Ferroelectricity Explained

Ferroelectricity is a characteristic of certain materials that have a spontaneous electric polarization that can be reversed by the application of an external electric field.[1] [2] All ferroelectrics are also piezoelectric and pyroelectric, with the additional property that their natural electrical polarization is reversible. The term is used in analogy to ferromagnetism, in which a material exhibits a permanent magnetic moment. Ferromagnetism was already known when ferroelectricity was discovered in 1920 in Rochelle salt by Joseph Valasek.[3] Thus, the prefix ferro, meaning iron, was used to describe the property despite the fact that most ferroelectric materials do not contain iron. Materials that are both ferroelectric and ferromagnetic are known as multiferroics.

Polarization

When most materials are electrically polarized, the polarization induced, P, is almost exactly proportional to the applied external electric field E; so the polarization is a linear function. This is called linear dielectric polarization (see figure). Some materials, known as paraelectric materials,[4] show a more enhanced nonlinear polarization (see figure). The electric permittivity, corresponding to the slope of the polarization curve, is not constant as in linear dielectrics but is a function of the external electric field.

In addition to being nonlinear, ferroelectric materials demonstrate a spontaneous nonzero polarization (after entrainment, see figure) even when the applied field E is zero. The distinguishing feature of ferroelectrics is that the spontaneous polarization can be reversed by a suitably strong applied electric field in the opposite direction; the polarization is therefore dependent not only on the current electric field but also on its history, yielding a hysteresis loop. They are called ferroelectrics by analogy to ferromagnetic materials, which have spontaneous magnetization and exhibit similar hysteresis loops.

Typically, materials demonstrate ferroelectricity only below a certain phase transition temperature, called the Curie temperature (TC) and are paraelectric above this temperature: the spontaneous polarization vanishes, and the ferroelectric crystal transforms into the paraelectric state. Many ferroelectrics lose their pyroelectric properties above TC completely, because their paraelectric phase has a centrosymmetric crystal structure.[5]

Applications

The nonlinear nature of ferroelectric materials can be used to make capacitors with adjustable capacitance. Typically, a ferroelectric capacitor simply consists of a pair of electrodes sandwiching a layer of ferroelectric material. The permittivity of ferroelectrics is not only adjustable but commonly also very high, especially when close to the phase transition temperature. Because of this, ferroelectric capacitors are small in physical size compared to dielectric (non-tunable) capacitors of similar capacitance.

The spontaneous polarization of ferroelectric materials implies a hysteresis effect which can be used as a memory function, and ferroelectric capacitors are indeed used to make ferroelectric RAM[6] for computers and RFID cards. In these applications thin films of ferroelectric materials are typically used, as this allows the field required to switch the polarization to be achieved with a moderate voltage. However, when using thin films a great deal of attention needs to be paid to the interfaces, electrodes and sample quality for devices to work reliably.[7]

Ferroelectric materials are required by symmetry considerations to be also piezoelectric and pyroelectric. The combined properties of memory, piezoelectricity, and pyroelectricity make ferroelectric capacitors very useful, e.g. for sensor applications. Ferroelectric capacitors are used in medical ultrasound machines (the capacitors generate and then listen for the ultrasound ping used to image the internal organs of a body), high quality infrared cameras (the infrared image is projected onto a two dimensional array of ferroelectric capacitors capable of detecting temperature differences as small as millionths of a degree Celsius), fire sensors, sonar, vibration sensors, and even fuel injectors on diesel engines.

Another idea of recent interest is the ferroelectric tunnel junction (FTJ) in which a contact is made up by nanometer-thick ferroelectric film placed between metal electrodes.[8] The thickness of the ferroelectric layer is small enough to allow tunneling of electrons. The piezoelectric and interface effects as well as the depolarization field may lead to a giant electroresistance (GER) switching effect.

Yet another burgeoning application is multiferroics, where researchers are looking for ways to couple magnetic and ferroelectric ordering within a material or heterostructure; there are several recent reviews on this topic.[9]

Catalytic properties of ferroelectrics have been studied since 1952 when Parravano observed anomalies in CO oxidation rates over ferroelectric sodium and potassium niobates near the Curie temperature of these materials.[10] Surface-perpendicular component of the ferroelectric polarization can dope polarization-dependent charges on surfaces of ferroelectric materials, changing their chemistry.[11] [12]

Notes and References

  1. Book: https://books.google.com/books?id=7yFWuc_YL3UC&q=ferroelectricity&pg=PA5 . 4 . 5 . Werner Känzig . Ferroelectrics and Antiferroelectrics . Frederick Seitz . T. P. Das . David Turnbull . E. L. Hahn . 978-0-12-607704-9 . 1957 . Academic Press . Solid State Physics.
  2. Book: M. Lines . A. Glass . Principles and applications of ferroelectrics and related materials . Clarendon Press, Oxford . 1979. 978-0-19-851286-8.
  3. See J. Valasek . Piezoelectric and allied phenomena in Rochelle salt . Physical Review . 15 . 6 . 537 . 1920. 10.1103/PhysRev.15.505. 1920PhRv...15..505. . and J. Valasek . Physical Review . 17 . 475 . 1921. 1921PhRv...17..475V . 10.1103/PhysRev.17.475. Piezo-Electric and Allied Phenomena in Rochelle Salt. 4 . 11299/179514 . free .
  4. Chiang, Y. et al.: Physical Ceramics, John Wiley & Sons 1997, New York
  5. Book: Safari. Ahmad. Piezoelectric and acoustic materials for transducer applications. 2008. Springer Science & Business Media. 978-0387765402. 21. 2008pamt.book.....S.
  6. Book: J.F. Scott . Ferroelectric Memories . Springer . 2000. 978-3-540-66387-4.
  7. M. Dawber . K.M. Rabe. Karin M. Rabe . J.F. Scott . Physics of thin-film ferroelectric oxides . Reviews of Modern Physics . 77 . 1083 . 2005. cond-mat/0503372 . 2005RvMP...77.1083D . 10.1103/RevModPhys.77.1083. 4 . 7517767.
  8. 10.1103/PhysRevLett.94.246802. M.Ye. Zhuravlev . R.F. Sabirianov . S.S. Jaswal . E.Y. Tsymbal . Giant Electroresistance in Ferroelectric Tunnel Junctions. Physical Review Letters. 94. 246802–4. 2005. 2005PhRvL..94x6802Z. cond-mat/0502109. 24 . 15093350 .
  9. R.. Ramesh. N.A. Spaldin. Nicola Spaldin. Nature Materials . 6 . 2007. 2007NatMa...6...21R . 10.1038/nmat1805 . 17199122. 1. 21–9. Multiferroics: Progress and prospects in thin films. W. Eerenstein . N.D. Mathur . J.F. Scott . Nature . 442 . 2006. 2006Natur.442..759E . 10.1038/nature05023 . 16915279 . 7104. 759–65 . Multiferroic and magnetoelectric materials. 4387694 ., N.A.. Spaldin. Nicola Spaldin. M.. Fiebig . Science . 309 . 5733. 391–2 . 10.1126/science.1113357 . 2005. The renaissance of magnetoelectric multiferroics . 16020720. 118513837. M. Fiebig . Journal of Physics D: Applied Physics. Revival of the magnetoelectric effect . 38 . 8. R123 . 2005. 10.1088/0022-3727/38/8/R01. 2005JPhD...38R.123F . 121588385.
  10. Parravano . G. . Ferroelectric Transitions and Heterogenous Catalysis . The Journal of Chemical Physics . February 1952 . 20 . 2 . 342–343 . 10.1063/1.1700412 . 1952JChPh..20..342P .
  11. Ferroelectrics: A pathway to switchable surface chemistry and catalysis. 302–316. Surface Science. 650. 10.1016/j.susc.2015.10.055. August 2016. 2016SurSc.650..302K. Kakekhani. Arvin. Ismail-Beigi. Sohrab. Altman. Eric I.. free.
  12. Kolpak. Alexie M.. Grinberg. Ilya. Rappe. Andrew M.. 2007-04-16. Polarization Effects on the Surface Chemistry of $_$-Supported Pt Films|journal=Physical Review Letters|volume=98|issue=16|pages=166101|doi=10.1103/PhysRevLett.98.166101|pmid=17501432}.