 Lead indium niobate (PIN) PbIn 1/2 Nb 1/2 3 A-site complex Lead lanthanum titanate (PLT) Pb 1-x La x TiO 3 Both sites complex Lead lanthanum zirconate titanate (PLZT) Pb 1 x La x Zr y Ti 1 y O 3 L. Eric Cross 1 Smolenskii G.A Potassium lead zinc niobate K 1/3 Pb 2/3 Zn 2/9 Nb 7/ Pennsylvania State University, USA 2. A.F. Ioffe Institute, USSR AB1 (1-x) B2 x O 3 A1 (1-x) A2 x BO 3 A1 (1-x) A2 x B1 (1-y) B2 y O 3 typical complex oxides with perovskite structure 23
24 Perovskite Structure Perovskite is a mineral CaTiO 3. The mineral was discovered in the Ural Mountains of Russia by Gustav Rose in 1839 and is named after Russian mineralogist Lev Perovski. Gustav Rose Lev Perovski AB1 (1-x) B2 x O 3 A1 (1-x) A2 x BO 3 A1 (1-x) A2 x B1 (1-y) B2 y O 3 typical complex oxides with perovskite structure 24
25 Relaxors Regular ferroelectric BaTiO 3 Relaxor - PMN Pb(Mg 1/3 Nb 2/3 )O 3 T > T c (cubic) (cubic) Ba O Ti Pb O Mg +2 or Nb +5 25
26 Relaxors Regular ferroelectric BaTiO 3 Relaxor - PMN Pb(Mg 1/3 Nb 2/3 )O 3 T < T c (tetragonal) (cubic) Ba O Ti Pb O Mg +2 or Nb +5 26
27 mHz.35.3 max and T max depend on the measuring frequency '/ MHz / ' T (K).1.5 does not follow Curie-Weiss law Temperature dependencies of measured in a broad frequency range: 3mHz -1MHz 27
28 1 5 f max (Hz) T VF ~212K T max (K) f E f max exp T TVF 28
29 2 '/ K 22K 23K 25K f (Hz) 29
30 2 '/ K 22K 23K 25K f (Hz) (, T ) g(, T)ln 1 2 3
31 PNR polar nanodomains COR chemically ordered regions Figure 3. (a) ABO 3 perovskite structure. (b) Model for relaxor structure. PNR and COR represent the polar nano-region and chemically order region, respectively. (c) &(d) show two models of atom arrangement for COR. To maintain the electric neutrality, a Nb-rich layer is required for case (c). D. Fu, et all in "Advances in Ferroelectrics", ISBN , November 19,
32 (111) E PMN T f FC 2.62kV/cm 1 3 / '.2.15 '/ T>T f (111) E T (K). T<T f E DC is applied in (111) direction T f temperature of the induced relaxor ferroelectric transition Rhombohedral distortion 32
33 E DC (kv/cm) 6 PE FE RLX/FE E 1,T 1 RLX T (K) FC ZFC E-T phase diagram of PMN. Field applied in (111) direction '/1 ''/1 Ip (na) P ( C/cm 2 ) time (s) 19K 2.83 kv/cm time (s) 33
34 Solid solution relaxor-regular ferroelectric. (PMN).97 (PT).3 (PMN) (1-x) (PT) (x) phase diagram T c (K) 5 Literature data single crystals ceramics Paraelectric 4 (cubic) Ferroelectric PT: PbTiO 3, ferroelectric with Curie temperature 763K (PMN).6 (PT).4 3 Relaxor (PMN).9 (PT) (PMN).7 (PT).3 x 34
35 Courtesy of D. Tenne, Boise State University 35
36 Applications. Nonvolatile Memory Fast write speed (65-7ns) High endurance (1 14 cycles) Low power consumption 36
37 Applications. Actuators Atomic Force Microscope (a) (b) Piezo-injector for diesel engines, (b) Multilayer piezoelectric actuator scheme. Courtesy Technische Universität Darmstadt Lead Zirconium Titanate piezo scanner PI ( 37
38 Applications. Sonars Military Applications APPLICATIONS: Piezocomposite materials have been tested by the United States military since MINE HUNTING WEAPONS SONAR COUTERMEASURES ACOUSTIC COMMUNICATIONS PROJECTOR ARRAYS HYDROPHONE ARRAYS VIBRATION CONTROL 38
39 Applications. Sonars Civil Applications Fish Finder Courtesy 39
40 Applications. Adaptive Optics Soldered control and mass wires PZT Lead Zirconium Titanate Pb[Zr x Ti 1-x ]O 3 Reflecting surface Courtesy of 4
41 Ferroelectricity: Relaxors - aplications Actuators Transducers Adaptive optics Capacitors Line motors for SFM Material Dielectric constant Piezoelectric coefficient, (pc/n) Electromechanical coupling factor Quartz Rochelle salt (3C) Barium titanate ceramic Lead zirconate titanate PZT 45/55 PMN-PT (sc) PZN-PT (sc) Transducer stack for ultrasonic sonar application (TRS Ceramics) Piezoelectric properties of different materials 41
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